Archaeometry and Cultural Heritage The C

Seminarios de la Sociedad Espaola de
Mineraloga
Volumen 09
Archaeometry and
Cultural Heritage:
the Contribution of
Mineralogy
Seminario celebrado en
Bilbao, 27 de Junio de 2012
Editores:
Jos Miguel Herrero

Marius Vendrell
Cover photo
French faience test pieces from the Le Bois d'pense (Les
Islettes, NE France) factory, early 19th century. Width of the
clay balls 2-3 cm. Photo M. Maggetti (pers. coll.).
01
Mineral
og
So
ciedad Espa
e
ad
ol
Seminarios de la Sociedad de Espaola

de Mineraloga
Sociedad Espaola de Mineraloga
Museo Geominero del Instituto Geolgico y
Minero de Espaa
c/ Calle de Ros Rosas, 23
28003 Madrid
http://www.ehu.es/sem
sem@ehu.es
Editores
Jos Miguel Herrero
Marius Vendrell
Diseo y maquetacin
Soma Dixital, S.L.
Impresin
Lugami Artes Grficas, S.L.
Depsito legal
CA-602-2004
ISSN
1698-5478
Impreso en Espaa - Printed in Spain
2012
02
Foreword
The Spanish Mineralogical Society (SEM) has published eight previous thematic volumes
concerning different topics of interest for mineralogists. In this new volume we present
the key notes of six invited lecturers to the International Seminar "Archaeometr y and
Cultural Heritage: the Contribution of Mineralogy" held in Bilbao on June 27, 2012,
during the SEM-SEA 2012 congress, a joint meeting of the Spanish Clay Society and SEM.
These talks deal with the contributions in scientific disciplines like mineralogy, petrology
and geochemistr y to the characterization, dating and provenancing of ar tworks and manmade and natural ar tifacts that constitute par t of our tangible Cultural Heritage. New
advances in both conceptual and methodological studies are also reviewed. The aim of
the seminar is to open up to new ideas to researchers in this field and par ticularly, to
show how Mineralogy may provide critical clues in the study of Archaeology, Histor y,
Architecture and Fine Ar ts and Restoration. The interest for these studies in our countr y
is growing, as we can see in the SEM-SEA meeting proceedings, where 24 papers have
been presented about this topic.
The 2012 seminar is being addressed by scientists of international prestige covering a
wide range of leading topics: Dr. Domnguez-Bella, who talks about prehistoric lithic tools
and prestige objects, Dr. Prudncio, who focuses on archaeological ceramics or Dr.
Maggetti who make a study of glazed ceramic French faiences. The prehistoric smelting
technologies is the topic of the lecture of Dr. Ar tioli; Dr. Hradil introduces us to the noninvasive / non-destructive analysis of pigments in ar tworks; and Dr. Rodrguez-Navarro
explains the use of gypsum and lime in historical buildings.
We par ticularly wish to thank the authors who have accepted our invitation to par ticipate
with generosity. We are also ver y thankful to the institutions (Education Depar tment of
the Basque Government, The University of the Basque Countr y UPV/EHU, Science and
Technology Faculty), companies and entities (Ente Vasco de la Energa, Fisher Scientific,
Bilbao Turismo) and to the UPV/EHU Mineralogy and Petrology Depar tment staff. These
have provided financial and / or logistics suppor t to the organization of the Seminar and
for the preparation of this volume and its distribution to the SEM-SEA 2012 attendants,
and to SEM and SEA members.
Jos Miguel Herrero

Marius Vendrell
Bilbao, Junio 2012
03
Index / ndice
05
Archaeomineralogy of prehistoric artifacts and gemstones.

Arqueomineraloga de artefactos y gemas prehistricos.
Dr. Salvador Domnguez-Bella
29
Trace element geochemistry and mineralogy for solving problems in

provenance and production technologies of Pre-historic ceramics.
La geoqumica de elementos traza y la mineraloga en la resolucin de
la proveniencia y tecnologa de produccin de la cermica prehistrica.
Dra. Mara Isabel Prudncio
41
Technology and Provenancing of French faience.

La tecnologa e investigacin de la procedencia de la fayenza francesa.
Dr. Marino Maggetti
65
Archaeometallurgy: the contribution of mineralogy.

La arqueometalurgia: la contribucin de la mineraloga.
Dr. Gilberto Artioli
79
Microanalysis of pigments in art works.

Microanlisis de los pigmentos en obras de arte.
Dr. David Hradil & Janka Hradilov
91
Binders in historical buildings: traditional lime in conservation.

Ligantes en edificios histricos: la cal tradicional en la restauracin.
Dr. Carlos Rodrguez-Navarro
04
Archaeomineralogy of prehistoric
artifacts and gemstones
/ Salvador Domnguez-Bella
Dpto. de Ciencias de la Tierra. Universidad de Cdiz. Campus Ro San Pedro. 11510 Puerto Real (Cdiz), Spain
Abstract
The study of the compositional nature, geological and geographical origin of the tools and jewellery used by man in prehistoric times has been since the nineteenth century the scientific goal
of some researchers in the fields of mineralogy and petrology. This interest in heritage research
studies is experiencing a significant growth in recent decades, with a great development of interdisciplinary collaborations, both from the field of archeology as for the conservation, restoration
and management of artistic and cultural heritage. The application of physico-chemical techniques,
common in studies of mineralogy, petrology and analysis of materials to the resolution of the fascinating questions posed from the archaeometry and the fact that we dispose of a growing number of analytical techniques with higher experimental performance make that this line of research
has grown in the interest of researchers. Here several studies worldwide about some of the most
widely used mineral substances throughout history and in different geographical areas and the
tools and prestige objects manufacture, used by human societies are summarized. Finally, we present several examples of archaeometric studies carried out on minerals and fossil resins, used
during the Prehistory of the Iberian Peninsula, western France and North Africa in the elaboration
of tools, jewellery and objects of prestige.
Resumen
El estudio de la naturaleza composicional y del origen geolgico y geogrfico de las herramientas y joyas usadas por el hombre desde la Prehistoria, ha constituido desde antiguo, el objetivo cientfico de algunos investigadores de las reas de mineraloga y petrologa. Este inters por los estudios patrimoniales est experimentado un gran crecimiento en las ltimas
dcadas, con un mayor desarrollo de las colaboraciones interdisciplinares, tanto desde el
campo de la arqueologa como de la conservacin, restauracin y gestin del patrimonio artstico y cultural. La aplicacin de tcnicas fsico qumicas, habituales en los estudios de mineraloga, petrologa y anlisis fsico-qumico de materiales, a la resolucin de las apasionantes
incgnitas planteadas desde la arqueometra y el hecho de disponer de cada vez mayor nmero de tcnicas analticas y con mayores prestaciones experimentales, hacen que esta lnea
de trabajo haya crecido en el inters de los investigadores. Se resumen varios de los estudios a nivel mundial sobre algunas de las sustancias minerales ms utilizadas a lo largo de
la historia y en diferentes reas geogrficas, en la elaboracin de herramientas y objetos de
prestigio, usados por las sociedades humanas. Finalmente se muestran varios ejemplos de
estudios arqueomtricos realizados sobre sustancias minerales y resinas fsiles, utilizadas
durante la Prehistoria de la pennsula Ibrica, el oeste de Francia y el Norte de frica, en la
elaboracin de herramientas, joyas y objetos de prestigio.
Key-words: mineralogy, archaeometry, cultural heritage, Iberian Peninsula, raw materials, prehistoric
jewels, conservation.
1. Introduction
The archaeomineralogy is itself a mineralogical sub-discipline with a history of not very long
tradition, at least in the Iberian Peninsula. This specialization of mineralogy has been developed in parallel to archaeometry studies applied to materials in archaeological and artistic heritage. The first reference to this term appears in Mitchell, 1985 and contrary to the disciplines
05
Archaeomineralogy of prehistoric artifacts and gemstones

Salvador Domnguez-Bella
ground in geology and mineralogy should

be considered a fundamental and necessary part, both for research archaeometric
to those relating to heritage conservation.
So we need a good understanding of what
have been the physical-chemical systems
and processes involved in the genesis of
each mineral or rock.
of Geoarchaeology, has not yet had recognition as such, although in recent years there
has been a large increase in the interest of
mineralogists in the study of archaeological
materials (Turbanti Memmi et al. 2011).
A current definition of archaeomineralogy appears in Rapp (2003 and 2009), as "the study of
minerals and rocks used by ancient societies
across space and time, as tools, ornaments,
building materials and raw materials for metals,
ceramics and other processed products".
Besides it is particularly important that there

is reciprocity in the transmission of data
among mineralogists and scientists in general, working on heritage and humanistic
counterpart specialists, this is archaeologists, museum and collections curators and
cultural heritage managers (Artioli & Angelini
2011). This interdisciplinary collaboration,
consistent and objective, will provide a complete picture of the issues to be addressed
in each case and will avoid producing an
"innocent archaeometry" (Ramos et al.
1998) in which the analytical data are presented only as annexes to the archaeological work and very often with no connection
between the conclusions of both.
In recent years archaeomineralogy studies

have been increasing. This may be due to
several factors:
Increase in interdisciplinary studies in
archeology, with the participation of many
specialists from different scientific disciplines (Price & Burton 2011), including
among them the mineralogy and petrology.
Higher number of analytical techniques
available for studies of mineralogical and
geochemical characterization of the samples for study and greater analytical precision and capacity of them.
Recent contributions as book edition of Rap

(2009) on archaeomineralogy or monographic
works as the one published in the European
Society of Mineralogy (Turbanti Memmi et al.
2011) show the growing interest in this line.
Many minerals and rocks as prehistoric artifacts used as gems in antiquity have been
studied archaeometrically in recent decades.
Increased interest from the field of

archaeology and restoration of historic and
artistic heritage in the potential of these
techniques on obtaining more and better
archaeological and historical information.
2. Application of mineralogical studies in

different archaeological problematic
The variety of compositions, colors and geological origins that these present is very significant and there are many archaeological problems that are related to these lithologies
and raised by archaeological research, in
some cases for a long time (Damour 1864).
This is equally applicable to other minerals
used as pigments since prehistory to the present (Domnguez-Bella 2010a; Domingo et al.
2012).
Mineralogical disciplines provide valuable

information to design solutions to many of
the problems, from an archaeological point of
view, for the study of historical and artistic
heritage and the restoration of works of art
and monuments.
However there are problems inherent in developing partnerships, like this:
Ver y dif ferent mineralogical techniques

have been implemented for its resolution in
the last centur y, due to the evolution of
technological and analytical capacities for
its identification and characterization, in
constant evolution, especially in recent
decades (Ar tioli 2010).
From the mineralogy and geology in general, it is possible to have a perception of

materials, types and natural processes
that originated them within a broader regional geological context, so that the back-
06
Seminario SEM 09
Depsito legal: CA-602-2004 / ISSN: 1698-5478
3. Analytical techniques at the

archaeometry of prehistoric artifacts
and jewellery
Different work strategies can define, such as
combined techniques (ie, the analysis techniques applied to the same object at different
times) and / or simultaneous (ie, several
analytical techniques are applied to the same
object simultaneously), since in many cases,
a single technique is not sufficient by itself to
resolve complex problems.
The pre-treatment of the samples and the
amount of the same required for analysis
varies depending on the analytical technique to be employed as well as its nature. In
general for non-invasive techniques, samples can be analyzed without any preparation (Fig. 1 & 2), while in other more aggressive as the polarized light microscopy the
required amount of sample is generally greater. In most cases, samples can be prepared quite easily, as occurs in many geological laboratories available in research centers or companies.
Fig. 2. Sample-holder for direct and non-destructive WDXRF analysis of

a sillimanite adze from the Neolithic of Brittany (France). SCCYT, Cdiz
University
instruments in order to per form in-situ

analysis, in museums, institutions and the
field, including XRF spectrometers, optical
and Raman sensors, X-ray diffractometers
and other instruments. Scientific and protection of cultural world heritage institutions have been working hard in the last
years to have laboratories capable to make
fast and cheap analysis. Despite this, it is
especially impor tant to per form a study and
previous programming of the technique or
techniques that are most suitable for the
study of a par ticular type of material and to
have a knowledge of the protocols for measurement, the instrumental configuration,
procedures calibration, and ultimately, optimization and suitability of each technique
or set of techniques with respect to the
nature of the material to investigate.
Today a great effor t is being focused in the

development and optimization of por table
We currently have a wide range of analytical

techniques with more or less invasive in
relation to the amount of sample affected,
although many of them, traditionally destructive sample preparation, can be applied
on a non-destructive and analytical results
quite reliable. This would be the case, for
example, the X-ray diffraction (XRD) and XRay Fluorescence diffusion wave (WDXRF),
applied to archaeological materials of small
size and with a flat sur face (Figs. 1 & 2).
Among the usual techniques in archaeometry
we can mention: Optical microscopy (MSC),
Polarized light microscopy (PLM), X-Ray
Diffraction (XRD) (powder or direct method),
X-Ray Fluorescence diffusion wave (WDXRF),
Fig. 1. Direct XRD analysis of archaeological objects. Sillimanite axe

from a Neolithic site of Cadiz province, SW Spain. SCCYT, Cdiz
University
07

4. Prehistoric Artifacts
Fourier Transform Infrared Spectroscopy

(FTIR), Scanning Electron Microscopy with
Energy Dispersive X-ray Analyzer (SEM-EDX),
Raman microscopy (RM), Optical Emission
Spectroscopy (OES), Induced Coupled
Plasma Mass Spectrometr y with laser
Ablation (ICP-MS-LA), Inductively-coupled
Plasma Optical Emission Spectroscopy
(Laser Ablation) (ICP-OES-LA). Also other techniques reported as: Laser microprobe mass
analyzer or Laser induced mass analyzer
(LAMMA / LIMA), Atomic absorption spectrometry (AAS), Flame atomic emission spectroscopy (FAES), Atomic-emission spectroscopy (AES), Instrumental neutron activation
analysis (INAA), Electron diffraction (ED), ion
probe (secondary ion mass spectrometry)
(SIMS), radiometry, emission spectroscopy,
spectrophotometry, etc.
Many examples of minerals and rocks used

since the beginnings of prehistory for the elaboration of different kinds of artifacts and
tools can be mentioned.
We emphasize the use of silicate minerals
and rocks, and metamorphic rocks in relation
to mineralogical and petrological studies of
minerals and rocks used since the
Palaeolithic (Domnguez-Bella et al. 2010),
such as quartzite, volcanic and plutonic rocks
and sedimentary rocks as silicified sandstones, the group of flint and radiolarite (Navazo
et al. 2008), as well siliceous minerals as
microcrystalline quartz varieties (agate, carnelian, onyx, etc.), single crystals of rock
crystal (Domnguez-Bella and Morata 1995),
volcanic glass as obsidian (Tykot 2002) or
organic substances such as fossil resins
(Beck et al. 1964 & 1965), etc.
Many of these or other qualitative, semiquantitative or quantitative techniques, classified as

nondestructive analysis techniques are:
Optical microscopy with visible light (OM),
Cathodoluminescence microscopy (CL),
Ultraviolet microscopy (UV), Infrared microscopy (IR), IR absorption spectrometry (Fourier
transform
IR
microspectrometr y)
(FTIR/FTIRM), Laser Raman microprobe (or
Laser Raman spectroscopy) (LRM/LRS),
Portable X-ray Fluorescence (PRXF), micro XRay Diffraction (XRD) Electron microprobe
(EPMA), Transmission electron microscopy
(TEM), Synchrotron X-ray fluorescence (SXRF),
X-ray absorption fine structure (XAFS), Prompt
Gamma Activation Analyses (PGAA), Elastic
recoil detection analysis ERDA, Extended X-ray
absorption fine structure (EXAFS), Nuclear
magnetic resonance/Proton magnetic resonance (NMR/PMR), etc.
There is a extensive bibliography on the characterization and identification of source

areas for these materials based on the use of
many analytical techniques, including some
classical techniques predominant in the geological sciences as OM, XRD, XRF, and more
specific as RM, FTIR, ICP-MS-LA, PIXE, PIGE,
INAA, XRD, PXRF, CL, Carbon-Oxygen-SulfurStrontium isotopes, etc. These specific techniques vary depending on the substance
under consideration and the technological
development of new analytical techniques in
recent decades (Price & Burton 2011).
Through these studies, we have nowadays
great information on mobility of raw materials
in prehistory, such as obsidian in the central
basin and the western Mediterranean (Tykot
2002), in Central Europe (Rosania et al.
2008) or in Mesoamerica and South America
(Jimnez-Reyes et al. 2001; Rivero-Torres et
al. 2008; Tenorio et al. 1997; Seelenfreund
et al. 2005); of siliceous materials as flint
and radiolarite in Europe by using more or
less sophisticated techniques as AAS, XRD,
ICP-MS and ICP-AES (Navazo et al. 2008), or
with simple microfacies studies with MO
(Della Cassa 2005).
An important role is played by isotopic

(Carbon-Oxygen-Sulfur) determination techniques, especially in provenance of, for example, metamorphic rocks as marbles or in
minerals as cinnabar used as pigment
(Minami et al. 2005).
The experimental parameters and the features and availability of each of these techniques are very different, and its use alone or
in combination, depending on the type of
substance and the specimen to analyze.
The bulk of the analytical work on polished
08
Seminario SEM 09
rocks, has taken place on the most common

lithologies in the Neolithic and Chalcolithic,
which have a regional or continental distribution from production centers, such as the
axes of prestige elaborated in jadeite and HP
green rocks of alpine origin (Petrequin et al.
2012; Cassen et al. 2012; D'Amico et a.l
2003), or the dolerites of Plusulien, France
(Le Roux 1999), the amphibolites in the West
of Iberian Peninsula (Lillios 1997), hornfels in
NE Spain (Risch & Martinez 2008; Clop
2004), sillimanites-fibrolites of the Iberian
Peninsula and France (Goer de Herve et al.
2002; Domnguez-Bella et al. 2004; Aguayo
de Hoyos et al. 2006; Pailler 2009) or flint
from Casa Montero, Madrid (Bustillo et al.
2009) or Benz, Ceuta (Ramos et al. 2008).
which would have given an adjudication of the

analyzed rock type with a definite geological
outcrop. At that time, works of geological cartography were beginning to start, with the creation of the Commission of the Geological Map
of Spain. On the other hand, in those days, a
great number of prehistorians still considered
more important the object itself than its
archaeological significance.
Rocks formed under conditions of high pressure (HP), deserve a special attention such
as green rocks as jadeite, eclogite, etc.,
which have been used in different periods
and geographical areas since prehistoric
times (Ruvalcaba et al. 2008; Cassen et al.
2012), often polished and with a high value
as prestige goods.
In recent years archaeomineralogical studies

have been ongoing on archaeological materials
abiotic prehistory, especially the so-called
stone industry, these materials can separate
two groups, industry and polishes carved.
To these obstacles we also have to add the fact

that the analysis methods were expensive and
destructive. It is not till the 80 and 90 decades
of the XXth century that more or less systematic petrographic studies will return, in this type
of materials in Spain. (Domnguez-Bella y
Morata 1995; Domnguez-Bella et al. 2004).
The study of the lithic industry has a strong

mineralogical and petrographic and geochemical component, so that participation of
these disciplines is very important to determine the mineral nature of the object and
their petrographic, paleontological and geochemical features. These factors are of great
interest both from the determination of the
source area of these raw-materials and the
features and physical properties of the rock.
Mineralogical, petrological and geochemical

study techniques have been used for the classification and determination of their source areas
(D'Amico et al. 2003; Sheridan et al. 2010).
4.1. Archaeomineralogy of prehistoric artifacts,

examples in the Iberian Peninsula, West of
France and North Africa
The determination of the source areas of mineral raw materials is one of the main issues of
concern archaeomineralogical studies, these
studies allow to obtain great archaeological information, both on the strategies for obtaining of
lithic resources, by prehistoric societies, their
exploitation techniques if they exist (underground mining for example) (Camprub et al.
2003; Bustillo et al. 2009), mobility of these
groups in the territory, the use of the lithic material and determination of transport over short,
medium or long distances, in case there are
organized networks for such distribution, as
occurs with some precious or exotic materials,
which can travel long distances (up to thousands
of kilometers), from its geological source areas
to where they are deposited (Domnguez-Bella et
al. 2002; Cassen et al. 2011; 2012; Querr et
From the end of the XIXth century to the

beginning of XX, geologists worked with the
prehistorians in the examination of archaeological materials that composed these lithic
elements to attempt the characterization of
the constituent rocks and their geological and
geographical origin. The works of Quiroga
(1885) and of San Miguel de la Cmara
(1918) were the pioneer studies in mineralogy and petrography of archaeological
objects in Spain.
But these petrographical studies were not continued for many reasons since this information
could not be correlated with that one given by
the geological outcrops, mainly because the
basic geological works had not been done,
09

al. 2012; Rubalcaba et al. 2008).
les. This relatively wide distribution in metamorphic areas makes it difficult to define the
source area of the samples, usually very
homogeneous in macroscopic appearance.
The study and determination of mineralogical

and textural properties of many rocks and minerals is also of archaeometric interest, as these
properties can be direct determining factors for
a particular use by prehistoric societies of the
material. These first steps in the "materials
science" are interesting examples in many of the
studies currently being developed, such as lithic
assemblages in the Palaeolithic and Neolithic,
indicating high levels of technical knowledge,
obtained certainly through the experimentation.
By means statistical analysis applied to mineralogical-petrological classifications of tools and
their relationship with their technological type, is
verified in many cases a deliberate selection of
certain raw materials for a particular use, such
as flint and radiolarite in the Palaeolithic environment of the Strait of Gibraltar as Embarcadero of
Palmones river, Algeciras or Benz rock-shelter,
Ceuta (Domnguez-Bella et al. 2004).
The size of the nodules of sillimanite seems

to be a determining factor when a geological
outcrop is susceptible of constitute a source
area for the manufacture of polished stone
tools of sufficient size.
Polished tools of these lithologies, are widely
represented in the recent prehistory of the
Atlantic Band of Cdiz and other peninsular
areas and of the Northwest of France, the
problem of their possible origin is still open to
new theories and analysis, even in progress.
In the case of SW Spain and Portugal, we
think that sillimanites can be completely
allochthonous materials to this region, given
the scarcity and small size of sillimanite
nodules that appear in the Betic Cordilleras.
However some small outcrops have appeared
with this mineral in the province of Malaga
(Aguayo de Hoyos et al. 2006) that according
to these authors could be the source area for
the productions in the area.
In the studies that we are doing since 1994

on these materials, in southern Spain and
northern Africa it has been shown or inferred
allochthonous or autochthonous provenance
(Domnguez-Bella and Morata 1995;
Domnguez-Bella, Perez and Morata 2000;
Ramos and Giles 1996; Domnguez-Bella et
al. 2000, 2004 and 2006).
We are currently working on the possible

determination of the source areas of this
mineral, relating the geological material
analysis of the most important sites in the
Iberian Peninsula, North Africa and France,
as are those of the province of Segovia,
Madrid and Avila (Sierra de Guadarrama),
points of the Serrana de Ronda, Sierra
Morena, west peninsular zone (Zamora,
Salamanca), Brittany and Massif Central
(France), Tetouan area (Morocco), among
others.
Within the group of analyzed knapped stone

materials, many minerals and rocks, especially siliceous, constitute in percentage the
main group in prehistoric lithic industry.
These include flint, radiolarites and jasper;
we can join with other siliceous sedimentary
and metamorphic rocks as silicified sandstones and quartzites (Hernndez et al. 2012).
4.2. Metamorphic rocks in the Atlantic Band of

Cdiz, SW Spain
Within these lithologies, generally scarce in the

southern Iberian geological environments, the
most important in terms of their proportion in
the archaeological record in the Atlantic region
of Cadiz are amphibolites, some metamorphic
rocks such as marbles and quartzites and a
few volcanic as tuffs (Domnguez-Bella et al.
2004). Some of these exotic lithologies would
be possible source area, outside the scope of
the Betic Cordilleras. In the Iberian Peninsula
there are several places you could find amphibolites similar to those described in the
4.2.1. Sillimanite/fibrolite, amphibolites, marbles

The sillimanite-fibrolite (Al2SiO5) is a metamorphic mineral of high temperature and
variable pressure, which appears in highgrade metamorphic rocks. This is not an
exceedingly rare mineral in metamorphic environments, although it is more limited when it
comes to centimeter or decimeter-sized nodu-
10
Seminario SEM 09
currently under study geochemical and mineralogical XRD-XRF and MO.
archaeological record of the Atlantic Band of

Cdiz. The possible source areas closer to the
area would be in volcano-sedimentary sequences, the southwest sector of the peninsula, particularly in the Ossa-Morena zone (provinces of
Huelva, Seville, Badajoz and Alentejo area,
south Portugal) and the amphibolites, the source could also be in the zone north of Huelva,
Seville and south of the province of Badajoz
(Domnguez-Bella & Morata 1995; DomnguezBella et al. 2004) and various points in
Portugal (Lillios 1997). A future line of work
should address the petrological, geochemical
and mineralogical different outcrops of these
rocks in the western peninsula and the Betic
Cordillera in order to be able to establish a
database that allows discrimination of different
exposures and allow the determination of -source areas for these archaeological materials
widely distributed in recent prehistory, of which
there is already evidence that were exploited by
means open pit quarry, somewhere in the western peninsula.
5. Prehistoric Jewellery
The wide variety of minerals and organic materials used as luxury or prestige jewellery (Bard
1999), their geological origin or source areas,
exploitation and trade routes of transportation
and exchange, make these studies from the
analytic sciences of great interest for archaeologists and museum and collections curators.
It is one of the most exciting in the archaeomineralogy (Guillong & Gnther 2001;
Kosmowska-Ceranowicz 1990 & 2003;
Domnguez-Bella 2004; Ruvalcaba et al.
2008; Querr et al. 2012; Calligaro et al.
1998 & 1999) and one of the archaeological
materials that has attracted more interest
from the archaeometric point of view, the gemmological minerals and substances.
There are interesting examples in the human
historical record since the Palaeolithic, but a
special abundance of these objects appear in
the recent prehistory of Europe and Africa
(Neolithic-Chalcolithic) or pre-Columbian times
in America. Gemmological materials have
been widely distributed over large commercial
networks throughout history, as in the case of
rubies, sapphires and emeralds, etc., highly
appreciated in Roman times and later
(Calligaro et al. 1998; 1999; Aurisicchio et al.
2005; Giuliani et al. 2000).
Regarding the articles made of marble, they

highlight the bracelets in one piece, made by
turning from fragments of this rock type and
relatively common in the Late Prehistory of
the area. We have analyzed some significant
records in areas bordering the Atlantic Band
of Cdiz, including: El Jadramil (Arcos de la
Frontera) (Domnguez-Bella 2003), Ardales
(Mlaga) (Domnguez-Bella et al. 2001 and
2004) and Villamartin, Cadiz. Its origin has
not yet been determined analytically.
Notable examples in the minerals used in

jewellery may also be some green minerals
from prehistory which have been a constant
across cultures and geographies.
4.2.2. Serpentinites and peridotites

In this type of ultrabasic rocks we have studied some objects recovered in the archaeological record of the area around the Strait of
Gibraltar. They are usually colored beads
made in dark green serpentine, as in the site
of Cantarranas-La Via (Domnguez-Bella,
Perez & Morata 2000) with an allochthonous
origin, due to the absence of these rocks in
the region. Other site is the cave of Benz
(Ceuta), placed in north Africa (Chamorro et
al. 2003 & Domnguez-Bella et al. 2006),
where the origin of these materials is local,
since there is an outcrop of ultrabasic rocks
in the city of Ceuta, close to the cave, which
may be the source area of these materials
They highlight examples such as jade in

Mesoamerica or Asia (Casadio et al. 2007),
turquoise in Mesoamerica and South America
(Domnguez-Bella & Sampietro 2005; Hull et
al. 2008), in Asia in the west Europe (Vzquez
Varela 1983; Domnguez-Bella 2004; Querr
et al. 2012).
From among the green mineral, as well as
other colors, deserves special attention jade,
a material highly valued since prehistoric
times in different cultures, chronologies and
geographical areas. During the last decade
11

Fig. 3. Multifactorial analysis distribution in geological and archaeological Neolithic variscites from ICP-MS-LA geochemical data (Domnguez-Bella
et al., 2002).
different methods of analysis of this mineral

substance using a wide range of analytical
methods have developed to determine their
geological sources, early jade working
methods, the detection of heating processes
in jade, burial and surface alterations.
field of mineralogy as OM, XRD, WDFRX,

PXRF, RM, CL, PIXE, PIGE, etc. Also of interest are some analytical techniques for the
study of fluid inclusions, especially important
in some of the gems, in relation to their genetic and therefore its source and origin area. A
synthesis of specific analytical techniques for
these studies has been described by
Anderson & Mayanovic (2003). The same
occurs with some applications of isotope studies in determining the source areas in gems
(Giuliani et al. 2000).
Of particular interest is the use of non-invasive Raman microscopy (RM) in the study of
Mesoamerican jadeite pebbles from
Guatemala (Gendron et al. 2002), This application of RM to jadeite could become a routine approach in archaeometry for identification and provenance studies, especially as
inexpensive portable Raman microprobes are
developed with improved spectral resolution
(up to 8 cm 1).
5.1. Archaeomineralogy of gemstones in the

Prehistory of Iberian Peninsula, France and
North of Africa
While the Iberian Peninsula and in general,

south-western Europe, are not rich in gemmological materials, there are some exceptions
that have been of great importance in the
exploitation, processing, transportation and
distribution of minerals and rocks used in the
production of precious or prestige objects,
not always gems, along prehistory in this geographical area.
Other techniques as X-ray fluorescence spectroscopy (XRF) and external beam particleinduced X-ray emission (PIXE) have been
applied to the study of jades. Chinese jades
dating from the Neolithic period (5000 to 1700
BCE) to the Han dynasty (206 BCE to 220 CE),
composed of nephrite, has been analyzed in
order to determine the minor elemental compositions of these objects, and their geologic
source in China (Casadio et al. 2007).
Minerals of the silicate group are also common in prehistoric jewellery, so we can find
examples similar to the Near East steatite
(Allen et al. 1975), such as beads of talc, clinochlore and micas in many different prehis-
Many analytical techniques already cited are

being used in the study of prehistoric jewellery, especially those of greater use in the
12
Seminario SEM 09
especially for the major elements in the sample and with a non-destructive character
(Domnguez-Bella & Bveda 2011).
toric sites in the Peninsula, where they appear as pendants or beads necklace. There are
many examples in the Iberian Peninsula in
recent prehistory sites as Katillotxu dolmen
in Biscay (Quintana 2009) or the site of
Leceia, Portugal (Cardoso 2002). Other silicate minerals such as clinochlore have been
analyzed in recent prehistoric sites, as in the
tumulus of the Higueras Valley, Toledo
(Domnguez-Bella 2010).
Depending on the type of material, its composition and origin have many different analytical techniques employed in the work of
archaeometric characterization carried out in
recent 50 years. Thus, for the majority of silicate compounds, oxides, sulfides, phosphates, carbonates, etc., has been used traditional techniques such as XRD, XRF, OM, FTIR
and in recent years, especially in samples
belonging to the funds of museums and
collections, new non-destructive techniques
such as PIXE, PIGE, XR microdiffraction, RM,
EDX, ESEM, LIBS, PXRF, etc., are being used.
Techniques such as mass spectroscopy,
inductively coupled plasma, laser ablation
(LA-ICP-MS) (Domnguez-Bella et al. 2003)
that can provide a detailed geochemistry of
the samples and that together with statistical
studies of factorial analysis of data have allowed us to identify possible source areas of
origin of products such as archaeological
variscites (Domnguez-Bella et al. 2002) (Fig.
3). The same occurs with techniques such as
PIXE, PIGE that we are applying to these
phosphate minerals within the project
CALLAIS, CHARISMA program, in development since 2010 and using the facilities of
AGLAE in the Louvre, Paris (Fig. 4). We are
currently working on multivariate statistical
treatment of data obtained over a wide sampling of variscitas and turquoise of the Iberian
Peninsula and France, as well as archaeological samples from all known geological sites
in Spain, Portugal and France, with the collaboration of Museums as Huesca, Braga,
Bilbao, British Museum, etc. Some of the
results of these and previous analyses have
been published (Querr et al. 2012).
Fig. 4. Variscite necklace beads from the Neolithic site of Saint

Michael, Carnac, France. Non-destructive analysis by PIXE-PIGE.
AGLAE, Louvre Museum, Paris. CALLAIS project.
5.1.1. Variscite and turquoise

Another green mineral of interest is the variscite
(Al2O3PO4nH2O), which geological rarity and
interest by the Neolithic man is a clear example
of precious material in prehistory. In Europe
there are not many geological areas containing
this phosphate, usually associated with its isomorphic variety, the strengite (FePO42H2O) and
sometimes other phosphates such as turquoise
(CuAl6(PO4)4(OH)84H2O) (Moro et al 1992a, b,
1995b). Underground mining techniques for
selective procurement of this mineral are well
known in Gav, Barcelona (Fernndez-Turiel et al
1990; Camprub et al 2003) and distribution of
this material in the N and NE of the Iberian
Peninsula (Munoz-Amilibia 1971; Guerra et al.
1995; Fernndez Vega & Prez Caamares
1988; Edo et al. 1998) and the SE of France
(Villalba et al. 1998).
Mineralogical and geochemical analysis by
ICP-MS-LA, XRF, etc., of these precious
objects in phosphate minerals were used to
determine their source and distribution areas
The X-ray fluorescence (WDXRF) and portable

(PXRF) also allows a quite precise analytical,
13

Fig. 5. Selection of objects made from jade, fibrolite and variscite from the cist at Saint-Michel (photos: S. Cassen and C. Le Pennec, collection
of the Soc. Polymatique du Morbihan, muse de Vannes).(in: Cassen et al., 2011) and in: www.jungsteinSITE.de
(Guerra et al. 1995; Domnguez-Bella et al

2002 & 2003).
These beads have a similar mineralogy, and

microscopic examination shows that it is
generally monomineral samples, massive,
fine-grained, pale green, colorless, non pleochroic and low relief, interference colors of
the second order. The qualitative chemical
analysis performed by means EDX as expected, showed the presence of P and Al.
The variscite appears among others in necklace beads recovered from the burials of the
dolmens of Alberite I (V and IV millenniums
BC) (Domnguez-Bella & Morata 1995) and
Tomillo (Domnguez-Bella et al. 2002), (IV-III
millennia BC) in the province of Cadiz. It is a
green mineral which has had a great importance in Neolithic-Chalcolithic societies in
southwest Europe.
The green beads of these chronologies present different mineral compositions (variscite, turquoise, talc, muscovite), with different
geological origins and many times geographical (Damour 1864; Cardoso 2000; Fernandez
Vega & Caamares Perez 1988; Huet B.
Gonalves 1980 & 1982; Muoz-Amilibia
1971; Rojo et al. 1995; Querr et al. 2012).
In this area and many others of the peninsula and in some places of France, it is relatively frequent the appearance of objects elaborated in this mineral, usually necklace
beads, which in the dolmen of Alberite represented 7% of over recovered 1000 necklace
beads.
It seems that the green color of these

minerals was the main feature wanted by
these communities for the elaboration of
these objects, whatever their composition,
hardness, etc. The green color should be a
sign of prestige or some ritual significance,
highly desired by the dominant members in
the communities. This idea is shown by the
fact that it is only in burials of the domi-
The XRD study of some of these beads revealed a monomineral nature, corresponding
with the type variscite Palazuelos. IR spectra
of these samples showed absorption bands
characteristic of the molecular groups (OH)and (PO4)3-, coinciding also with the variscite.
14
Seminario SEM 09
The emergence and expansion of variscite

necklaces become important in the Neolithic
south-western Europe from the sixth millennium BC and their use lasts until the Roman
Empire, where it is mined in western Spain,
replacing and / or imitating emeralds.
nant groups in which the large necklace

beads and pendants of these minerals
appear, as in the megaliths of French
Brittany (Cassen et al. 2011 & 2012),
Galicia (Dominguez-Bella & Bveda 2011),
Por tugal, Extremadura and Andalusia, or
the pit burials Culture in Catalonia
(Domnguez-Bella 2004).
The variscite outcrops in south-western

Europe with special geological features are
found almost exclusively in the Iberian
Peninsula. Vein deposits of this mineral,
associated with Silurian slates with black siliceous levels and quartzites, appear in the
Palaeozoic of North Portugal (Ervedosa), the
provinces of Zamora (Palazuelo de las
Cuevas, Bercianos, El Bostal, etc.) and
Huelva (Encinasola), Galicia (Punta Montalvo)
The variscite and turquoise beads are associated in these funerary environments (Fig. 5)
with other minerals that also had to have a significance of prestige or ritual, such as cinnabar, amber, rock crystals and large flint blades
and axes, chisels and adzes polished rocks,
idols and palettes for pigments (Ramos and
Giles 1996; Cassen et al. 2011).
Fig. 6 Large distribution networks over long distances for Iberian variscites have been identified from these sources in the French Brittany (Querr
et al., 2012)
15

Fig. 7. Selection of turquoise beads from the Taf Culture, Tucumn province, Argentina and direct XRD diagrams of the representative lithologies of the beads (turquoise, green mica, opal). (Domnguez-Bella & Sampietro, 2005).
16
Seminario SEM 09
studies for these variscite materials as a complementary line of future research in the determination of source areas.
and the Catalan Coastal Cordillera (Gava,

Moncada) in Barcelona. For the studies conducted so far, it seems that the only deposits
of variscite and turquoise exploited in
Prehistoric Europe were in the Iberian
Peninsula. Mines of prehistoric turquoise and
variscite at Gav (Barcelona) are well known,
although there are clear indications already
confirmed of prehistoric exploitation in
Encinasola (Huelva) and Palazuelos de las
Cuevas (Zamora), where exploitation is manifest in Roman times (Campano Rodriguez &
Sanz 1985; Domnguez-Bella 2004).
In the case of turquoise, very different analytical techniques have been used for mineralogical characterization and source areas identification. Techniques as Arc emission spectrometr y analysis, Electron microprobe,
Instrumental neutron activation analysis,
Spectrometry, X-ray diffraction and X-ray fluorescence are employed throughout the world.
As an example, we can cite the study on a set
of cylindrical beads and zoomorphic of Taf
Culture (300 B.C. - 800 A.D.), Tucuman,
Northern Argentina, possibly from the turquoise deposits in northern Chile (Fig. 7)
(Domnguez-Bella & Sampietro 2005). The
same method as the variscites has been
Variscite mining of Catalonia (Gav mines)

seems that supplied the northern and northeastern Spain and southern and western
France (Guerra et al. 1995; Edo et al. 1998).
The deposits of western Spain seem that
variscites distributed to the southwest and
western half of the Iberian Peninsula
(Domnguez-Bella 2004), although there is
evidence of a large distribution networks over
long distances, variscites have been identified from these sources in the French Brittany
(Querr et al. 2012) (Fig. 6).
Other variscite deposits of the Iberian
Peninsula that has certainly been exploited
since prehistoric times are Encinasola (Huelva)
and the area of Palazuelos-The BostalBragana (Moro et al. 1992 a-b; Moro et al.
1995 a-b; Domnguez-Bella 2004) located in
the SW and NW of the Iberian Peninsula, which
have been analyzed in the last 18 years
(Dominguez-Bella & Morata 1995; Merielles et
al. 1989; Domnguez-Bella 2004 ; DomnguezBella et al. 2004; Odriozola et al. 2010; Querr
et al. 2012). We have made in recent years, different geochemical analysis along with statistical studies by factor analysis of analytical data
obtained by ICP-MS-LA, XRF and SEM-EDX, with
a geochemical model of 13 variables, carried
out both on geological samples and archaeological samples (Dominguez Bella et al. 2002).
Recently, further analysis by PIXE-PIGE, XRF,
PXRF, XRD are being carried out on these geological sites of the Iberian Peninsula, including
minor ones like Punta Montalvo, Corua and
several archaeological sites in Spain, Portugal
and France, in an International Project,
CALLAIS, in the CHARISMA program of the EU
7th Framework. We also propose new isotopic
Fig. 8. Smoky rock crystal, monocristaline quartz from the Dolmen de

Alberite I, Villamartn, Cdiz, SW Spain. (Domnguez-Bella & Morata,
1995).
17

employed in the Iberian turquoise, since it

has the same paragenesis in the studied
deposits.
times, we could include in this group of

substances other compounds of organic
origin as fossil resins, which also have
been used in jeweller y or as objects of
prestige, from prehistor y to present.
5.1.2. Single cr ystal quar tz
From the Upper Palaeolithic, pieces of

amber are recorded at sites attributed to
the Magdalenian in locations of Central
Europe, also in enclaves of the
Hamburgian culture. The Neolithic records
are also ver y prominent and many beads
are well known since ancient in the
Megalithism of the Iberian Peninsula,
especially dolmens in Por tugal. They have
generally been classified as jet, due to the
total absence of analysis.
The presence of quar tz cr ystals is relatively common in Prehistoric funerar y environments, in the southwest peninsular, in
the province of Cadiz, as in many other
par ts of the Iberian Peninsula and Europe.
Spectacular examples are the large single
cr ystal of smoky quar tz that appeared in
the dolmen of Alberite (Fig. 8) , a rock
cr ystal in the dolmen of El Juncal, Cadiz or
a quar tz cr ystal of Triassic age, as found
in the silos of La Esparragosa archaeological site (Chiclana).
The first is a pegmatitic quar tz, accompanied by small traces of feldspar. The possible source area of that can be located,
according to Dominguez-Bella and Morata
(1995) in pegmatitic rocks environments,
perhaps in the Sistema Central of Spain,
with which pegmatite quar tz cr ystals have
strong similarities in their morphology, and
located several hundreds of kilometers
away where it appeared.
The ambers of Baltic origin are composed

mainly by succinite (Beck et al. 1965;
Stout et al. 2000) and are used in Europe
since at least the Iron Age, with a widespread use during the Roman Empire, at
both the European and Mediterranean
areas, where amber routes were well established, crossing Europe from nor th to
south. This characterization has been worked since the 70's (Savkevich & Shaks
1964; Beck & Vilaa 1995; KosmowskaCeranowicz 1990, 1999 & 2003) on geological and archaeological ambers, especially in European sites.
In the case of the bipiramidal quar tz

cr ystal appeared in La Esparragosa
archaeological site (Chiclana), it is a
cr ystal type Jacinto de Compostela , grey
in color and a size of about 3 cm. These
cr ystals are common in gypsum and clay
deposits of the Keuper facies, of Triassic
age in the Betic Cordilleras. Outcrops of
these materials extending along a band
from southwest to nor theast across the
province of Cadiz, according to the predominant direction of the Betic Cordillera,
several of them exist in this area of the
Atlantic band of Cdiz, in Iro River Basin in
where the site of La Esparragosa is placed. Thus, the origin of this cr ystal would
probably be local, being of an exceptional
size, it was possibly collected.
For organic compounds such as amber,

the fundamental techniques that have
been used since the beginning of the
analytical archaeometric have been FTIR
(Beck et al. 1964) and some other partially destructive as elemental analysis
(Domnguez-Bella
et
al.
2001) .
Considering the great experience on the
topic of the schools in Nor thern and
Eastern Europe, it follows that one of the
best methods of identification and classification of resinites is infrared spectroscopy
(FTIR) (Savkevich & Shaks 1964; Beck et
al. 1965).
5.1.3 Amber in the Prehistor y of the

Iberian Peninsula and Europe
Angelini & Bellintani (2005) published a

study about five dif ferent localities and
types of European geological ambers, and
also included Italian geological ambers
from seven dif ferent deposits. They emplo-
In addition to many of the minerals and

gems known and used since ancient
18
Seminario SEM 09
yed in the analysis Fourier transform infrared spectroscopy (FTIR) and dif fuse-reflectance infrared Fourier transform (DRIFT).
Other techniques of analysis of geological
and archaeological ambers are the GC-MS
and thermal pyrolysis analysis, X-ray diffraction and scanning electron microscopy
and mass liquid chromatography with
spectrometric detection. In some cases,
the use of polarizing transmitted light
microscope in the study of natural polymers in thin sections is another impor tant
technique for the identification of the
mineral inclusions in the sample, the textural relationships between them, the
Investigations of the fluid inclusions and
the fossil animals and plants fragments. In
order to obtain a fingerprint related to the
origin amber, good results are obtained by
direct mass spectrometric techniques, as
the atmospheric pressure photoionization
(APPI) (Tonidandel et al. 2008) . The
results using the X-ray dif fraction vir tually
does not allow in general, to obtain information of interest (Domnguez-Bella et al.
2001). However there are cases where it
provides information about the type of
amber inclusions or minerals, such as
occurs with the romanite (Teodor et al.
2009).
Fig. 9. Neolithic necklace of amber and variscite from the Chousa

Nova dolmen, Galicia, NW Spain (reconstruction). (see DomnguezBella & Bveda, 2011).
These new techniques for this cataloguing of

deposits and varieties of ambers and the creation of analytical databases of the same,
will undoubtedly improve the determination of
the origin of archaeological ambers. This is
especially important to identify the source
areas of different ambers of local origin,
which are different chemically and genetically
in relation to the Baltic succinite (Teodor et
al. 2009; Kosmowska-Ceranowicz 1999).
These studies have been generally associated
with the search of the geological source sites
in each region. In the Iberian Peninsula, some
ambers have been characterized in different
archaeological sites; in southern peninsular
(Dominguez-Bella & Morata 1995), Portugal
(Vilaa et al. 2002), north of Spain (Alvarez et
al. 2005; Pealver et al. 2007), central Spain
(Domnguez-Bella 2010) and Galicia
(Domnguez-Bella and Bveda 2011) (Fig. 9).
Fig. 10. FTIR diagram from three archaeological amber beads of the
necklace from Chousa Nova dolmen, Galicia, NW Spain, and comparison with a succinite Baltic amber sample. (Domnguez-Bella &
Bveda, 2011, modified).
19

years, at least at European level, with programs

such as CHARISMA, the 7th Framework
Program for transnational access to large
equipment.
In the case of amber there are several

records in the area of the province of Cadiz,
SW Spain, with necklace beads made of
amber and in a Neolithic chronological context, such as the Dolmen Alberite I, whose
origin seems to be far off, since the samples
corresponds to a simetite, species unknown
in geological outcrops of the Iberian
Peninsula, at least until the present
(Domnguez-Bella et al. 2001). We are
currently working on Galicia archaeological
ambers (Domnguez-Bella & Bveda 2011)
(Fig. 10) and on two new Neolithic sites in
this region of southern Spain, having identified new ambers beads or pendants without
Baltic provenance.
The development of analytical databases for

different substances such as amber, ancient
metallurgical products, marble, flint, ceramic,
etc. undoubtedly facilitate future research in
the field of archaeometry, but require large
investments or transnational projects which
must overcome many administrative difficulties, economic and technical to be of homologated use. The different analytical techniques
and technological developments, and experimental protocols make it difficult to homogenize the results contained in these bases, at
least for specific techniques. Databases of
images of OM, CL, in research areas such as
marbles and rocks or ceramics in ancient times
are for example very interesting.
6. Conclusions
The interest from the fields of archeology and
heritage management and study of the mineralogy and archaeometry is growing in recent
decades in a very strong worldwide, with an
increasing number of scientific publications
and outreach related to the archaeometric
application of techniques, where the mineralogy plays an important role in the study and
conservation of heritage.
A massive growth has been experienced in the

Iberian Peninsula in recent years regarding the
number of researchers involved in archaeometry work, although there is still a long way
off, given the historical gap in relation to other
neighbouring countries. The increasing international collaborations are softening rapidly these
differences.
We agree with the idea of mineralogists colleagues in the need for a real interdisciplinary
work in the archaeomineralogical and
archaeometric determinations which we have
been doing in our research field in recent
decades.
From our own experience we can note that the

information provided by mineralogical techniques applied to archaeometry is providing
valuable data for historical reconstruction in different periods of the Prehistory Peninsular,
European and North African. This is applicable
to the aspects related to daily use objects in
stone, ceramic, bone, metal, etc., as to others
related to rituals, symbolism and power, where
minerals like pigments and minerals, rocks and
substances used in jewelry and votive or prestige objects would be taken into consideration.
There are a great number of mineralogical

analysis techniques currently available, the
choice of which one or ones are best suited to
each case studies posed problems and it is an
important matter to determine a priori. It is
usually necessary more than an analytical technique for a complete study of the samples and
the resolution of the issues raised.
We have not only been able to characterize geochemically many compounds mineralogical and
minerals, rocks, ceramics and pigments, but
we have also obtained interesting information
about the source areas of these materials and
hence their mobility at short, medium or long
distance, during prehistory. Notable examples
can be used as a pigment cinnabar in many
megalithic tombs of the Neolithic and the
Undoubtedly, the physical availability of equipment and the economic cost of the use of certain analytical techniques will largely condition
their use in solving archaeometric problems,
the number of samples to be analyzed, the
existence of scientific equipment in the
surroundings and the available budget. Access
to large facilities has been provided in recent
20
Seminario SEM 09
and taught me to increase knowledge and

passion for this branch of mineralogy. My sincere thanks and apologies for mistakes to all
of them. Financial help from different research projects contribute (for example,
PB96/1520 and HAR2008-0669-C03-02,
Ministry of Education and Science of Spain
and Callais Project, CHARISMA PROGRAM.
7th Framework Program and Research Group
HUM-440 of Junta de Andaluca). Their contributions are greatly appreciated. Finally I
would like to thank the organization of this
seminar, especially J.M. Herrero for their invitation and assistance in the editorial work
and A. Durante for her unconditional help.
Chalcolithic, in which the determinations mineralogical, geochemical and especially the S isotopes seem promising lines of work. Amber,
with a presence since the Paleolithic in caves
of the North Spain, has been used as a jewel
in the Neolithic-Chalcolithic of Galicia, Castile
and Andalusia, with a possibly peninsular origin, while from the Iron Age, is becoming a priority Baltic provenance.
Tools or prestige objects manufactured in polished rocks have also provided valuable archaeological information, after determining their local
or distant origin, possibly transported over long
and organized exchange networks during
recent prehistory. So it is with some knapping
stone products, especially in siliceous rocks as
flint and radiolarite, where objects such as
large blades of flint, are transported hundreds
of kilometers along the peninsula and Europe.
Another of the minerals used in the manufacture of polished stones, used as tools or objects
of prestige are the sillimanite axes and adzes,
with great peninsular diffusion which extends
to the West European and even the British
Isles, with relatively few areas-source and in
which analytics we are still immersed.
8. References
Aguayo de Hoyos, P., Puga Rodrguez, E., Lozano
Rodrguez, J.A., Garca Gonzlez, J.D. & Carrin
Mndez, F. (2006) Caracterizacin de fuentes de
materias primas para la elaboracin de herramientas de silimanita, de los yacimientos de la
Depresin de Ronda, durante la Prehistoria
Reciente. In: G. Mar tnez Fernndez, A. Morgado
Rodriguez y J.A. Afonso Marrero (coords).
Sociedades prehistricas, recursos abiticos y
territorio. Ed.: Fundacin Ibn Al-Jatib. Ser vicio de
Publicaciones Universidad de Granada. 249-277.
Materials used as jewels of prestige as variscite and turquoise, with geological source areas
quite well known and almost exclusive to the
Iberian Peninsula, show large geographical
mobility, exceeding of a thousand kilometers as
occurs with jadeite and other HP alpine rocks in
their distribution network throughout Western
Europe. In this case, mineralogy, geochemistry
of trace elements and multivariate statistical
treatment of analytical data, are allowing their
potentially-source geological areas.
lvarez Fernndez, E.; Pealver, E. & Delcls, X.

(2005) La presencia de mbar en los yacimientos prehistricos (del Paleoltico Superior a la
Edad del Bronce) de la Cornisa Cantbrica y sus
fuentes de aprovisionamiento. Zephyrus 58,
159-182.
Allen, R.O., Luckenbach, A.H. & Holland, C.G.
(1975) The application of instrumental neutron
activation analysis to a study of prehistoric steatite
ar tifacts
and
source
materials.
Archaeometr y, 17, 69-84.
These are undoubtedly exciting topics and with

great future expectations in the scientific development of archaeometry and mineralogy,
which certainly are of great importance in
understanding the complex human history and
for some mineralogists, continue to constitute
a fatal attraction.
Anderson, A.J. & Mayanovic, R.A. (2003)

Electron, nuclear and X-ray probe microanalysis
of fluid inclusions. In: I. Samson, A. Anderson
and D. Marshal, (eds.) The Analysis and
Interpretation of Fluid Inclusions. Mineralogical
Association of Canada shor t course. 32. 323351.
7. Acknowledgement
I thank many archaeologists, geologists, chemists, etc. colleagues and collaborators
which over the past two decades have helped
Angelini, I. & Bellintani, P. (2005) Archaeological

ambers from Nor thern Italy: an FTIRDRIFT study
21

of provenance by comparison with the geological

amber database. Archaeometr y, 47, 441-454.
racterization of flint raw materials from the

Iberian Neolithic mine of Casa Montero.
Archaeometr y, 51, 2. 175-196.
Ar tioli, G. (2010) Scientific methods and the

Cultural Heritage. An introduction to the application of materials science to archaeometr y and
conser vation science. Oxford University Press,
Oxford, 536 p.
Calligaro, T., Mossmann, A., Poirot, J.P. & Querr

G. (1998) Provenance study of rubies from a
Par thian statuette by PIXE analysis. Nuclear
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Ar tioli, G. & Angelini, I. (2011) Mineralogy and

archaeometr y: fatal attraction. Eur. J. Mineral.
23, 849-855
Calligaro, T., Poirot, J.-P. & Querr, G. (1999)

Trace element fingerprinting of jeweller y rubies
by external beam PIXE. Nuclear Instruments and
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Rubalcaba-Sil, J.L.; Manzanilla, L.; Melgar, E. &

Lozano Santa Cruz, R. (2008) PIXE and ionoluminescence for Mesoamerican jadeite characterization. X-Ray Spectrom. 37. 2. 96-99.
Tenorio, D., Jimnez-Reyes, M. & Lagarde, G.

(1997) Mexican obsidian samples analysed by
PIXE and AAS. International Journal of PIXE. 7, 12, 17-24.
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LXXXIII, 125-144.
Tonidandel, L., Ragazzi, E., Roghi, G. & Traldi, P.

(2008) Mass spectrometr y in the characterization of ambers. I. Studies of amber samples of
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petrogrfico de siete hachas neolticas pulimen-
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different origin and ages by laser desorption ionization, atmospheric pressure chemical ionization
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spectrometr y. Rapid Commun. Mass Spectrom.
22, 630638.
Trevisani, E., Papazzoni, C.A., Ragazzi, E. &
Roghi, G. (2005) Early Eocene amber from the
Pesciara di Bolca (Lessini Mountains, Nor thern
Italy). Palaeogeography, Palaeoclimatology,
Palaeoecology, 223. 260-274.
Turbanti Memmi, I., Ionescu, C. & Schssler, U.
(eds.) (2011) Mineralogical Sciences and
Archaeology. Eur. J. Mineral, 23, 6, 847-1008.
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Tykot, R.H. (2002) Chemical Fingerprinting and
Source Tracing of Obsidian: The Central
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Vzquez-Varela J. M. (1975) Estudio mineralgico
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Vilaa, R.; Beck, C. W. & Shout, E. C. (2002)
Provenience analysis of prehistoric amber ar tifacts in Por tugal. Madrider Mitteilungen.
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Villalba, M. J., Edo, M. & Blasco, A. (1998)
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28
Trace element geochemistry

and mineralogy for solving
problems in provenance and
production technologies of
Pre-historic ceramics
/ Maria Isabel Prudncio
Instituto Tecnolgico e Nuclear, Instituto Superior Tcnico, Universidade Tcnica de Lisboa, Estrada Nacional 10,
Sacavm, Portugal.
Abstract
Compositional analysis of archaeological ceramics and raw materials, together with archaeological
data is a powerful approach to solve questions dealing with provenance, production technology, and
regional and interregional interaction patterns. The chemical and mineralogical characterization of the
regional potential raw materials is very important when there is a lack of kilns structures, which is the
case of prehistory. The vessels are made mostly by clays, the composition of the ceramics reflecting
the original raw materials. Conclusions may be inferred concerning the type of raw materials and the
establishment of the resource procurement zones. A special care has to be paid when interpreting the
compositional results of the archaeological ceramics, since the composition of the broken fragments
that archaeologists recover in excavations is the combination of several parameters, starting with the
initial composition of the raw materials, its manipulation to make the vessel, the use and the burial
environment. Compositional studies of Chalcolithic ceramics from archaeological sites in Portugal played a very important role, particularly the trace elements distribution, to determine provenance. In
general, the results point to local productions, and thus to the circulation of the idea rather than the
products. These results help to conceptualize the diffusion models and to recognize the importance
of certain typologies and their significance in an archaeological point of view.
Resumen
El anlisis composicional de las cermicas arqueolgicas y sus materias primas, junto a los datos
arqueolgicos, son una potente herramienta para resolver cuestiones relativas a la proveniencia, tecnologa de produccin y modelos de interaccin regional e interregional. La caracterizacin qumica
y mineralgica, de las materias primas potenciales de la regin, es muy importante cuando se carece de estructuras de hornos, como es el caso de la prehistoria. Los recipientes se han realizado
principalmente con arcillas, en los que la composicin de la cermica refleja las mater-ias primas
originales. Se pueden extraer conclusiones, teniendo en cuenta el tipo de materias primas, estableciendo las zonas de aprovisionamiento de recursos. Hay que considerar como un caso especial la
interpretacin de los resultados de composicin de las cermicas arqueolgicas, ya que los fragmentos rotos que recuperan los arquelogos en sus excavaciones suponen una combinacin de
varios parmetros, desde la composicin inicial de las materias primas, su manipulacin para realizar la vasija, el uso y finalmente el ambiente de enterramiento. Los estudios composicionales, y en
especial los de distribucin de elementos traza, de la cermica del Calcoltico de yacimientos arqueolgicos portugueses, han jugado un papel muy importante para determinar la proveniencia. En general, los resultados apuntan a producciones locales y por tanto, a la circulacin de la idea, ms que
de los productos. Estos hallazgos ayudan a conceptualizar los modelos de difusin y a reconocer la
importancia de ciertas tipologas y su significado en el punto de vista arqueolgico.
Key-words: ceramics, clays, trace elements, mineralogy, production technology, provenance, pre-history
29
Trace element geochemistry and mineralogy...

Prudncio, M.I.
1. Introduction
conclusions one can get from the results;

and
Ancient ceramics are well known for their

enormous potential of information in archaeological studies, being used to date
sites, trace trade patterns, understand social
and economic relationships, and so forth. In
archaeology the term ceramics usually refers
to cooking and serving utensils and art
objects manufactured of clay. For potters the
term clay means the basic ingredient in ceramic manufacture, composed of plastic particles (clay) and natural nonplastic grains.
Compositional analyses of pottery together
with classical archaeological approaches
have been largely used in solving a broad
variety of questions. In fact, the application of
the techniques of chemistry, physics, geology, and materials science provide a basis
for understanding many questions about
manufacturing techniques, history of technology, production organization, functional relationships between specific resource manufacturing combinations, and patterns of local,
regional, or extraregional distributions of
potery. Thus, better understand a culture,
time period or human interaction. These are
the main re-search issues of ceramic technological (and ecological) analysis. An overview
of these types of studies is well shown in the
litera-ture (Rice 1987; Chappell 1991; Hector
1992; Velde & Druc 1999).
the translation of mineralogical and geochemical data to archaeological proposals.

The use of resources is very important to
deciphering the provenance of a ceramic
object, i.e., the geographic area where the
object was produced, especially when no
archaeological evidence of potter y workshops are found which is the case of the
majority of prehistory. Compositional characterization, as applied to pottery, is oriented
toward quantitative and qualitative description of its mineral and chemical components.
Establishing local and regional patterns
needs a regional clay deposits inventory,
followed by studies of minera-logical and chemical characterization.
Mineralogical analysis of ancient pottery is
particularly useful in the understanding of the
manufacture process, and appropriate techniques may provide information about temper
addition, oxidation-reduction conditions and
temperatures of firing. Results may also be
obtained about post-depositional processes.
Petrographic analysis is an important tool in
the determination of pottery provenance by
the identification of fingerprint minerals,
when comparing different clay deposits.
The compositional analysis of ceramic materials in archaeological studies is carried out

aiming particularly to understand how the
ceramic might have been used and to determine the location and techniques involved in
its manufacture. Furthermore, these objectives can be achieved on broken fragments as
well as intact vessels. Numerous issues deserve significant attention at the start of a
mineralogical and chemical characterization
study:
Chemical analysis of sherds, especially

concerning trace elements, is a power ful
approach in ceramics characterization and
provenance studies, since geochemical
interpretations may contribute largely to
solve archaeological problems.
Among the materials and processes involved
in making a pot, the most important is clay
and its manipulation to make the vessel.
the objectives of the analysis must be defined so they can be translated into chemical and mineralogical terms;
Therefore it is important to know how the different elements make clays, what the leftovers are in the claymaking process, and the
mineralogical and geochemical fingerprints
which can give one a clue to the geographic
origin of the clay and temper materials found
in the finished product. Hence a discussion
the requirements of sample selec-tion for

each technique must be understood;
the understanding of the limitations of the
30
Seminario SEM 09
Fig. 1. Surficial clay materials derived by weathering of schists (A) and sediments (B).
of pottery must include clay and its origin,

composition and properties.
Compositional data are independent of

other common categorizations of potter y
used by archaeologists, such as styles,
type classes, or shape categories, yet they
can be used for comparing such groupings
or creating new ones. In combination with
ceramic ecology, ceramic technology can,
for example, characterize proper ties of both
resources and potter y and permit comparisons between them. The resources should
be compared with care to the possibilities
of a given production site.
In ancient times, sources of clays tended to

be those easily available. Soils or surface
sediments are likely candidates (Fig. 1).
Some soils or sediments can be adapted to
form a ceramic without further treatment. If
the proportions of clay, silt and sand are not
adequate, tempering by mixtures of materials
of the same source or from different sources
can be done. All these procedures during
manufacture, together with eventual modifications of the ceramic composition during
use and burial, can lead to compositional
alterations that can difficult the establishment of provenance.
Today clay and other ingredients used for

ceramic production can come from sites thousands of kilometres from the production site.
However, in the past, the potter was more
tied to the local resources for his production,
since clays did not travel more than several
kilometres; tens at most if water transport
did not intervene, sands and so forth even
less. In this way the potter would have adapted local resources to answer specific needs,
functional and aesthetic.
Studies of the mineral transformations of clays

induced by firing and their comparison with the
mineralogical composition of sherds may help
to determine the type of clay used and the temperatures range they could have been exposed
to during their production. In this comparison it
is necessary to take into account that ceramics
are not merely fired clays. Their composition
depends not only on the chemical and mineralogical composition of the clays, but also on the
grainsize distribution, possible addition of different types of nonplastic grains as temper, mixture of clays, maximum heating temperature, heating ratio, duration of firing, redox atmosphere
and post-depositional alteration (Maggetti,
1982; Rice, 1987; Moropoulou et al., 1995;
Velde & Druc, 1999; Trindade et al, 2010).
The methodological approaches to study

archaeological ceramics vary depending on
the nature of the raw materials used and the
manufacturing techniques. Research began
by a careful examination of the broken pottery fragments that archaeologists recover in
their excavations. Ceramic characterization is
done with three main objectives classification, production technology and provenance.
The more commonly used techniques to cha-
31

Prudncio, M.I.
the larger number of chemical elements as

possible, is particularly useful in provenance
studies. In this way, large data sets are generated, which need to be processed by computer with statistical programs. One important
thing to not forget is that statistics analysis
is only a tool to help us with very large
amount of data matrixes (variables and samples) and remember that the results obtained
are an approximation of the reality. The attribution of one pot to one particular site or
composition group is based on statistical probabilities. The results obtained by statistical
analysis must be checked taking into account
geochemical considerations.
racterize archaeological vessels focus on the

mineralogical and chemical constituents.
There are several methods that can be
employed. However it should be noted that
special considerations in applying these
methods to archaeological pottery must be
taken into account.
The very first step (and one of the most
important) in an archaeological ceramics
study concerning a compositional study, is
the selection of sherds from a large collection. In general there is an enormous range of
recognized variation in visible characteristics,
and it is a difficult task to break down a
collection into a much smaller number of
sherds that represent the variations in the
entire collection. The ideal starting point is
the identification of a problem and the categories of archaeological pottery from which
the sample will be drawn are generally those
traditionally used in archaeology - types,
decorative classes, and wares, as well as
In some cases, an important step prior to any

statistical analysis is normalization of the chemical elements contents. To compensate for
grainsize and mineralogy effects on trace element concentrations, thus diminishing erroneous interpretation of ceramic provenance, a
common approach used in determining regional geochemical baselines is to normalize geochemical data using one element as grainsize
and mineralogical proxy, that is to express the
ratio of the concentration of a given element to
that of the normalizing factor.
Normalization using a conservative element
has been commonly used in environmental
studies, especially in verifying whether the
variation of elements in sediments is indeed
the result of anthropogenic and/or natural
activities. Hence normalization in archaeological ceramics studies is defined as a procedure to compensate for the influence of natural (geological and ceramic burial time) and
anthropogenic (technology of production) processes on the measured variability of the
concentration of elements, emphasizing the
importance of taking into account geochemical behaviour of the element chosen for normalization, and not purely based in statistical
considerations (Prudncio et al., 2006; Dias
& Prudncio, 2008).
Fig. 2. Pre-historic sherds with different pastes and decorations (photographs by Antnio Valera).
chronological and regional variations (Fig. 2).

Compositional analyses of the archaeological
ceramics aim to know texture features, and
the mineralogical and chemical composition.
Several techniques can be used such as optical microscopy, X-ray diffraction (XRD),
Mssbauer spectroscopy, instrumental neutron activation analysis (INAA), X-ray fluorescence, among others. Chemical analysis of
ceramics and of raw materials, determining
Normalization of elemental concentration to

an immobile, conservative element provides
deeper insights about other elements distribution than the consideration of the absolute
concentration itself alone. Therefore, the
best option appears to be the use of a con-
32
Seminario SEM 09
formation of new mineral phases, sedimentary sorting, and diagenesis. These elements
have very similar chemical and physical properties, which is the result of the nature of
their electronic configurations. The dominant
oxidation state is the +3 state, and there is a
small but steady decrease in ionic radius with
increasing atomic number (for a given coordination number). The REE, therefore, tend to
occur in nature as a group. They are lithophile, in that they concentrate predominantly in
the silicate rather than the metal or sulphide
phases when they coexist. The differences
existing among the REE lead to differences in
their relative behaviour in response to the
chemical environment, making this group particularly useful in geochemistry since they
can be a pointer of the genesis processes of
the rocks and minerals and subsequent alterations (Prudncio et al. 1993, 1995;
Gouveia et al. 1993; Burt, 1989).
servative element, and among these, Sc

appears to be the more appropriate to normalize chemical data then other elements; even
their variability is higher, since the raw materials are related with a specific geological
context which has to be considered. Sc is
structurally combined in clay minerals and
micas, being a good tracer of phyllosilicates,
particularly in sediments containing Al-silicates in all size fractions.
Several multivariate statistical methods can
be employed by using statistic programs (e.g.
STATISTICA, Statsoft, 2011). The results
obtained must be integrated and interpreted
taking into account the significance of correlations between the chemical elements
(variables) found in ceramics and their meaning in terms of raw materials composition,
and possible alterations due to the production technologies (sieving, sedimentation,
add of temper, mixing clays, etc.), eventual
modifications during the use of pots, and
postdepositional processes.
The application of the INAA method in support of provenance research has been largely
used over the past few decades in the
Instituto Tecnolgico e Nuclear (IST/ITN). The
first analyses of archaeological ceramics
were conducted in the late 1970s by using
the Portuguese research reactor (RPI), and
proceeded generating a large database for
ceramics and raw materials from different
A number of different analytical techniques

have been applied with varying degrees of
success to characterize archaeological materials, but all of them need to have multielement capability and sufficient sensitivity to
detect traces of elements in the various
matrices. Among them the analytical method
with one of the longest and most successful
histories of application for provenance research has been instrumental neutron activation analysis (INAA). The real success story of
this technique, however, comes from the
investigation of ceramics dating from throughout archaeological times. INAA is a sensitive technique useful for quantitative multielement analysis of major, minor, and trace elements, which concentration can have different meanings in minerals or in rock descriptions, as well as in ceramics (Prudncio,
2009; Glascock & Neff, 2003).
Among trace elements, rare earth elements
distributions can be particularly useful in distinguishing clayey materials resources. The
subtle variations in the properties of REE
make them sensitive to mineral/melt equilibria, as well as to weathering conditions after
the breakdown of primary minerals and the
Fig. 3. Map of Portugal, with the location of the archaeological sites Fraga da Pena, Monte do Tosco and Porto Torro.
33

Prudncio, M.I.
chronologies and archaeological sites (Dias

et al., 2000; 2001; 2002; 2003a, 2003b;
2005; 2007; 2010; Prudncio et al., 1988;
2003; 2006; 2009). In the late 1990s, a
research group especially devoted to
archaeometry (measurements techniques in
archaeology), particularly compositional and
dating studies (TL-OSL) of ceramics and raw
materials, was formed in ITN Cultural
Heritage and Sciences, nowadays named
Applied Geochemistry & Luminescence on
Cultural Heritage (GeoLuC). INAA has also
been used for precise and accurate determination of the contents of natural radioactive
elements such as potassium, rubidium, thorium and uranium aiming to evaluate the
dose rate, which is fundamental for TL-OSL
dating of cultural materials and archaeological contexts, as well as geological contexts
(Prudncio et al, 2007; Burbidge et al.,
2009; 2010).
porous, with poorly oriented particles, and lowfiring, is more defected resistant. It is a multipurpose paste often found in prehistoric wares.
However in some cases a careful selection of
the clays or a preparation of the materials to
obtain a particular paste for the production of a
specific kind of ware was also done in pre-history (Velde & Druc, 1999).
2. Case studies. Geochemical and mineralogical characterization of Chalcolithic

ceramics from Portuguese sites
Three relevant case studies of ceramics from
Chalcolithic to early Bronze Age archaeological sites from Southern and Central Portugal
(more recent up to north) are presented (Fig.
3). They are specially focused on a chemical
and mineralogical characterization of both
pottery and potential raw materials from the
region, aiming the establishment of provenance and production technology, thus contributing to the discussion of the circulation
/diffusion of this kind of pottery (Cabral et
al., 1988; Dias et al., 2000; 2002; 2003a;
2005; Dias et al., in press; Valera, 2006).
The making of pots in pre-history

Potters clay is a material of high clay content, with a high or certain plasticity when
wetted and worked. In addition to clay minerals, nonplastic grains may occur in different
proportions. Also non-plastic grains may be
added by the potter to the clay material to
improve the working to make the pot that is
reducing the plasticity of the waterloving clay
particles. The material added is in general
termed as temper. Inclusion is also a term
used by archaeologists to refer any nonplastic material in the paste (mineral grains, rock
fragments, grog or crushed shells).
Chalcolithic ceramics from the three sites include the typical typologies of this chronology, particularly the combed incisions and the Bell
Beakers. These typical pots were decorated
with patterns stamped on the surface in parallel bands, sometimes filled with white paste,
but there are often traces of lime and paint
decoration as well. Cord impressions are common, some are all over cord or all over ornamented, others are incised or stamped with
various geometric motives, often arranged in
zones (Valera, 2006).
The manufacturing process include several

steps (forming, drying and firing), which lead to
physical and chemical reactions influencing
ceramic production: plasticity and the role of
temper, shrinkage during firing, and nonplastic
expansion during firing. The visible reactions
are mainly change in colour, and retraction and
expansion processes related to the quality of
the paste, the type and quantity of the raw
materials, the particle size, the amount of
water present, the preparation of the paste and
the forming techniques used.
Classical archaeological studies regarding

the prehistoric ceramics together with laboratory research has been providing significant
results concerning questions related with production technology, raw materials exploitation
strategies, provenance and mechanisms of
circulation.
2.1. Porto Torro, Ferreira do Alentejo

Bell Beakers from the Chalcolithic settlement
of Ferreira do Alentejo (Beja, Portugal), Porto
Torro archaeological site, as well as pre-
The function or quality of a pot is influenced by

the raw materials used. A coarse paste, fairly
34
Seminario SEM 08
Among the chemical elements studied REE

patterns, particularly the europium anomaly,
showed that weathered gabbros and diorites
were used as raw materials to produce Bell
Beakers and also pre-Beaker ceramics. The
geographic area of origin of this type of geological materials is shown in Fig. 5. The same
type of surficial soils is still used to produce
ceramics by the local potters.
Beaker ceramics, modern ceramics, and

potential raw materials from site surrounds
were studied in order to establish whether
the Bell Beakers found at the site were imported or produced locally (Fig. 4).
The geological context of the site comprises
gabbrodiorites, quartz, porphyries, Silurian and
Devonian schists, greywackes, PalaeogeneMiocene and Pliocene sediments. Nowadays
local potters prefer to use raw materials derived by weathering from gabbros and diorites,
the so called Barros de Beja.
Thus the results obtained for ceramics from

Porto Torro Chalcolithic site and for available
clay materials, give an important contribution
to the Bell Beakers circulation problematic, as
they clearly indicate that they were not introduced in the area as a result of some trade or
prestige good distribution network, but were
produced locally.
The materials studied included:

sherds from two different archaeological
contexts - the pre-Beaker and the Beaker
levels;
clay samples from available geological background in the area, including soils derived by
weathering from gabbros and diorites, and
from schists and greywackes, as well as
Palaeogene-Miocene and Pliocene sediments; and
samples of modern ceramics made by local
potters.
Fig. 5. Geological map of southern Portugal with the location of the

Porto Torro archaeological site and the area of the gabbro-diorite
complex (red dashs).
2.2. Monte do Tosco, Alentejo

Monte do Tosco is an enclosure Chalcolithic
site, reoccupied during the early Bronze Age,
where a late Bell Beaker context has been
excavated (Fig. 6). The sherds studied include Chalcolithic ceramics, Bronze Age ceramics from the Bell Beakers context, common
ware, and crucibles. Raw materials samples
were collected from regional/local clays (weathered schists, greywackes, diorites and gabbros and Tertiary sediments).
Fig. 4. Sherds from Porto Torro archaeological site, Ferreira do

Alentejo (photographs by Antnio Valera).
35

Prudncio, M.I.
duction for all ceramic typologies can be delineated, including Bell Beakers. Still a few
outliers are defined comprising the analysed
crucibles and three Bell Beakers (Fig. 7),
pointing to the use of different raw materials,
probably a different provenance.
2.3. Fraga da Pena, Beira Alta

The Fraga da Pena archaeological site is a
fortified settlement located in a huge granitic
tor, impressively conspicuous in the surrounding countr y, occupied at the transition
Chalcolithic - early Bronze Age (last quarter of
the third millennium BC) (Fig. 8).
Fig. 6. Monte do Tosco archeological site (Alentejo, Portugal (photographs by Antnio Valera).
Ceramics from Monte do Tosco were divided

in three chemical groups (Fig. 7):
Group one (1) embraces 80% of Chalcolithic
ceramics;
the second group (2) comprises all the
Bronze Bell Beakers (60%) and other
Bronze and Chalcolithic ceramics;
the third group (3) is mainly composed of
Bronze Age ceramics (80%)
Fig. 8. Fraga da Pena archeological site, central Portugal (photograph

by Antnio Valera).
The material culture indicates an occupation

where symbolic activities could overcome the
domestic ones (Valera, 2006).
Among the several typological groups identified, four were selected for an archaeometric study: Bell Beakers (Fig. 9) decorated
vessels with combed incisions; vessels with
morphological and decoration patterns of
Chalcolithic tradition; and Bronze Age new
morphologies.
Fig. 7. Plot of means for each cluster (K-means method) using chemical results of Monte do Tosco ceramics as variables.
Chalcolithic ceramics can be differentiated

from Bronze Age ceramics by a chemical composition more correlated with the basic rocks of
the region, namely clays derived by weathering
of quartzodiorites, diorites and gabbros. Bell
Beakers ceramics have a more homogeneous
composition than other Bronze Age ceramics.
Bell Beakers and other Bronze Age ceramics
present a similar chemical composition, with a
chemical signature also found in local clays weathered schists and sedimentary clays.
Clays
available
in
the
settlements
Fig. 9. Bell Beakers from Fraga da Pena archaeological site, central

Portugal (photographs by Antnio Valera).
Hence, at Monte do Tosco site, a local pro-
36
Seminario SEM 09
aspect of the orientation of the clays. Thus

the claytemper mixture materials used to
make the vessels were cer tainly not
ground and sieved.
surrounding area are residual materials of

granites, veins of quar tz, aplitedolerite,
and schists. Dolerites provide the most
clayey samples. The aplite pegmatite
veins also provide argillaceous materials,
ver y rich in alkali feldspars. Plagioclase
reaches the higher levels in granites. Iron
oxides and pyroxenes reach the higher
levels in dolerites. Micas occur in all
cases. A good dif ferentiating indicator
within these samples is the phyllosilicates, plagioclase, iron oxides and pyroxenes propor tion.
Compositional studies of all ceramic typologies from Fraga da Pena revealed that
Bell Beakers have in general a similar
composition. The main geochemical features enhance three main groups, which are
related with the regional geological materials:
Group 1 comprises mostly Bell Beakers;
Clays derived by weathering of granite and

dolerite can be distinguished by their Na and
K contents related to plagioclase and alkali
feldspar, and other elements with geochemical affinity to ferromagnesian minerals, such
as Cr, Co, Sc and Fe. Although it is possible
to clear differentiate these geological materials, significant variations of the REE contents may occur within the same type of clays
depending on the weathering degree of the
parent rock.
Group 2 is mainly composed of Chalcolithic

and Bronze Age typologies, combed inc
sions ceramics, and a few Bell Beakers;
Group 3 includes Bell Beakers and Chalcolithic
and Bronze Age typologies (Fig. 10).
Phyllosilicates, mainly mica, illite, chlorite
and smectite occur in Fraga da Pena ceramics. XRD allowed the identification of significant amounts of smectite and interstratifieds in some sherds. The results obtained point to low temperature firing processes, not higher than 500 C 600C (Dias
et al., 2005).
Macroscopic obser vation and petrographic

analysis showed significant amounts of
nonplastic grains, a high irregularity of the
grain size distribution, lumps of clay joined
to form the paste, giving a ver y irregular
texture, and a ver y nebulous and irregular
The chemical patterns of the Bell Beakers are
Fig. 10. Plot of means for each cluster (K-means method) using chemical results of Fraga da Pena ceramics as variables.
37

Prudncio, M.I.
similar to the dolerites samples, with significant amounts of elements associated to ferromagnesian minerals. The dissimilarities found
may be due to the differences among different dolerite veins and/or different stages of
weathering as revealed by the REE fractionation. The chemical composition of Chalcolithic
and some Bronze Age typologies points to the
use of more acid rocks, like local/regional granites, with higher contents of elements related with the presence of feldspars (Na, K, Rb,
Cs), higher amounts of REE, specially LREE,
Zr, Hf, Ta and Th, and a depletion in elements
of the first transition series.
dence to solve ceramics mechanisms of

circulation, including the Bell Beakers
issue, has been ver y useful. In the three
case studies (Por to Torro, Fraga da Pena
and Monte do Tosco archaeological sites),
local production was ascer tained for the
majority of the cases. Never theless some
exogenous ceramics were found.
Textural features obtained by petrography,

together with mineralogy and chemistry, indicate that weathered dolerites were used for
the production of fine pottery. Coarser pastes
appear to have been done using weathered
granites. In both cases non-plastic grains of
granite origin are found. For the production of
the Bell Beakers, specially the nail printed
ones, a careful production technology occurred, with the use of well selected materials
of dolerite origin.
In general, the results obtained point to

local productions including Bell Beakers.
However in some cases a careful selection
of the clays and/or a dif ferent preparation
of the raw materials to obtain a more fine
paste for the production of special wares
like nail printed were also done in the
Fraga da Pena archaeological site.
The mineralogical assemblage of pre-historic ceramics in general does not present

high temperature mineral phases, pointing
all of them to low firing temperatures below 500C.
In a few cases the circulation of the

Product was suggested. In the three
archaeological sites most of the outliers
found are Bell Beakers. The transpor t of
these fragile ceramic objects over great
distances, enhance the impor tance of
these typologies over a cer tain period.
This approach helps to conceptualize the
dif fusion models of ceramics.
In general non plastic grains occur in great

amounts added by the potter in the process
of assembling the paste to produce ceramics. The high irregularity of grain size distribution, the irregular texture, and the very
nebulous and irregular aspect of the orientation of the clays indicate that raw materials
were not ground or sieved and well mixed.
Thus, the results indicate that several

ceramic types including Bell Beakers were
made with local/regional resources and
only occasionally impor ted.
Bell Beakers, especially the nail printed

ones, present a thinner paste with well
selected nonplastic grains, indicating a
careful mixing and working of the clay
resource and temper grains, thus a different process of making the pot. Therefore
most of the Bell Beakers from Fraga da
Pena, especially the nail printed ones,
were produced using a careful local production technology.
Acnowledgements
The help of Jose Miguel Herrero by improving and editing the manuscript is gratefully acknowledged.
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40
Technology and Provenancing of

French faience
/ Marino Maggetti
Department of Geosciences, University of Fribourg, Fribourg, Switzerland.
Abstract
An overview is given of the recipe and the chane opratoire of French faiences, as revealed in
ancient textbooks and archives of the 18th and 19th century. The preparation of the calx, the glaze,
the glazing, the decoration with in-glaze and on-glaze colours, the kiln and the three firings (first,
second, third) are described and the chemical, mineralogical and technological aspects assessed.
Archaeometric analyses of French faiences are scarce. Scientific analyses of such crockery, mainly
from the workshops of Le Bois dpense/Les Islettes and Granges-le-Bourg, constrain the nature
of the clay, the firing temperatures, the glaze composition and the colour pigments. Successful attributions of faience objects are shown. However, such provenancing need much more robust and
wellknown chemical reference groups.
Resumen
Se presenta una vision general de la receta y la cadena operativa de la Fayenza francesa, tal
como se conceba en antiguos manuales y archivos de los siglos XVIII y XIX. Se describen los procesos de preparacin de cenizas, vidriado, la aplicacin del vidriado, la decoracin con colores en
el vidriado o post-vidriado as como los aspectos qumicos, mineralgicos y tecnolgicos involucrados en el proceso. Hay poca informacin arqueomtrica de fayenza francesa. Los anlisis cientficos de vajillas vidriadas, principalmente de los talleres de Le Bois dpense/Les Islettes y Grangesle-Bourg, ponen de manifiesto la naturaleza de la arcilla, temperaturas de coccin y composicin
de los vidriados y pigmentos. Se muestran los resultados de asignar piezas de fayenza a los talleres de procedencia. Sin embargo, los estudios de proveniencia necesitan consolidarse an ms y
disponer de grupos de referencia qumicos conocidos.
Key-words: Tin glazed earthenware, French faience, calcareous clay, glaze, biscuit, firing temperatures,
archaeometry.
1. Introduction
Ancient and modern ceramic products can be studied from different perspectives. To the petrologist,
they are artificial rocks subjected to relatively high temperatures and recrystallized to become thermometamorphic products, analogue to those naturally formed through metamorphism (Maggetti
2001). In contrast to natural rock forming processes, pressure is insignificant in the genesis of such
objects, because the kiln can be considered as a technical system. In such open systems, neither
pore solutions, present before firing, nor gaseous reaction products, which may have been produced
during the high temperature process, have an influence on the transformation, because they can
leave the system at any time. Similar to natural rocks, ceramic objects consist of an assemblage of
crystalline and amorphous phases, which can be analysed with the same petrographic, mineralogical and chemical methods such as micaschists, which are formed from clay during metamorphism.
Faience is, in the French nomenclature, an earthenware body coated with a white glaze opacified
by tin oxide (SnO2) crystals (Fig. 1). These cassiterites are present as small particles up to 10 m
across or as bigger clusters. The finely distributed tiny crystals refract and reflect light almost
without absorption losses (Vendrell et al. 2000). Hence the ceramic object takes on a white and
opaque appearance even though it is coloured in the bulk. Tin-glazed earthenware pottery resembles therefore, from the outside, porcelain.
41
Technology and Provenancing of French faience

Maggetti, M.
2. Discovery and spreading of tin-glaze

technique
This paper deals with the technique and the

origin of 17th to 19th century French faience
tableware. Faience tiles and older faiences of
this country are not addressed.
2.1. Mesopotamia and China

The origin of the tin glaze technique can be
traced to what today is Iraq (Caiger-Smith
1973, Soustiel 1985). An important production centre was Baghdad, the palace city
erected by the second Abbasid Caliph Abu
Jafar al-Mansur in 762 AD in the location
where the Silk Road crosses the Tigris River
(Fig. 2).
It is still a matter of debate if the tin-glaze
technique was invented as reaction of Islamic
potters from Mesopotamia and Persia to the
Chinese competition, trying to emulate the
gleaming white surface and the hard, compact body of Chinese porcelain (Watson
1987) or if this technology appeared in Basra
as a genuine local invention already during
700-750 AD, several decades prior to the
known import date of Chinese ware (Mason &
Tite 1997, Mason 2004).
At the end of the 9th century, in Baghdad,
Basra, Samarra and other places, the tin-glazed pottery technique was well established.
This novel glaze technique resulted in two
advantages. On the one hand, the off-white
colour of the ceramic body was masked by the
opaque glaze and on the other hand, the white
glaze surface provided an ideal canvas for painted decorations. Consequently, the Islamic
Fig. 1. Backscattered electron images of end 18th century faiences

from the workshop Le Bois dpense/Les Islettes. (a) Sample BEI 6a
showing on top of the tin oxide opacified glaze a stroke of blue in-glaze
painting; (b) Sample BEI 54 with a yellow in-glaze painting on top of the
glaze. Photo M. Maggetti.
Fig. 2. Major centres of Islamic potter y

manufacture in the Middle East.
42
Seminario SEM 09
craftspeople discovered the inglaze blue,

brown, green and yellow colours, which were
later adopted by the Chinese potters.
A further innovation of the Islamic crafts people was the lustre decoration, possibly inspired by the religious ban on using gold for profane purposes. Hence only gold-like lustre
vessels conformed to the religious commandments and statutory laws. In terms of technology, lustre ware was a transfer from glass to
ceramic technology, invented in Basra and
Fustat during the 8th and 9th centuries AD
(Caiger Smith 1985).
At the end of the 12th centur y AD the first
ceramic objects appeared in Iran, showing
overglaze decoration, a technique called
painting with seven colours (blue, green,
brown, violet, red, black and white) (Weiss
1970, Soustiel 1985) and known as minai
or ladjvardina wares. Analyses by Mason &
Tite (1997) and Mason (2004) throw much
light on the development of Mesopotamian
tin glazes. The oldest (c. 700-750 AD) tinopacified glazes from Basra were an improvement of the traditional local opaque glazes that owed their opacity to gas bubbles
and fine cr ystallites of quar tz, feldspar,
wollastonite and diopside. Cassiterites are
concentrated in a slip-like layer at the interface ceramic body/glaze. PbO is ver y low
(around 1 wt.%, Fig. 3). Slightly younger
(750-800 AD) glazes contain like earlier
glazes gas bubbles, silicates and cassiterites as opacifying agents. The latter, however, are spread throughout the entire glaze
and SnO2 contents are slightly elevated (34 wt.%, Fig. 3). The glassy coatings are
alkali-lime glazes with 1-2 wt.% PbO. Tin
oxide concentrations of later glazes (800975 AD) reach 4-8 wt.%, sufficiently high to
eschew additional opacifying agents. Owing
to the elevated PbO content (3-11 wt.%)
these glazes can be classified as alkalilead-lime glazes. Glazes from Baghdad
dated c. 800-900 AD show substantially
increased PbO (31-41 wt.%) and SnO2 (6-8
wt.%) contents. Tin-opacified lead-alkali
glazes with 25-35 wt.% PbO from Egyptian
Fustat of 975-1025 AD show even higher
SnO2 contents (9-16 wt.%) compared to the
Basra or Baghdad glazes.
Fig. 3. SnO2 and PbO concentrations in Mesopotamian tin glazes

(Mason & Tite 1997, Mason 2004).
The Mesopotamian Islamic tin-glazed wares,

painted or not, with or without lustre, were all
produced from calcareous (16-22 wt.% CaO)
clays very similar in composition (50-55 wt.%
SiO2, 10-12 wt.% Al2O3, 5-7 wt.% MgO, 5-6
wt.% FeO and 1-2 wt.% Na2O; Mason, 2004).
Firing temperatures of blue-painted wares
from Basra were estimated at 850-1050C
(Tite 1988). Since Baghdad paste contains in
addition some glass fragments it is conceivable that this ceramic production centre used
a technology different from Basra.
Mesopotamian lustres were studied by
Pradell et al. (2008 a, b) and Colomban &
Truon (2004).
2.2. Spread of tin-glazed pottery

Very early the Arabian westward expansion
reached via North Africa Spain that was conquered between 711 and 719. In the wake of
the new rulers Islamic potters settled in
Spain and introduced this technology.
However, it is unknown when the first
Spanish tin-glazed ceramic objects were produced. From the 12th to the 15th centuries tin
glazing flourished in pottery centres such as
Talavera-Puente, Paterna-Manises and
43

Maggetti, M.
2002, Dufournier et al. 2004, Marco de

Lucas et al. 2006, Rosen et al. 2007,
Maggetti et al. 2009a, b).
Sevilla. In the 13th century the HispanoMoresque lustre decoration technique was
developed to high perfection, in particular in
manufactories of Malaga and Manises.
These potters combined the cobalt-blue painted decoration with the metallic lustre coating
and thus revived a technique that had been
lost in 1224 by the destruction of Rajj in
Persia by the advancing Mongols.
4. Technology of French faience

4.1. First French faience productions
The first French tin-glazed earthenware was
produced in Marseille at the beginnings of
the 13th century (Marchesi et al. 1997,
Rosen 2000a). Local workshops created
there glaze-less objects or objects with a
transparent lead-glaze, both in a Middle-Age
tradition, as well as tin-glazed pieces in a
new, Islamic technique. This technology spread rapidly throughout France. But during the
first 300 years (end of the 13th until the early
16th century), only tin-glazed tiles were produced for a wealthy clientele (Rosen 2000a).
Italian potters moved ca. 1550 to France and
opened before the end of the 16th century tin
glaze pottery workshops in Lyon, Montpellier,
Nevers and Cosne-sur-Loire.
Many lustre-decorated ceramic plates and

cups display the coat-of-arms of French and
Italian noble families thus showing how highly
esteemed this tableware was. These objects
did not serve their foreign clients as dinnerware for daily use anymore but were considered
prestigious objects of art fit to grace their
ostentatious sideboards. From Spain this type
of ceramic ware was introduced to France
where in mid-13th century in Marseille tin glazed pottery was made, and eventually to Italy.
From there the knowledge of production of tinglazed ceramic crossed the Alps and extended
into the northern parts of Europe. In its wake
a continuous stream of new manufactures was
established in France, Germany, The
Netherlands, England, Switzerland etc.
Eventually the faience technology reached the
New World (Olin et al. 1978, Maggetti et al.
1984, Olin and Blackman 1989, Jamieson and
Hancock 2004). Tin glazed ware is called
Hispano-Moresque ware in Spain, maiolica in
Italy, faience in France and delftware in
Northern Europe.
3. Archaeometric studies of French

faiences
Such studies are very scarce. Some show no
chemical analyses at all (Dmians
dArchimbaud & Picon 1972, Picon &
Dmians dArchimbaud 1978, Vallauri et al.
1978, Picon 1993, Rosen 1997a,b), other
only mean values (Vallauri & Leenhardt 1997,
Picon 2000, Rosen 2001, 2007) and few the
complete list of analyses (Carette et Deroeux
1985, Dufournier & Deroeux 1986, 1987,
Dufournier 1989, Schmitt 1990, Pellet 1993,
Rosen 2000b, Bernier 2003, Meunier &
Bouquillon 2004, Maggetti et al. 2009a, b,
Rosen 2009, Rosen et al. 2009). Glaze and
pigment analyses are discussed in these and
other papers (Bouquillon 2000, Oger et al.
Fig. 4. Map of 17th century French faience manufactures. Redrawn

from Fa-Hall & Lahaussois (2003) and completed.
These establishments were the starting point

for the extraordinary expansion and success
of French faience in the 17th and 18th centuries (Figs. 4, 5). Around the mid-16th century
in Faenza the biscuits were coated with a particularly thick pure white and matt glaze.
These bianchi di Faenza were so popular and
commanding throughout Europe that to this
day in France the name of the city became
the synonym for French tin-glazed pottery,
44
Seminario SEM 09
manufactured from clays in several production steps (Fig. 6). The composition of ideal
faience clays is 58 wt.% SiO2, 30 wt% Al2O3,
5 wt.% Fe2O3 and 7 wt.% CaCO3 (BastenaireDaudenart 1828). In order to obtain the calcareous body typical of tin-glazed potteries
(Caiger-Smith 1973, Tite et al. 2008, Tite
2009), either clays which already contain the
ideal amount of carbonates (calcite and dolomite), or artifical mixtures of several kinds of
clay are used. The French faience makers of
the 18th and 19th centuries preferred mixtures by far, ranging from two as in the case of
Le Bois dpense (Linard 1877), Nevers
(Bosc dAntic 1780) and Rouen (de la
Hubaudire & Soude-Lacombre 2007) to
three (Aprey, Froidos, Lavoye, Paris,
Rarecourt, Salvange, Thionville, Tours and
Waly, Bosc dAntic 1780, Brongniart 1844,
Linard 1877) or even four clays (Paris,
Bastenaire-Daudenart 1828). French faiences with non or low calcareous paste are rare
and show technical drawbacks (Munier 1957,
Caiger-Smith 1973, Picon et al. 1995,
Thornton 1997).
Fig. 5. Map of 18th century French faience manufactures. Redrawn

from Rosen (2001)
faence. In the time span 1550-1600, Lyons

tin glaze potters were named white earth
potters or vase makers in the style of
Venice, and those from Nevers white crockery makers in the style of Venice (Rosen
2000a). The term faience appeared for the
first time in 1604 in Nevers (France) where
the ceramist Jean-Baptiste Conrade was labelled sculpteur en terre de fayence (sculptor
of faience earth) (Rosen 2000a).
Archaeometric analyses confirmed the blending

of two clays, a low and a high calcareous one,
for Meillonnas (Rosen 2000b) and Nevers
(Rosen 2009), and the use of one clay in
Granges-le-Bourg (Maggetti et al. 2009c).
Chemical analyses proved the calcareous nature of faiences from Arth (25-32 wt.% CaO,
Pellet 1993, Rosen 2001), Dijon (14-26 wt.%,
Rosen 2001), Le Bois dpense (17 24 wt.%,
Maggetti et al. 2009a), Montpellier (17-28 wt.%,
Rosen et al. 2009), Moustiers (15-32 wt.%,
Rosen et al. 2009), Nevers (19-30 wt.%, Rosen
et al. 2009, Rosen 2009), La Rochelle (11-21
wt.%, Rosen et al. 2009), Villers-le-Pot (21-28
wt.%, Rosen 2001). CaO mean values of faiences from Ancy-le-Franc (20 wt.%, Rosen 2001),
Chevannes (17 wt.%, Rosen 2001), Meillonnas
(17 wt.%, Rosen 2000b) and Vausse (23 wt.%,
Rosen 2001) fit well in this scheme. Faiences
from Granges-le-Bourg are magnesium-rich
(MgO 5-10 wt.%) and were made from dolomitic
marls (Maggetti et al. 2009c, d). Five faiences
from Varages (South of France) have more than
11 wt.% MgO (Schmitt 1990).
4.2. Technical treatises of the 18th and

19th centuries
The manufacturing techniques of this special
kind of pottery are well known thanks to contemporary publications (Diderot 1756, Bosc
dAntic 1780, Anonymous 1783, Boussemart
1786, Boyer 1827, Bastenaire-Daudenart
1828, Harl 1831, Brongniart, 1844), more
recent papers (Deck 1887, Munier 1957,
Montagnon 1987, Rosen 1995, 2009,
Peiffer 2000, Bastian 2002-2003, Maggetti
2007a) and the mid 18th century Caussy
manuscript (de la Hubaudire & Soude
Lacombe 2007).
4.3. Chane opratoire of French faience

4.3.1. Nature and treatment of the clays
There are five reasons why calcareous

clays were widely used (Tite 2009):
18th and 19th centuries French faience is
45

Maggetti, M.
Fig. 6. Chane opratoire of the four faience types (without lustred faience). (A) White faience. Below, photo of a plate from the faience manufacture Du passage de la Cour-Robert in Fribourg, Switzerland, ~1790-1810. Archaeological Survey of the Canton Fribourg, Switzerland, inv. FPLCRI No 1646. Photo G. Bourgarel. (Bourgarel, 2007); (B) Faience with in-glaze decoration. Below plate from the faience workshop of Le Bois dpense/Les Islettes, France, ~ 1800, diam. 22,5 cm, inv. 943.1.32. Collection and photo of the Museum Bar-le-Duc (Rosen, 2007a); (C) Faience
with on-glaze decoration. Below plate with a cock, after 1830 (?), from a Lorraine manufacture, most probably Lunville or Saint-Clment. (pers.
coll.). Photo M. Maggetti; (D) Faience with in- and on-glaze decoration. Below plate with stamp Paul Hannong from Strasbourg, ~ 1735-1748, diameter 24,8 cm. Collection and photo J. Bastian.
(5) Microstructures remain essentially unchanged over the 850-1050C firing range.
(1) They are very common;

(2) High CaO-bodies shrink considerably during
cooling, putting the glaze under compression;
Calcareous bodies show significantly less

firing shrinkage and have a greater rigidity
and compressive strength as non calcareous
wares.
(3) CaO acts like a bleach during firing, giving

pale buff colours;
The raw materials extracted from river sediments or a quarry must undergo several operations to remove the rougher elements and
to make them homogeneous. Finely ground
(4) The thermal expansion coefficient of calcareous bodies matches those of lead-alkali
glazes and
46
Seminario SEM 09
any air it could still contain.
temper can also be added, or two or more

clays mixed. The clay was first ground, then
placed in suspension in water in vats or
barrels and well stirred to separate the grains
(washing). The suspension was filtered, poured into a large earthen pit and once again
well stirred. The suspension was then allowed to decant, the unwanted coarse particles
settled to the bottom to form a coarse inferior
layer. Specialized workers removed the finer
superior layers and poured them into another
vat. This decanting process was repeated
several times.
Fig. 8. Schematic view of the inside of a manufacture with a worker

"walking" the clay (b), mounds of kneaded clay (c), a worker shaping
an object (d) and long shelves to dry the moulds and the objects either
thrown or moulded. Diderot (1756, plate II).
Fig. 7. Clay washing pools. Faience manufacture of Les Auges, middle

of the 19th century (Langres, France). Excavations J. J. Thvenard.
Photo M. Maggetti
The excavations made by Jean-Jacques

Thvenard in the faience manufacture of Les
Auges in Langres, revealed the presence of a
whole series of clay pools (Fig. 7). The paste
was then stocked in a cellar and allowed to
rot for several weeks, even months. Before
the material taken from these rotting-cellars
could be used, it had to have the exact
amount of water necessary, obtained either
through drying to remove a surplus, or by
adding liquid.
Fig. 9. Wheel throwing. The worker in front is shaping and his colleague
behind is turning, i.e. finishing the object (Brongniart, 1844, plate XLV).
4.3.2. Shaping, dr ying and first firing

Once prepared, the mass of plastic clay could
be shaped according to two main techniques,
throwing and moulding. The first makes it
possible to obtain symmetrical objects such
as platters, jugs, etc. (Fig. 9). The second is
used to shape non-symmetrical objects such
as handles, spouts, decorations but also for
symmetrical shapes (Fig. 10).
Homogenization was the following step, during

a process called marching (Fig. 8). The paste
was spread on a hard surface, in the shape of
a circle a few centimeters thick. A specialized
worker, trained in this delicate task, tread on
the clay, walked it, going from the center out,
and then the reverse. The effect of this operation was not only to homogenize the clay, but
made it also possible for the worker to detect
numerous undesirable tiny par ticles and
foreign bodies. Then the paste, shaped into
balls of different sizes was forcibly beaten with
wooden bats or iron bars in order to extract
In order that they may dr y, the objects

thrown on the wheel or moulded were placed on long wooden planks, placed on shelving in a specific, well-aired room, or even
in the shaping workshop (Fig. 8) .
Consequently, a lot of space was necessar y
for this impor tant and delicate phase, as in
the case of the dr ying of the moulds, whose
aim it was to remove as much water as possible from the objects to prevent their shattering during firing.
47

Maggetti, M.
Fig. 11. Biscuits from the faience manufacture Le Bois dpense/Les

Islettes, France (pers. coll.). Photo M. Maggetti.
Fig. 10. Different gypsum moulds from the Bois d'pense/Les Islettes
manufacture with a few biscuits from these moulds (pers. coll.). Early
19th century. Photo M. Maggetti.
those of the faiences from the manufacture

of Granges-le-Bourg are shown in Fig. 12.
During the drying process, water evaporation

progresses outward in and its consequence
is a loss in volume, called drying shrinkage.
The pieces are thus subjected to tensions
and it was necessary to ensure that this evaporation took place very slowly and uniformly,
without any risk of cracking or distortion.
The X-ray diffraction patterns of biscuits from

the manufactures of Le Bois dpense/Les
Islettes (Maggetti 2007b) and Granges-leBourg (Maggetti et al., 2009c) were compared
with published results (and Fig. 12), giving estimated maximum firing temperatures of 950C
for the first (or biscuit) firing. This holds most
probably for all other French manufactures, as
a highly fired biscuit wouldnt be enough
porous to adsorb sufficient tin glaze suspension (Bastenaire-Daudenart 1828, p. 395).
The usual procedure, in the production line of

fine ceramics, is to examine the objects to
detect any cracking before placing them in
the kiln, because even a very fine crack can
turn into breakage of the raw (green) object
during firing (Casadio 1998). These dry and
cracked pieces are not rejected, but recycled
in the shaping phase, as the raw mass can
be crushed and rehumidified. This type of discard leaves no trace and is not quantifiable.
After forming and drying, the green leatherhard ceramic bodies were fired in a kiln giving
a porous, coloured biscuit (Fig. 11). During
firing water and other volatile compounds will
evaporate.
4.3.3. Preparing the tin oxide bearing

glaze
This lead glaze, opacified with tin oxide, begins
to melt at low temperatures around 900C and
should show a thermal dilatation coefficient
similar to that of the biscuitted ware to avoid
crazing or scaling. The raw material is always
quartz sand (SiO2), as pure as possible, with a
significantly low iron content, to avoid the development of a yellowish color during the oxidative second firing. In order to lower the melting
point of quartz from 1713C to approximately
900-950C, it is necessary to add fluxes such
as lead oxide and alkalis (potassium, sodium).
French faience makers in the 18th and 19th
centuries used sodium rich fluxes, mostly sea
salt (NaCl) and less soda (Na2CO3), as indicated in contemporaneous glaze recipes, which
vary greatly from one manufacture to the next.
Mineralogical changes and textural evolutions

of calcareous illitic clays during oxidative
firing were studied by many authors (Peters &
Jenni 1973, Maniatis & Tite 1975, Tite &
Maniatis 1975, Heimann 1982, Maggetti
1982, Shoval 1988, Echallier & Mery 1992,
Diminuoco et al. 1998, Cultrone et al. 2001,
Trindade et al. 2009 and literature therein). Xray diffraction analysis of experimentally fired
samples of a given clay is a popular method
to estimate ancient firing temperatures. Such
heat related phase changes of a dolomitic
clay with a chemical composition matching
The tin glaze, in its final stage, is a whitish powder obtained through a series of complex ope-
48
Seminario SEM 09
Fig. 12. Mineral stability in experimental firing of a dolomitic marl (sample GLB 1) from the manufacture Granges-le-Bourg. Portlandite is a postfiring hydrate of lime CaO.
rations. This begins with the preparation of a

calx or calcine which consists in merging and
oxidizing tin with lead in proportions going
roughly from 1/3 tin to 2/3 lead up to 1/5 tin
to 4/ 5 lead (in weight), which means 50 to 16
kg of tin for 100 kg of lead. To cut down on tin,
a costly metal, it was even possible to go down
to 10 kg of tin for 100 kg of lead, by adding
quartz to the frit (see below). The quantity of tin
bears a direct influence on the quality of the
vitreous glaze, which becomes whiter and shinier as the amount of tin increases. Both
metals were heated together in a small oven of
a specific type. Tin melts at 232C, lead at
327C. When both metals are melted, the heating process is continued, the oven door is opened allowing air to enter. The liquid becomes
oxidized, producing yellowish ash, pushed to
the back of the kiln by a worker with an appropriate tool. The oxidation process continues as
soon as the surface of the metallic liquid
comes once more in contact with the oxygen in
the air and the process of ash raking is continued until there is no more liquid.
Alkaline fluxes are highly soluble in the

aqueous suspension of the tin glaze. They therefore have to be stabilized, like the lead oxides, harmful to the workers' health. This is the
second stage consisting in preparing a vitreous
mass called frit. The lead stannate ashes, that
is the calcine, are removed from the oven,
mixed with very pure sand and flux. The proportions vary greatly according to the place where
the production occurs and even inside the
same factory. As an example, a recipe of
Bastenaire-Daudenart (1828, p. 330) shows
100 parts calcine (Sn:Pb = 30:100 parts) +
100 parts Nevers sand (SiO2) + 12 parts salt
(NaCl) + 6 parts minium (Pb3O4) + 5 parts
Alicante soda (Na2CO3), or recalculated by
Brongniart (1844, vol. II, p. 25) 44 calcine + 44
sand + 8 salt + 2 minium + 2 soda (Total
100%). Bosc dAntic (1780) gives three recipes
without any supplementary flux, estimating that
the calcines PbO acts as flux. Some recipes
mention the addition of a colouring metallic
oxide to lightly tint the glaze, such as cobalt for
example or copper.
X-ray diffraction analyses of a calcine from the

manufacture of Arth detected three phases:
massicot (PbO, 64.55%), lead stannate
(Pb2SnO4, 31.46%) and cerussite (PbCO3,
3.52%). The chemical composition is 91.01
wt.% PbO, 7,94 wt.% SnO2 and 0.58 wt.% CO2
(Total 99.53 wt.%, Pellet 1993). Lead stannate
is a well-known yellow pigment in artist painting
(Maggetti et al. 2009b).
The mixture calcine + sand + fluxes was finely

ground and then placed on a sand layer in the
lower part, that is on the hearth of the faience
kiln. The exception is the workshop of
Clermont-en-Argonne where the mixture was
fired in ceramic containers at the hearth of the
kiln (Linard 1877, p. 169). It melted almost
completely thanks to the high temperatures in
this area. These were estimated 60 or 70
49

Maggetti, M.
(Parmelee 1948). "Often, potters would add to

the glaze some organic product such as flourbased glue, gum or honey to make its suspension in water easier, since the high density of
these coatings drove them speedily to the bottom. In other cases, clay is added to the suspension; it will act in the forming of the glaze
during the firing. All these additions give, moreover, greater cohesion to the film deposited on
the surface of the ceramic. [] When a transparent or opaque glaze has to be tinted throughout, the coloring agent, carefully crushed, can
be added to the aqueous suspension, but it
can also be mixed to the lead and tin oxides in
the frit." (Picon et al. 1995, p. 49).
degrees of the Wedgwood pyrometer

(Brongniart (1844, II, p. 26), corresponding to
ca. 1100C. After cooling, the frit was seen as
a whitish vitrous product, where the grains of
the sand bed stuck to its base can still be seen
(Fig. 13). Scanning electron microscopy revealed the inhomogeneous granulometry and distribution of the cassiterite particles. X-ray fluorescence analyses of three representative samples from Granges-le-Bourg show rather constant SnO2 concentrations (9-12 wt.%), and
wider variations in SiO2 (38-51 wt.%) and PbO
(26-40 wt.%). A sample from the manufacture
of Pr dAuge has 10 wt.% SnO2 (Dufournier et
al. 2004). Such concentrations match those of
the faience tin glazes. The frit was then crushed, extracted from the place where it was
fired, kneaded by hand to separate it from
impurities and very finely ground in mills to
obtain powdered opaque and white tin glaze.
The tin glaze suspension can theoretically be

added to the leather-hard, unfired object, as is
the case for other glazes, but French treatises
only mentions the application of the glaze onto
biscuitted ware. Powdered tin-lead glaze, placed directly onto a dry and unfired clayey objet,
tends to shrink when fired. To avoid this, the
glaze must be applied in a thick, costly layer.
The advantage of a biscuit is that it does not
react when the aqueous suspension is placed
on its surface, and that the dissociation of the
carbonates already took place during the first
firing. A well fired, calcareous biscuit will theoretically no longer give off carbon dioxide during
the second firing. On the other hand, an unfired
calcareous paste will give off a lot of CO2,
which appears after firing in the shape of gas
bubbles in the vitrous tin glaze.
The bisquitted pieces were dipped either by
hand or with pincers (Fig. 14). To glaze the
interior of an object, the acqueous glaze
slurry was poured inside and the surplus poured out after a certain time. Another technique consisted in using brushes or cloths dipped in the suspension. Thanks to the high
degree of porosity of the biscuits, the water
was rapidly absorbed and a layer of powdered
glazed formed on the surface of the ware.
Fig. 13. A piece of tin-glaze frit showing a smooth vitrous break (a) and
the rough base (b). To the latter, grains of quartz are stuck from the
sand bed on which the powdered mixture was deposited before the
firing. Sample GLB 80. Width 3 cm. Faience manufacture of Grangesle-Bourg (France), excavations D. Morin. Photo M. Maggetti
4.3.4. Glazing
The objects were removed and let dry (Fig.

15). The traces left by fingers or holes due to
the use of pincers then had to be smoothed
over with a brush. The objects were ready for
the second firing, if the aim was to produce
white dishes (Fig. 6A). Uniformly white tableware was in all French manufactures the gre-
The powdered raw glaze was then diluted in

water, in which clay or other substances could
be added to maintain the frit particles in suspension and to ensure adhesion between the
glaze powder and the body after drying
50
Seminario SEM 09
feldspars and a SiO2-polymorph, probably cristobalite acording to its shape (Fig. 1).
Cassiterite particles are not homogeneously
dispersed, but form small SnO2-clusters. The
glazes of Granges-le-Bourg have similar chemical compositions with SnO2 around 9.1 wt.%
(Maggetti et al. 2009d).
4.3.5. Decorating
Painters decorated the pieces freehand, basing
themselves on illustrations, often engravings,
or by using the technique of stencilling (Bastian
2002, p. 99). The use of stencils, generally
made of metal, became widespread only in the
19th century (Rosen 1995, p. 41). The drawing,
first made on paper and pierced through by a
needle, was rubbed with a stamp containing a
powder which disappeared during the firing,
such as wood charcoal, and made it possible,
by transfer, to obtain a preliminary outline
which would guide the painter's hand. As
Rosen (1995, p. 41-42) notes: "Only a few pieces received elaborate designs. Most of them
only bore elementary patterns executed rapidly
by workers who were not always qualified painters. In that case, they could place the object
on the girelle of the wheel, and traced with an
unmoving hand the outlines which they then
filled in with different patterns."
Fig. 14. Glazing and touching up. Two workers are dipping biscuit plates in the liquid containing the glaze powder. In the background, two
female workers are touching up the raw glazed objects. The one in
front is removing the glaze powder from the bottom of a plate with a
brush or a piece of felt, so that it will not adhere to the support during
firing, the other is removing with a blade the excess thickness of the
glaze or their drops. (Brongniart, 1844, Plate XLVI).
The printed design, a process started in

England towards the middle of the 18th century,
was not used very much for tin-glaze faience,
even though it appeared early on in France on
porcelain (ca. 1759, Praud & dAlbis 2003, p.
346) and white earthenware or terre de pipe
(Garric 2006, p. 16-17).
Fig. 15. Faience biscuits covered with raw white tin glaze, drying in the
sun. Grottaglie, Italy. Photo M. Maggetti.
atest part of the production.

SEM-EDS analyses of 23 tin-glazes from Le
Bois dpense revealed an overall content of
46 wt.% SiO2, 9 wt.% SnO2, 31 wt.% PbO, 4
wt.% K2O and 2 wt.% Na2O (Maggetti et al.
2009a). Chlorine (1 wt.%) indicates the addition of salt, a common practice in this manufacture. The relatively high alumina content indicates the addition of a clay phase to the aqueous
glaze suspension, which was totally dissolved
in the tin-glaze during the firing. However, it cannot be ruled out that some alumina present in
the glaze results from diffusion processes
occurring from the body into the glaze (Tite et
al. 1998, Molera et al. 2001).
4.3.6. Ceramic colours

French ceramic colours of the 17th and 18th
century were, with few exceptions, coloured
glass, finely crushed, in order to make it possible to draw lines, even very fine ones. Their
colour is due to:
(1) The addition of colouring metallic oxides
to a colourless glass melt;
(2) The incorporation of natural or synthetic
crystals in a colourless or coloured glass
melt;
The tin-opacified lead-alkali glaze shows very

few bubbles and relictic quartz grains, as well
as newly crystallized phases, such as potash
51

Maggetti, M.
Fig. 16. Test pieces from the faience manufacture Le Bois d'pense / Les Islettes manufacture (pers. coll.). Width of the clay balls 2-3 cm. Photo
M. Maggetti.
bility in a glass such as the Armenian bole or

synthetic refractory products prepared on the
spot or that could be purchased. They were
mixed in a crucible with a transparent or
coloured crushed glass, then placed in a kiln
and melted. After cooling, the procedure was
the same as for transparent colours.
3) A mixing of milled, coloured crystals with a

colourless or coloured glass powder.
Thus we can divide ceramic colours into two
large categories, transparent colours and
opaque colours. D'Albis (2003, p. 162) characterizes them as follows: "If a colouring
oxide is melted into a colourless substance
and has passed on its colour to it, the colour
is then transparent. It is said that the colour
is "in solution" (in the glass). If on the other
hand, the colouring oxide or the blend of
colouring oxides is merely mixed in its powder
state to the colourless substance and if the
latter, then called flux, only agglomerates the
colouring grains between themselves and on
the porcelain during the firing, without as a
rule becoming coloured itself, then the colour
is opaque. The colouring grains themselves
are responsible for this. It is then said that
the colour is "in suspension" (in the glass).
Brongniar t (1844, II, p. 505-688) devotes a

large par t of his treatise to the technique
and the preparation of ceramic pigments
and colouring agents, which shows how
impor tant he felt this technological aspect
was. In the 18th and at the beginning of the
19th centuries, each workshop normally
prepared its own colours and kept its secret
ver y closely. The archive sources and the
treatises published reveal countless recipes and numerous trials, whether successful or unsuccessful. These essays are
brought for th by archaeological excavations
as test pieces, that is to say small tumblers
or ceramic objects (Fig. 16).
One of the methods for preparing transparent

colours consisted in putting transparent
glass powder in a crucible, adding a low percentage of a colouring oxide, melting the
whole in a kiln, crushing the newly formed
glass, reducing to a powder in the colour mill,
washing it and filtering it. This process of fritting-crushing-washing-filtering was usually
repeated several times.
It is easy to understand the reticence there

was to reveal these recipes because the
colours, these transparent or opaque vitreous powders, the tin glaze and the biscuit, all
three submitted to the same second or third
firing temperatures, must have had thermal
dilation coefficients which were comparable
among themselves. Moreover, if the objects
were used for culinary purposes, there was
the need to find on-glaze colours with a che-
For opaque colours, one could either use

naturally refractory substances, with low solu-
52
Seminario SEM 09
Yellow (Normally Pb2Sb2O7) is a very ancient

opaque colouring agent used by the
Egyptians as early as 1600 BC (Clark et al.
1995). Its synthesis is a result of a dry mixture of powdered antimony and lead oxides,
obtained by oxidizing antimony and lead sulphides (Stibnite Sb2S3 and galena PbS), the
whole melted in a crucible at temperatures
around 900C (Shor tland 2002). These
yellow crystals, finely crushed, are then
mixed to powdered colourless, transparent
glass, or coloured glass, if the painter wanted
other shades and tones for the desired
colour. Black is often obtained through manganese and iron oxide crystals, either alone,
or mixed. Red, a delicate colour to obtain
because it is not very stable at high temperatures such as those of a second firing and
turns into drab brown, is therefore little used
in faience. What were used instead were calcined ferruginous sands such as Armenian
bole or, later on, Thiviers red (Rosen 1995,
Rosen et al. 2007). White is a colour containing more tin oxide as the tin glaze, used for
example in the technique called Bianco sopra
Bianco.
mical composition which would resist liquids

such as vinegar, tea or coffee and with a high
resistance to abrasion to avoid being scratched by metallic objects such as knives or
forks. All these requirements were not easy
to bring together and one understands that
each factory needed a lot of time, energy and
financial backing to put the finishing touches
to their recipes, using local and foreign
resources to prepare the paste, the tin glaze
and the colours, while at the same time keeping in mind their specific physicochemical
properties.
4.3.7. In-glaze painting

In this decoration technique (Bastian 2002,
p. 95 ff.), painters worked directly onto the
dry tin glaze powder of the biscuitted pieces,
which was very fragile (Fig. 17).
The powdered ceramic in-glaze colours were

mixed with water and a binder, for example
starch, in small bowls. During glaze firing the
pigment particles were coated by a thin sheath of molten glaze.
In-glaze colours of the manufacture Le Bois
dpense were studied by Maggetti et al.
(2009 a, b). Electron microscope examination showed that the blue drawings are inclusion-free glazes with wavy boundaries to the
underlying tin-glaze (Fig. 1a). They are leadalkali glazes with a small amount of dissolved
cobalt (0.2-0.8 wt.%). NaCl was used to make
the blue glass, as evidenced by the presence
of chlorine. Significant arsenic concentrations
classify these blue pigments (smalts) into
group 4 of Gratuze et al. (1997), deriving
from cobalt ores of the Saxonian Schneeberg
(Germany). Purple colours contain minor
amounts of cassiterite and relictic Mn-Fecrystals. Manganese and iron contents in
these transparent colours lie between 2.5
and 4.6 wt.% respectively.
Fig. 17. In-glaze painting on tiles at the manufacture Schreiber

Keramik AG, Matzingen, Switzerland. Photo M. Maggetti.
It took someone with a steady and well-trained hand, because it was almost impossible
to repair an erratic brushstroke. When corrections were required the faulty part had to be
carefully scraped off and the glaze including
the colour pigments reapplied.
Considering the high temperature and the
long time of the second (glaze) firing, in-glaze
colours become closely fixed to the tin glaze.
But very few colours resist at such high temperatures, the palette contains but few
colours: blue, green, brown to violet, yellow,
black, red and white. The first three are transparent and their hue is due to the "diluted"
presence of cobalt in the case of blue, copper
for green and manganese for brown to violet.
The black colour is an association of very tiny
53

Maggetti, M.
and rounded particles. Elemental mappings

show that the latter consist of distinct iron-, manganese- or iron + manganese-rich pigments.
an iron-rich glaze matrix for the latter.
The rare opaque red colour is a complex mixture of: (1) very rare cassiterites; (2) rare,
large corroded potash feldspars; (3) large (up
to 10 m crumbly pigments (fired yellow or
red ochre); and (4) small (approximately 1
m) rectangular or square particles (Pb feldspars?) (Molera et al. 1993, Fortina et al.
2005).
The kiln is an essential structure in a faience

workshop. At the time under study here,
wood-burning kilns were used, intermittent,
with a vertical draught and direct flame (horizontal semi-cylindrical kilns). The kilns in
French faience workshops in the 18th and
19th centuries were made of refractory bricks
(Rosen 1995, p. 47). In the Middle Ages,
kilns had only one laboratory in which green,
leather-hard objects for the first firing and raw
glazed biscuits for the second firing were placed simultaneously. The latter were stucked
in saggars. These kilns can still be found
today (Caiger-Smith 1973, Amigues 2002).
French kilns of the 18th and 19th centuries
could have two floors or laboratories, separated by a perforated platform to let hot air
through (Fig. 18).
4.3.8. The faience kiln
Early 19th century antimony-based opaque

ceramic colours are yellow, tawny and green
(Maggetti et al. 2009b). The first is generated
by lead antimonate cr ystals (Pb2Sb2O7),
which are incorporated into an uncoloured
glassmatrix (Fig. 1b). According to SEM-EDS
measurements, these pigments contain iron.
The tawny colour is the optical result of the
combined presence of similar yellow, ironbearing lead antimonate particles in a Ferich, brownish glass matrix. The green opaque colour is produced by the combination of
a blue cobalt glass and yellow Pb-Sn-Fe-antimonate crystals. Relictic cores of zoned pigments lighten the recipes, according to which
the pigments were produced. First, they were
synthesised by calcination, ground and then
mixed with a colourless, brown or blue glass
powder. The resulting powder mixture was
added to a liquid agent and used as high temperature ceramic colour.
Analytical studies of red decorations from
four production centers (Argonnes, Nevers,
Rouen and Thiviers) showed a complex situation (Marco de Lucas et al. 2006, Rosen et
al. 2007). Thiviers used a particular, locally
available reddish sandstone called Grs de
Thiviers or Thiviers Red. This rock is composed of !-quartz grains cemented by goethite
(!-FeOOH). During firing, the latter transforms
to red hematite (!-Fe2O3). Raman spectra of
different Nevers red hues revealed that the
18th century pigments were a mixture of lead
antimonate Pb2Sb2O7 with iron oxide and
that Thiviers Red was used for the mid 19th
centur y faiences. The manufactories of
Rouen and Le Bois dpense/Les Islettes
didnt employ Thiviers Red, but Armenian
bole for the former and lead animonate with
Fig. 18. Schematic aspect of a faience kiln with its fireplace, the sole
and the laboratory for second firing. In the latter two different methods
of placing the wares are shown, that is with saggars or rafters and the
biscuit laboratory upon it. Diderot (1756, plate IX).
The bigger was used for the second firing of

raw glazed pieces and was situated in the
lower part of the kiln. The smaller, named
"globe" or first firing room was for biscuit
firing. There, the green leather-hard object
was thoroughly dried and became ceramised,
that is, it was transformed into a hard object
the biscuit and its shape was thus consolidated. The unfired pieces were normally
simply piled up "in charge" in the top laboratory where the temperature was not so high,
54
Seminario SEM 09
as much as possible the objects to be fired

from the projection of particles. The saggars
were piled up in the kiln, isolated from gases
and flames by round tiles pierced with a hole
and having all cracks filled in with clay putty.
and fired at the same time as the raw glazed

biscuitted pieces placed in the lower laboratory. When these objects were placed in the
kiln it had to be in such a way as to guarantee they would not touch to avoid becoming
stuck together with the molten glaze. It was
also necessary that the pieces be kept away
from the flames and substances resulting
from the combustion, such as ashes and
smokes, or from projections, to avoid the
deterioration of glaze and decoration.
To this purpose, potters used very specific
refractory materials when placing their wares in
the kiln, by using two techniques: rafters, also
called en chapelle (Fig. 18, to the left of the
second firing laboratory) and saggars, also
called encastage (Fig. 18, to the right of the
second firing laboratory). The first consists in
placing the objects to be fired on rafters or on
slabs separated by pegs or reels (Fig. 19).
These scaffoldings were wedged with bits of
clay of different shapes, named accots.
Fig. 20. Saggars and triangular, nail-like saggar-pins or pegs from the
faience manufacture Le Bois d'pense/Les Islettes (pers. coll.).
Height of the saggars ca. 16 cm. Photo M. Maggetti.
These technical or kiln ceramics which came in

direct contact with the flames and the atmosphere of the kiln, that is the saggars, the rafters used to place the objects in the kiln and
the reels had to be resistant at high temperatures, go through as many firing cycles as possible, and bear the weight of the pile up.
Refractory mixtures with a high mechanical
resistance had to be made. Each manufacture
had its own recipe. Non-calcareous clays were
commonly used, to which were added a temper
in the form of coarse sand and crushed ceramics (grog).
There is only one archaeometric study of kiln furnitures from a French faience workshop.
Maggetti et al. (2009d) studied thirty-nine samples (firing plates, saggars, spacers, props and
accots/wads) from the manufacture of Grangesle-Bourg. The kiln furniture is chemically inhomogeneous. Firing plates and saggars belong to a
CaO- + MgO-poor group, well suited to support
high firing temperatures as well as several firing
cycles. They correspond to decarbonatised top
layers of local dolomitic Triassic marls, tempered
with local quartz sands. Contrasting, props, spacers and wads show markedly higher CaO and
MgO, and were made using local dolomitic
marls, which were probably not as well processed as the faience paste.
Fig. 19. Slabs, firing plates or shelves for placing wares in the kiln and
columnar props or reels from the faience manufacture Le Bois d'pense/Les Islettes (pers. coll.). Width of the slabs ca. 20 cm. Photo M.
Maggetti.
In the second technique, the pieces were placed, according to their shape, in box-like containers either round, or oval, or rectangular, called
saggars (Fig. 20) where they rested on triangular supports, the saggar-pins (they can also
have other shapes, named cockspurs or trivets). The latter had to be as sharp-edged as
possible so as to leave only a very small trace
when in contact with the fired object. The inside of the saggars was usually glazed to protect
The potters obviously employed two major
55

Maggetti, M.
painting, glazing), while the faience of lesser

quality were sold at lower prices or incorporated into building materials (Amigues 2002, p.
197). Even the very worst quality was not lost
because it was used to fill in ditches or to
level the ground. The end products of the
glost firing were white faience tableware (Fig.
6A) or in-glaze decorated pottery (Fig. 6B).
recipes, based on refractory and non-refractory clays. Ceramic objects with high fluxes
will melt around 1100C and are therefore
not very well suited to resist the firing temperatures of a faience kiln or to support many
firing cycles. The use of such clays for the
second group of kiln furniture is therefore
puzzling and not yet understood. Plate and
saggars are covered inside with a tin glaze.
For obvious financial reasons, the potters
used significantly less tin oxide (< 6 wt.%
SnO2), added much more crushed quartz and
applied the watery glaze suspension with a
much thinner stroke as for the faience. The
absence of any significant reaction zone at
the body/glaze interface indicates that the
glaze suspension was applied on already
fired (biscuit fired) plates and saggars.
Experimental firings in kilns with one firing

chamber, built and functioning according to
ancient techniques, have given reliable temperature-time curves (see Amigues 2002;
Wolf 2002). On the other hand, no experimental firing was carried out in a two-chamber
kiln. It can be guessed that the temperaturetime curve of the second firing is quite similar to that of a one-laboratory kiln, but precise experimental data for the temperatures of
the biscuit laboratory are lacking. "The firing
is in two parts, first the objects are fired as
biscuit at a temperature ranging from cherry
red to whitish red, and then with the glaze at
a slightly higher temperature." (Brongniart
1844, 1877 tome II, p. 20).
4.3.9. Second (glost or glaze) firing

Each ceramic firing is divided up into two phases, the firing phase proper which includes the
rise in temperature up to the maturing temperature of 950-1050C, and a second cooling
phase in which the kiln is no longer stoked
(Picon 2002). In the first, reducing atmospheres alternate with oxidizing ones while in the
case of faience, the second phase is throughout oxidizing because air is allowed to penetrate inside the kiln. A vivid description of such
a faience firing is given by Amigues (2002).
According to Bastenaire-Daudenart (1828, p.
390-391) a French kiln would continuously fire
for 25-27 hours, with a first slow fire stage (56 h), a second more sustained fire stage (5h)
and a long sustained fire stage at maximum
temperatures (15-16h).
Inferred second firing temperatures in the

kilns from Le Bois dpense/Les Islettes and
Granges-le-Bourg were, according to X-ray diffraction analyses, between 950 and 1050C
(Maggetti 2007b, Maggetti et al. 2009c).
These results are in good agreement with the
microstructure of the well sintered bodies
with voids due to the dissociation of carbonates (Fig. 21) and tiny calcsilicate phases
(diopside, gehlenite, plagioclase) crystallized
during firing (Fig. 22).
The firing, the crowning step in the faiencemaking process, is not an easy matter, but
full of risks, because the distribution of the
heat inside a kiln is often very uneven, as
much as several hundred degrees difference
depending on the specific spot in the kiln
(Flame "T up to 550C, Wolf 2002), yielding
misfired pieces, either under or over fired, or
because the piled up objects crumbled as a
result of a poor saggar recipe or through
excessive heat. Therefore, one must not be
surprised at the large quantity of waste found
during workshop excavations. Biscuit wasters
could be used as testing material (drawing,
Fig. 21. Backscattered electron images of the body of a faience from

Granges-le-Bourg. D = void, former dolomitic grain, F = K-feldspar, Q =
quartz. Photo M. Maggetti.
56
Seminario SEM 09
mental diffusion profiles, for instance for alumina and lead oxides (Molera et al. 2001).
These phenomena must be taken into
account when measuring the chemical composition of a glaze.
4.3.10. On-glaze painting

This technique was introduced into the
French faience community around 1740 by
Paul Hannong of Strasbourg (Blondel 2001,
p. 261). For the on-glaze painting, a binder
was added to the powdered colour such as,
for example, natural gum or turpentine and
turpentine oil (Bastian 1986, p.134, Bastian
2003, p. 106) so as to obtain a more or less
viscous mixture. It was possible to use on the
one hand powders with pure tints and on the
other hand blends, for example blue and
green, which gave different colours. During
the firing process, the organic substances
evaporated, the powder melted and bound
with the mollified tin glaze. The applying of
colours on the glost fired tin glazed objects,
in-glaze decorated (Fig. 6D) or not (Fig. 6C),
needed a third firing intended to fix the pattern, in a special reverberatory furnace, also
known as muffle furnace. Temperatures in
this furnace used to be lower (estimated 400
to 850C, Rada 1989, p. 83, Endres et al.
1991, p. 42, De Plinval de Guillebon 1995, p.
20, Peiffer 2000, p. 97) than those of the
second high temperature firing (inferred 9501050C) and allowed for a much larger colour
palette to be used.
Fig. 22. Closer view of a well fired faience body from Granges-le-Bourg.
The tiny crystals around the quartzes and in the glassy matrix are calcsilicates (diopside, gehlenite, plagioclase). Photo M. Maggetti.
It has often been observed that the firing triggers the building up of a reaction zone between body and glaze, called interface body-glaze
or body-glaze layer. A detailed discussion of
this phenomenon can be found in technical
handbooks (Munier 1957, Hamer & Hamer
2004). With progressing firing, glaze melt will
soak into the porous biscuit. The fluxes of the
glaze (and the body) will selectively attack
and dissolve refractory particles of the body,
especially clay minerals. This is the reason
for the Al-richness of the reaction zone. On
cooling, Pb-feldspar will therefore crystallize
in the body-glaze layer (Molera et al. 1999).
The thickness of this interface depends on
several factors (Molera et al. 2001, Ben
Amara 2002):
(1)
(2)
(3)
(4)
Mineralogical nature of the clay;

CaO-content of the body;
Na-content of the glaze;
Green, leather-hard body or biscuitted
body;
(5) Firing conditions (T max., soaking time,
cooling time).
In rare cases, for the same object, artists

used the mixed technique (Fig. 6D). To do
this, they applied in a first step, certain inglaze colours on the unfired tin glaze, and in
a second step, after the glost firing, the onglaze colours which were then fired in the
muffle furnace. If the thermal dilatation coefficients or the fixation temperatures of the onglaze colours were too far apart, it was possible to fire each colour individually, which
meant placing the object several times in the
muffle furnace. Obviously, these techniques
entailed a higher cost.
Modern industrial applications favour the

development of such an interface as it prevent to a certain degree crazing and shivering. In the glaze, wollastonite and diopside
crystals can be concentrated in a small layer
close to the interface body-glaze (Mason &
Tite 1997, Molera et al. 2001, Bobin et al.
2003, Fortina et al. 2005, Zucchiatti et al.
2006). Body-lead glaze reactions (up to 300400 m from the body/glaze contact into the
glaze) are documented by conspicuous ele-
In order to obtain special effects, the painter

can use the luster technique which requires a
fourth firing under reducing conditions. This
57

Maggetti, M.
technique was not used in France in the

period studied here.
5. Provenancing of French faiences: two

case studies
Attributions of ceramics to a pottery workshop must be based on so-called chemical
reference groups. Each reference group comprises a minimum of 20-30 chemical analyses of unequivocally local products (biscuits,
wasters) from a specific manufacture. Up to
date, there are only four reference groups of
French faience workshops which fulfil all
requisites, i. e. (1) enough chemical analyses; and (2) all analyses published. These
are Granges-le-Bourg (Maggetti et al. 2009c),
Montpellier (Rosen et al. 2009), Moustiers
(Rosen et al. 2009) and Nevers (Rosen
2009). Three new reference groups (Le Bois
dpense, Lunville and Saint-Clment) will
be published very soon.
5.1. 17th century faiences: Nevers or Le

Croisic?
Fig. 24. Result of the cluster analysis of the 17th century Nevers reference group (Rosen, 2009) and the Le Croisic faience piece of Fig.
21. Redrawn and simplified from Rosen et al. (2009).
France had only few faience manufactures in

the 17th century (Fig. 4). A characteristic product painted in the compendiario style (Fig.
23) is attributed by many specialists without
any real proofs to the Le Croisic workshop
(Vince 1982).
Fig. 25. Factor analysis of the 18th century Nevers reference group
(blue rectangles), genuine La Rochelle faiences (from the excavations
of the La Rochelle manufacture, red dots) and faiences attributed to
La Rochelle, found in the waste dumps of the Nevers manufactures
(green rectangles). Redrawn from Rosen et al. (2009).
Fig. 23. Faience plate attributed to the Le Croisic manufacture

(Vince 1982). Photo J. Rosen.
58
Seminario SEM 09
The authors situated this hypotetical workshop at the estuary of the river Loire in the
Atlantic. Using the reference group of 17th
century faiences from Nevers (Rosen 2009)
it could be shown that this sample of socalled typical Le Croisic faience from the
Muse du chteau des Ducs de Bretagne in
Nantes (French Brittany) match the chemical
composition of the Nevers faiences (Fig. 24,
Rosen et al. 2009). It was therefore made in
Nevers and shipped on the navigable Loire to
Nantes and the Atlantic. Faiences from
Nevers eventually reached Canada and were
found in excavations in Quebec.
et Haguenau (1721-1784). PhD disser tation,

University of Strasbourg, France.
Bastian, J. (2002-2003) Strasbourg. Faences et
porcelaines 1721-1784. 2 tomes, Editions
M.A.J.B., Strasbourg.
Ben Amara, A. (2002) Interaction glaure plombifreterre cuite: recherches sur le mode dapplication du
mlange glaurant. PhD dissertation, Universit
Michel de Montaigne Bordeaux 3, France. 259-284.
Bernier, M. (2003) Caractrisation typologique,
microscopique et chimique des faiences du XVIIIe
sicle du site Saint-Ignace de Loyola en Guyane
franaise. Cahiers darchologie du CELAT no. 14,
srie archomtrique no. 4, Universit Laval,
Canada.
5.2. 18th century faiences: Nevers or La

Rochelle?
A comparative factor analysis using a
Nevers 18 th centur y reference group
against a reference group from the manufacture of La Rochelle, a harbour on the
West coast of France, clearly distinguishes
both (Fig. 25) . A whole set of faience pieces with so-called La Rochelle decorations (Morin 1990, p. 104), found in the
waste dumps of Nevers manufactures,
definitely belong to the Nevers reference
group (Rosen 2007b, Rosen et al. 2009).
Blondel, N. (2001) Cramique vocabulaire technique, Centre des monuments nationaux, Monum,
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Bobin, O., Schvoerer, M., Ney, C., Rammah, M.,
Daoulatli, A., Pannequin, B. & Gayraud, R. P.
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l'art des Forges, la Minralogie, l'Electricit, & sur
la Mdecine. Tome Premier, Paris, 258-283.
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64
Archaeometallurgy:
the contribution of mineralogy
/ Gilberto Artioli
Dipartimento di Geoscienze and Centro CIRCe, Universit di Padova. Via Gradenigo 6, I-35131, Padova, Italy
e-mail: gilberto.artioli@unipd.it URL: http://www.geoscienze.unipd.it/personal/artioli-gilberto
Abstract
Modern mineralogy is a discipline that is intrinsically suited to face archaeometric problems, especially
in the field of archaeometallurgy, which requires contributions from areas as diverse as geochemistry,
petrology, materials science, metallurgy, archaeology, engineering, and many more. Arguably, it is show
that mineralogy may provide the necessary frame to put into use the information derived from different sources, and combine it into a unifying interpretation. According to the mainstream of the metal
production cycle, the most significant areas of investigation in archaeometallurgy are: (1) the characterization and identification of ore sources (the mining stage); (2) the reconstruction of the smelting
technologies for reduction of the metal (the smelting stage); (3) the interpretation of the metallurgical
manufacturing processes in the production of the artefacts (the metallurgical stage); (4) the reconstruction of the use and diffusion of the metal objects (the physical lifetime of the object) and the incorporation in the archaeological record and their preservation (the afterlife stage). Examples will be discussed of the contribution of mineralogy to all steps of the archaeometallurgical cycle.
Resumen
La mineraloga moderna es una disciplina intrnsecamente adecuada para abordar los problemas
arqueomtricos, especialmente en el campo de la arqueometalurgia, donde se requieren aportes de
reas tan diversas como la geoqumica, petrologa, ciencia de los materiales, arqueologa, ingeniera
y otras. Podramos decir que la mineraloga puede proporcionar los fundamentos necesarios para usar
la informacin obtenida de diferentes fuentes y combinarla para ofrecer una interpretacin unificada.
De acuerdo con la lnea central del ciclo de produccin de los metales, las reas ms destacadas en
la investigacin arqueometalrgica son: (1) la caracterizacin e identificacin de las materias primas
(la fase de minera); (2) La reconstruccin de las tecnologas de fusin con reduccin del metal (la
fase de fundicin); (3) la interpretacin de los procesos de manufactura metalrgica en la fabricacin
de artefactos (la fase metalrgica); (4) la reconstruccin del uso y difusin de los objetos metlicos
(el tiempo de vida fsico del objeto) y su incorporacin al registro arqueolgico y su conservacin (la
fase postvida). Se discuten aqu distintos ejemplos de la contribucin de la mineraloga a todas las
fases del ciclo arqueometalrgico.
Key-words: Mineralogy, Metals, Archaeometallurgy, Archaeometry, Ore Minerals, Metallography, Texture,
Provenancing, Geochemical Tracers.
1. Introduction
For a long time mineralogy as a discipline has been confined to the application of optical mineralogy and X-ray diffraction to the characterization of natural minerals, mainly within academic curricula in the Earth Sciences. In the last decades however modern mineralogy has contributed to
many technical developments in collaborations with physics and chemistry, and now it is a mature discipline that is naturally suited to serve as a bridge and interface between the traditional
Earth Science areas (petrology, geochemistry, structural geology, sedimentology, etc.) and the
more materials science-oriented areas (physics, chemistry, engineering, metallurgy, etc.).
It is argued that mineralogy today may contribute deeply to cultural heritage studies in terms
65
Archaeometallurgy: the contribution of mineralogy

Gilberto Artioli
of thorough knowledge of materials and optimization of investigation techniques (Artioli

2010a, Artioli and Angelini 2011). Being a
truly interdisciplinary science, mineralogy therefore may well form a strong foundation for
scientists working with cultural heritage materials, especially in the area of archeometallurgy.
Copper Age (i.e. Chalcolithic, Eneolithic),

Bronze Age, and Iron Age. To these we may
well add the Steel Age, dominating technology and production after the industrial revolution. We are now in a period of extensive
recycling and use of advanced alloy composites (Ashby 1987 & 2001).
Archaeometallurgy deals with all aspects of
metal production, distribution and usage in
the history of mankind (Fig. 3, Rehren and
Pernicka 2008). To date the vast majority of
archaeometallurgical investigations deal with
the early part of the use of metals (i.e. up to
the 2nd millennium BC), which include the
technological use of a limited numbers of
metallic elements (Cu, Pb, Au, Ag, Sn, Fe)
and their alloys: mostly copper-based binary
and ternary alloys (bronzes and brass: Cu-Sb,
Cu-As, Cu-Sn, Cu-Zn, Cu-Sn-Pb, Cu-Sn-Zn), silver-based alloys (Ag-Cu, Ag-Au), and pewter
(Sn-Pb) (Table 3.14 in Artioli 2010 summarizes the approximate time and place of introduction of the different metals and alloys in
the past).
As a matter of fact mineralogy naturally deals

with complex mineral systems most often composed of a large number of chemical elements
and several crystal-chemical phases, it has
solid roots on crystallography and the atomic
structure of matter, and it is technically and
conceptually equipped to face the methodological and experimental challenges involved in the
technical analysis of complex materials, and in
the interpretation of the processes acting upon
them (Fig. 1). Therefore mineralogy may well be
the discipline possessing an adequate balance
of the interdisciplinary knowledge required to
face archeometallurgical problems (Artioli
2010b: pp 305-348).
2. Archaeometallurgy
However, the archaeometallurgical aspects

concerning the introduction of Fe and its
alloys (steel: Fe-C, Fe-C-P, etc.) and the subsequent use of all other known metals are
equally fascinating. The recent paper by
Bourgarit and Plateau (2007) dealing with
Pure and alloyed metals played a major role

in the technological evolution of mankind (Fig.
2). It is indeed not surprising that postNeolithic archeological periods are mostly
defined on the basis of the metal technology:
Fig. 1. The schematic diagram of some of the disciplines and knowhow forming the backbone of modern mineralogy (modified from Artioli and
Angelini 2011.
66
Seminario SEM 09
analysis.
the early use of Al and the possibility to distinguish the later electrolytic production
from the early chemical reduction is a nice
examples of the problems and techniques
involved in modern archaeometallurgical
A shortlist of reference textbooks and monographs is listed at the end of the paper as an
introductory aid to archaeometallurgy.
Fig. 2. Relative importance of the use of materials through the prehistory and history of mankind following Ashby (1987, 2005).
Fig. 3. The archaeometallurgical cycle (from Rehren and Pernicka 2008).
67

Gilberto Artioli
3. The contribution of mineralogy to

archeometallurgy
Arabah (Timna and Faynan) region in the

Near East where, over thirty years, long projects have investigated and detailed out all
available evidence at different levels
(Rothenberg and Merkel 1995, Rothenberg
1999, Weisgerber 2003, Hauptmann 2007),
reaching a sound and complete interpretation
of the regional archaeometallurgy.
Based on the schematic diagram shown in

Fig. 3, we may distinguish several steps in
the production and life cycle of metallic
objects. The examples below are intended to
show the contribution of mineralogy to the
characterization and to the archaeometallurgical interpretation of the materials pertaining to some of the major stages of the cycle.
A recent long term project is the HiMAT one

(www.uibk.ac.at/himat/), aimed to investigate the history of mining activities in the Tyrol
and adjacent areas, with impact on environment and human societies (Tropper and
Vavtar 2009, Schibler et al. 2011).
3.1. The mining stage: ore extraction and

provenancing
Our knowledge on mining and ore treatment
in historical times has the support of written
sources, oral accounts, toponyms and family
names, and even direct evidence of galleries,
mine surveys and maps, treatment plants,
written records of production and trades, and
the like. However, the more we venture into
the past the more the evidence is confused
and fragmentary.
In general, the main questions involved in the

investigation of prehistoric metal extraction
sites are:
(1) what metal was extracted and what was
the nature of the mineral charge?
(2) can we trace the provenance of the smelted or treated ore minerals?
(3) when did the extraction activity started
and how long did it last? and
(4) what was the technology for metal extraction from the ores?
When we deal with prehistory, there are no

direct sources of information, and the material evidence is scarce and very often contaminated or altered by successive exploitation
in late periods. Therefore the investigation of
prehistoric archaeometallurgy is a fascinating
and challenging task, aimed to reconstruct
the links between ore deposits, mining activities, ore treatment, and metallurgical sites.
The answers often require investigations at

very different scales: from the submicron
scale of segregations and impurities in
metals and slags, to the large geographic
scale of the regional distribution of ore deposits and metal objects.
One of the major problems is that the available

pieces of archaeological evidence (prehistoric
mines, roasting and smelting sites, technical
ceramics, smelting slags, furnaces, crucibles,
raw metal ingots) are almost never found in the
same site: there are lots of pieces in the puzzle, though there is hardly a complete image. In
the most general case it is virtually impossible
to complete all aspects of the investigation for
an individual site or area, simply because of
time, cost, and record biases.
As an example, many of these questions concerning the rise and development of copper
mining and metallurgy in the Alpine area
from the end of the Neolithic (approx. in the
5th millennium BC) to the end of the Bronze
Age (approx. the beginning of the 1st millennium BC) are still unanswered.
Our knowledge before the Iron Age is very
fragmentary and we are confronted for example with mines showing early exploitation but
little or no evidence of reduction slags (i.e.
Libiola and Monte Loreto, Ligurian Alps, Italy:
Maggi and Pearce 1998; Saint Vran,
Queyras, France: Bourgarit et al. 2008,
2010), or with several smelting sites where a
substantial amount of slags have been
Only a few extensive long-term projects come

close to delineating all the major features of
the metallurgical chain in a geographical
area, from the mine survey to the production
and diffusion of metal. These are the cases
of the prehistoric copper extraction in the
68
Seminario SEM 09
models can be applied to the smelting slags

and to the unalloyed raw copper extracted
from the ores (Artioli et al. 2008b).
found, but they show no straightforward connection with the ore deposits (i.e. Luserna,
Trentino: Nicolis et al. 2007; Renon, Alto
Adige).
Application of the tracing models to the

manufactured objects requires a careful chemical and metallographic examination of the
metal, in order to understand the nature of
the alloy, the presence of remnants of the original charge as inclusions and segregations,
and possible biases due to alteration or contamination. It may indeed be dangerous to
pursue separately the investigation of the
ores, of the slags, and of the metal objects:
strict synergy is needed to understand the
complexity of the metallurgical cycle.
One further paradox is that there was abundant metal circulating since at least the 4th
millennium BC, as exemplified by the Iceman
copper axe (approx. 3200 BC: Fleckinger
2007) and a number of coeval artefacts, but
there is no clear evidence of large scale
mining or smelting until half a millennium
later. The only earlier recognized smelting
sites are small scale metallurgical activities
confined to the Brixlegg site, in Tyrol
(Hppner et al. 2005) and Belovode, Serbia
(Radivojevic et al. 2010). Several sites with
Chalcolithic slags are known in the Eastern
Alps (Artioli et al. 2007) although they mostly
date to the mid 3rd century BC or later. They
apparently indicate a sizeable mass copper
production only towards the latter part of the
Alpine Copper Age.
Recent applications of the models based on

the database of geochemical tracers have
met some success in
firmly locating in the Monte Fondoli area
(Pfunderer Bergwerk, Chiusa, Alto Adige)
the source of the copper ores used for all
known Chalcolithic smelting slags in the
Brixen
area
(Millan,
Gudon,
Circonvallazione Ovest: Angelini et al.
2012), and
identifying the source of the ores used for
the production of the Late Bronze Age
objects found in the Monte Cavanero
hoard (Chiusa di Pesio, Cuneo, Western
Alps: Artioli et al. 2009).
In the last few years a long-term project focused on prehistoric Alpine copper metallurgy
(AAcP, Alpine Archaeocopper Project:
http://www.geoscienze.unipd.it/aacp/welcome.html) was launched in order to investigate in detail the relationship between ores,
slags, and metal in the area. The core of the
project is the development of an extensive
database of Alpine copper mines containing
mineralogical, petrological, chemical, isotopic, and genetic information on the ore deposits (Artioli et al. 2008a).
These examples highlight the patient work of

the mineralogist in provenancing studies, that
is to critically filter the geological, geochemical, mineralogical, and archaeological information into a consistent and unifying interpretation. Key issues to be discussed are:
Solid minerogenetic interpretation of the

deposits (Nimis et al. 2012) and advanced
statistical analysis of the ore chemical and
isotopic data is the basis to understand the
applicability of the measured geochemical
tracers (Pb and Cu isotopic ratios, nearly 60
minor and trace elements, including REE elements) to metallurgical processes, including
slagging and reduction smelting. The discriminant analysis developed on the copper ore
database was tested on the well-characterized area of Agordo, Alpi Bellunesi, Veneto,
whose Valle Imperina copper mine was the
principal source of copper for the Republic of
Venice. The results of the Agordo case study
indicate that the developed discriminant
(1) the development, consistency, and dataretrieval protocols of geochemical and

isotopic databases;
(2) the availability of chemical and isotopic
databases for different ore deposits; and
(3) the mineralogical, geochemical and statistical significance of the chemical and isotopic tracers used for provenance discrimination.
69

Gilberto Artioli
Fig. 4. Title pages of the two fundamental volumes on mining and metallurgy published in the 16th century: (left) De la pirotechnia of Vannoccio
Biringuccio and (right) De re metallica of Georg Agricola.
3.2. The smelting stage: metal production
location of the metallurgical smelting sites

with respect to the ore mines is out of place
here, it is sufficient to say that only in a few
places there is a clear and recognized connection between mining and metallurgical activities: for example in the cited Faynan area
(Hauptmann 2007) or at Cabrires, France
where a small metallurgical village has been
excavated close to a known mining area
(Ambert and Vaquer 2005).
Our knowledge concerning the ancient extraction processes of metals from the ores is more
and more fragmentary as we go back in time,
in analogy to our knowledge about mining operations. For recent times, starting from the fundamental 16th century volumes of Vannoccio
Biringuccio (De la pirotechnia, published in
1540) and Georg Agricola (De re metallica,
published in 1556) (Fig. 4), we have ample
documentation, though sometimes the details
are difficult to interpret and reproduce.
However for earlier times there are no direct
accounts of the metallurgical operations, so
that we have to rely on the archaeometric analysis and the archaeological reconstructions of
the objects found in archaeometallurgical sites
(see table 2.1 of Hauptmann 2007). The scarce evidence is based on: stratigraphy of the
sites, furnaces, crucibles and other technical
ceramics, ore fragments and smelting slags.
Generally most of these evidences are sparse
and removed from the mining sites.
In many instances furnaces and slag heaps

are quite far from the ores, or even in areas
totally deprived of ore minerals, especially for
pre-Bronze Age activities (Hauptmann 2007,
Artioli 2010). The reasons for the transportation of the ores are subject to debate: in the
case of early Chalcolithic smelting the following of Neolithic trade patterns from sources
to settlements have been postulated
(Hauptmann 2007), whereas the Bronze Age
smelting sites are close to the ores, though
their geographical distribution may follow the
requirements for large amount of fuel or other
technical considerations.
A discussion of the logistic rationale for the
Concerning the smelting technology, if furna-
70
Seminario SEM 09
ces and technical ceramics (crucibles, tuyeres, bellows, etc.) are available, they may greatly help in the technical reconstruction of the
reduction process.
Here, it is important to remind that a neat

change in copper smelting technology appears to take place at about the ChalcolithicBronze Age transition, as evidenced by the
marked differences in the Chalcolithic slags
Mineralogical analysis of the ceramics and

the furnace components may be important to
the identification of the ores being treated,
the temperatures of firing, and the parameters of the smelting operations, though most
commonly these data are obtained by the
detailed investigation of the smelting slags
(Bachmann 1982). The mineralogical, textural, and chemical analysis of the slags yield
information on the type of minerals in the
charge, the smelting temperatures, the viscosity, the different steps of metal reduction,
the efficiency of the process, the redox conditions, the cooling rates, etc. The information is commonly extracted by a combination
of X-ray diffraction, optical microscopy, scanning electron microscopy, electron probe
micro-analysis, and X-ray fluorescence spectroscopy (see Artioli 2010: box 3.k).
The great majority of the ancient smelting
slags were derived from the processing of
copper, iron, and lead ores, mostly sulphides.
Tin, antimony, and zinc slags are also known;
they are scarce but they can be rather important to pinpoint the source of alloying elements in bronzes and brass.
Fig. 5. Optical micrographs of fayalitic olivine (top: crystal chains, bottom: euhedral crystals) crystallized in the glassy matrix of Chalcolithic
copper slags from Bressanone (Angelini et al. 2012).
(Bourgarit 2007) in terms of texture, heterogeneity, incompleteness of the melting process, absence of fluxing, low density, and low
reducing conditions with respect to the later
Bronze Age slags (Anguilano et al. 2002,
Mette 2003). Fig. 5 shows typical microscopic textures of Chalcolithic copper smelting
slags in the Alpine region.
One further note should be mentioned on the
investigations of the smelting sites. Very frequently in the past during the archaeological
excavations of the sites the metallurgical
slags were not considered as important as
the metals, technical ceramics, or other
archaeological finds, thus producing loss of
valuable knowledge.
By far most of the slag studies in the literature involve copper smelting and iron smelting/smithing. The major difference between
the two processes is that metallic copper
(melting temperature 1080C) can be produced through a fully molten state (i.e. the gangue and the slag are more viscous than the
running matte and metal), whereas the molten state of metallic iron (melting temperature 1540C) could not be reached before
modern cast iron production, so that the preindustrial technologies required squeezing
the fluid slag out of the solid metal at high
temperature by forging.
The chemical, mineralogical and textural characteristics of the different types of smelting
slags can be found in the cited literature
(Bachmann 1982, Hauptmann 2007, Artioli
2010, and references therein).
Modern excavations now pay due attention to

the distribution and quantification of the
slags (even micro-slags, such as the ham-
71

Gilberto Artioli
Fig. 6. Reflected light optical metallographic images of copper crystallites that underwent different thermo-mechanical processes: (a) copper dendrites produced by casting, (b) thermally annealed and partially recrystallized cast copper still showing remnants of the original dendrites, (c) slip
systems produced by mechanical working of the metal, and (d) worked copper through several cycles of mechanical hardening and thermal annealing, showing recrystallized grains and twin boundaries.
merscales produced during iron smithing and

forging, for example Angelini et al. 2011) in
the archaeological record, so that this information can be fully used to interpret and
reconstruct the metallurgical activities.
Interaction between the archaeometallurgist
and the archaeologist during excavation is
fundamental.
3.3. The manufacturing stage: metallurgy
and metallography
on the other hand archaeometallurgical investigations aim to measure the physical properties
in order to reconstruct the ancient manufacturing processes of the objects. Both investigations rely in the measurement and quantification of the metal texture, which may be experimentally performed by optical metallography,
electron backscattering diffraction, or crystallographic texture analysis (see details in Artioli
2010, box 3.l).
The physical properties of a metal object (i.e.

hardness, ductility, etc.) are dependent on the
size, shape, and orientation of the crystallites
(i.e. the micro-texture) in the material. In turn,
the metal texture is determined by its thermomechanical history, that is the temperaturetime path (i.e. cooling rates, annealing temperatures) and the mechanical stress imposed
during manufacturing. On one hand, modern
metallurgical engineering is interested in designing and optimizing the production processes
in order to meet specific physical properties,
Reflected-light optical metallography (Scott

1991, Wang and Ottaway 2004), based on
polishing and chemical etching of a small portion of the metal surface, is by far the most diffused, fast and cheap technique, though it is
generally invasive and only yields 2D information of the crystalline arrangement (Fig. 6). It
can be used as a micro-invasive technique only
by careful micro-sampling of pertinent areas of
the unaltered metal (Angelini et al. 2009).
Electron backscattering diffraction (EBSD) is
72
Seminario SEM 09
Fig. 7. (a) Eneolithic copper axe from Castelrotto/Kasteruth, Bolzano, Italy (Courtesy of the Museo Archeologico dellAlto Adige), with the diagram
showing the reference orientation directions (RD, TD, ND) used in the diffraction experiment; (b) direct pole figures projected from the calculated ODF; and (c) inverse pole figures recalculated from the ODF along the main directions of the object (modified from Artioli et al. 2003). The
data indicate that the axe was cast in a bivalve mould and subsequently cooled very slowly, allowing for an extreme iso-orientation of the crystallites.
based on the point-by-point analysis of the

orientation of the crystallite through interpretation of the Kikuchi lines (Schwartz et al. 2000);
the 2D texture is obtained by mapping the
domains with equal crystal orientation. It may
be performed micro-invasively on submillimetersized samples, though the analysis and
interpretation of polyphasic metals may be a
complicated issue.
are generally represented graphically by

means of the pole figures in direct (i.e. the
sample space) or inverse (i.e. the crystal
space) space (Monaco and Artioli 2011). The
measurement of the crystallographic textural
features of the sample (CTA: crystallographic texture analysis) therefore is a powerful
alternative to perform metallographic analysis in a totally non-invasive mode (Artioli
2007, Artioli 2010 pp 343-348).
The non-homogeneous spatial distribution of

crystallites in a metal sample implies a nonhomogeneous distribution of Bragg intensity
in the Debye diffraction rings. The measurement of the variation in intensity along the diffraction rings allows recalculation of the socalled orientation distribution function (ODF)
of the crystallites, that is the function statistically describing the crystallographic orientation of the crystals in the samples with respect to the sample orientation (Kocks et al.
1998, Popa 2008). Orientation distributions
It should also be reminded that for metals

and average absorbing materials, texture
analysis performed with X-rays gives only an
appropriate description of the surface layer
of the sample, whereas the same analysis
performed with deeply penetrating neutrons
may yield a more appropriate interpretation of
the bulk. Fig. 7 shows an example of the pole
figures resulting from the full CTA analysis of
a prehistoric copper axe: the data allow complete interpretation of the thermo-mechanical
73

Gilberto Artioli
Fig. 8. A sealed Buddha figure (left) (about 20 cm in height, photo) Sakyamuni, Bhumisparsa Mudra, West-Tibet, 14th15th century. It was investigated with X-rays (150 kV tube voltage, middle) and thermal neutrons (right). The X-ray image only shows the outer metallic brass cover, whereas neutrons can penetrate the metal and show the hidden organic cultual enclosures (wood, dried plants, rope) (from Lehmann 2008).
history and the interpretation of the metallurgical techniques employed to produce the
object.
verify the presence of marks derived from

the manufacturing process, polishing, and
tool use (Fig. 9);
analyse the composition of the surface
layers to check for original patinas, protective layers, or chemical treatments; and
assess the alteration and corrosion state
of the metal for conservation purposes
(Scott 2002, 2009).
Further information on the manufacturing techniques and assemblage of composite objects

may be obtained by routine and advances imaging techniques (i.e. 2D radiography and 3D
tomographic reconstructions). Neutron imaging
is especially useful for metals because of the
penetrating power of neutron beams (Lehmann
et al. 2005; Casali 2006). Fig. 8 (from
Lehmann 2008) shows the comparison of high
energy and neutron radiographies on a complex
composite statue.
A number of characterization techniques are

used to investigate the external metal surfaces, through the corrosion layers, to the pristine metal: high magnification optical microscopy, scanning electron microscopy, X-ray diffraction depth profiling, X-ray and neutron
imaging, X-ray fluorescence spectroscopy,
proton induced X-ray emission, X-ray photoemission spectroscopy, and many more.
3.4. The life and death of metal objects

Surface analyses of archaeological metal finds
and art objects are aimed to
Fig. 10 shows the use of hard X-ray tomographic reconstruction techniques for the noninvasive visualization of the alteration layers
in a strongly corroded Bronze Age copper
ingot (Artioli et al. 2011).
The interpretation of the surface layers of the
metal in terms of the original composition
and the subsequent corrosion processes
may be very difficult, particularly in presence
of polymetallic alloys, original surface treatments and patinas, or complex soil-metal and
atmosphere-metal interactions.
Fig. 9. Example of manufacturing tools marks on the surface of an Iron

Age cauldron. See the Iron Age Chiseldon cauldrons project at the
British Museum for details. http://www.britishmuseum.org/research/projects/featured_project_chiseldon.aspx)
The archaeometrical problems involved in the

characterization of metal surfaces are com-
74
Seminario SEM 09
Simple chemical analysis is sometimes not sufficient to resolve the issue and careful analysis
of the micro-textural features (such as the
interstitial position and the morphology of the
re-precipitated crystalline phases, presence of
chemical coring, etc.) are needed.
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Bachmann H (1982) The identification of slags
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78
Microanalysis of pigments in
painted artworks
/ David Hradil (1, 2) / Janka Hradilov (2)
>
>
(1) Institute of Inorganic Chemistry of the AS CR, v.v.i., ALMA laboratory, 1001 Husinec-Rez, Czech Republic, hradil@iic.cas.cz
(2) Academy of Fine Arts in Prague, ALMA laboratory, U Akademie 4, 170 22, Prague 7, Czech Republic
Abstract
This paper summarizes the current knowledge concerning the materials analysis of painted
artworks. In the introduction materials analysis is interrelated with other disciplines within a
broad context of the research of cultural heritage. Current methodological and instrumental
developments in the area are described with a special attention given to non-invasive analytical methods. The article also briefly deals with the relation of natural science, technology and
humanities in the investigation and conservation of the fine art. In more detail historical painting techniques are discussed and paint layers are described as composed materials containing both organic and inorganic compounds in characteristic layer sequences. The aim of
materials microanalysis of paints is to get both technological and materials signatures, which
both could be specific for the period, region or workshop. Therefore the identification of organic and inorganic materials in paints should always be accompanied by the description of the
layer stratigraphy and finding other detailed characteristics that relate to the origin of the painting. Mineralogy plays an important role in the analysis of paint layers, because the majority
of historical pigments are minerals. When using the tools of mineralogical analysis, particularly the X-ray diffraction methods, one can get an idea of the process of formation and/or
fabrication of pigments and its regional provenance. It also helps to identify the provenance
of the painting itself. A substantial part of this paper deals with the mineralogical analysis of
historical pigments. Carefully selected case studies demonstrate the usefulness of the
method to solve important tasks of the origin of artworks.
Resumen
En este artculo se hace un resumen del estado actual de conocimiento del anlisis de los
materiales que constituyen las obras de arte pintadas. En la introduccin se interrelaciona el
Anlisis de Materiales con otras disciplinas dentro de un amplio contexto de la investigacin
del Patrimonio Cultural. Se describen los actuales avances metodolgicos e instrumentales
en esta rea, con especial atencin a los mtodos analticos no invasivos. El artculo tambin
trata brevemente la relacin de las Ciencias Naturales, la Tecnologa y las Humanidades en
la investigacin y conservacin de las obras de arte. Se discuten con ms detalle las tcnicas pictricas histricas y se describen las capas pictricas como materiales compuestos,
que contienen tanto compuestos orgnicos como inorgnicos en secuencias de capas caractersticas. El inters del microanlisis de los materiales de las pinturas es encontrar huellas,
tanto tecnolgicas como materiales, que puedan ser especficas de un perodo, regin o taller.
Por esto, la identificacin de los materiales orgnicos e inorgnicos en las pinturas debe venir
siempre acompaada por la descripcin de la estratigrafa de las capas y el hallazgo de otras
caractersticas de detalle relacionadas con el origen de las pinturas. La Mineraloga desempea un papel importante en el anlisis de las capas pictricas, ya que la mayora de los pigmentos histricos son minerales. Al recurrir a los instrumentos del anlisis mineralgico, y en
particular a los mtodos de Difraccin de Rayos X, podemos hacernos una idea de los procesos de formacin y/o fabricacin de los pigmentos y su proveniencia regional, Esto tambin
ayuda a identificar la procedencia de la misma obra pictrica. Una parte importante de este
artculo se extiende sobre el anlisis mineralgico de los pigmentos histricos. Se han selec-
79
Microanalysis of pigments in painted artworks

Hradil, D. & Hradilov, J.
Fig. 1. Interrelation of the fields of science (in grey), technology (in blue) and humanities (in yellow) in the cultural heritage investigation and protection.
ve arguments for an art-historic evaluation of

works of art (Fig. 1).
cionado a este propsito algunos casos prcticos que demuestran la utilidad de este
mtodo para resolver cuestiones importantes sobre el origen de las obras de arte.
It should, however, be said that without the

participation of other scientific branches, a
comprehensive analysis is only hardly possible this is simply given by the diversity of
materials that form cultural heritage objects
(stones, paper, plaster, glass, pigments etc.).
Substantial limitations of any analysis of
works of art are given by the fact that no sam-
Key-words: Conservation science, materials microanalysis, powder X-ray microdiffraction, painting

technique, mineral pigments, clay minerals.
1. Introduction
Materials analysis of tangible cultural heritage is a key part of conservation science.
Conservation science is a branch of natural
science that is concerned with the material
aspects of works of art, their deterioration
and conservation. Conservation science, contrarily to conservation technology, falls to the
fundamental research of materials, describes
the processes of their interactions and develops new tools for their description. Technical
and technological solutions are then derived
from the current knowledge obtained.
Conservation science relies on measurements
of physical and chemical properties. Such measurements are central to analytical chemistry,
that branch of chemistry concerned with determining the qualitative and quantitative identity
of a substance (Mazzeo et al. 2011). Recently,
non-destructive analysis of cultural heritage
objects represents one of major trends in analytical chemistry (Chiari 2008; Martin et al.
2010). Better understanding is the first necessary step for better preservation, conservation,
restoration and protection and gives also decisi-
Fig. 2. Sampling. Conservators should make a compromise between

representativeness of the collected sample and minimizing a risk of
the painting damage
80
Seminario SEM 09
pling is usually allowed or only minute samples are possible to get. Furthermore their
internal heterogeneity can be considerable
(Fig. 2).
instruments (Jonge and Vogt 2010; Yonehara

et al. 2010). The necessity of an interdisciplinary approach to solve this problem is evident.
Because of these reasons in Europe in last

decades, non-invasive (integrity of the object
is preserved, no sampling is necessary) and
non-destructive micro-analytical (sample is
taken, but analyzed as is, not consumed or
modified) methods were widely tested in cultural heritage field especially in the case of
paintings. This growing trend can easily be
demonstrated on the increasing number of
publications in top-impacted analytical journals. Current developments can be divided
into two directions
In a routine practice of the investigation of paintings, imaging and analytical methods are not
yet fully interrelated. Conservators use conventional UV-Vis photographs, IR reflectography
(IRR) or radiography (XR) and/or computer tomography (CT) to visually interpret technical signatures of the author visually without any knowledge of materials used (Fig. 3). Analytical chemists, on the other hand, frequently perform
blind analyses of materials without any knowledge of how they are organized in the layer
sequence, what are their interrelations and
what these textural patterns mean in terms of
the painting technique. Materials and structural/technological signatures should be, however, studied together in a substantially higher
level of understanding than is common today.
developments in physical principles and

instrumentation e.g. portable instruments (Grieten and Casadio 2010; Miliani
et al. 2010) and
Cultural heritage objects can be categorized

according to technological signatures. Using
this clue, easel and wall paintings together
developments in measuring and interpretation strategies including unconventional

approaches (Cardell et al. 2009; Palmieri
et al. 2011).
2. Paints as composed materials

In cultural heritage, composed materials appear as an integral part of historic objects, artifacts and works of art of any kind. The most
important fact is that their internal heterogeneity brings a crucial information related either
to the technology of manufacturing, natural process of formation, or the process of secondary
modification, deterioration etc. From the analytical point of view composed materials taken (if
ever) in minute amounts from objects represent unconventional samples that cannot be
homogenized or modified without a risk of
loose of information described above.
A comprehensive methodology that includes
an advanced description of internal structures and materials composition of different art
objects made of composed materials is not
developed yet. Close collaboration and composite action of several scientific branches is
needed to achieve inevitable synergic effects
routing to develop such a methodology based
on using up-to-date analytical and imaging
Fig. 3. Use of infrared reflectography (IRR) and X-ray radiography (XR)

to visualize internal structure of the painting or, like in this case, to
uncover an original painting completely over-painted by another painting (adopted from Hradil et al, 2006).
81

Fig. 4. Simplified description of the layer stratigraphy in cross-section of the painting fragment embedded in polyester resin (in the middle) as visible in white (a) and UV (b) lights and
in backscattered electrons (c)
In the European fine art, one of the first

famous manuals of technical experiences,
material preparations and painting itself, is the
early renaissance work by Cennino Cennini
issued first in 1437 (Cennino 1978). A very
good review of treatises and recipe-books
from the 12th to the 18th centuries is given by
with polychrome sculptures, for example,

belong to one single group all these objects
are classified as fine art (not applied art) and
contain color (painting) layers applied in logical sequences following similar technological
rules (Fig. 4). This group of painted artworks
will only be considered in the following text.
Paint layers represent composed mixtures of
organic and inorganic compounds (pigments
and their binders) of very different properties,
which are further composed to characteristic
layer sequences; the description of this internal structure of paints together with the identification of organic binders (glue, egg yolk,
whole egg, linseed oil etc.) is relevant for interpreting of historical painting technique with
period and regional specificity.
In the traditional European paintings, the technological principles were held relatively strictly.
The layer sequence starts with ground layers
that served as a coating material to prepare
the surface of a wooden panel or canvas. By
their color, they were also closely related to the
techniques and materials in the subsequent
painting. Different types of (under)drawings
and/or priming (imprimitura) belong also to
the so-called preparatory layers.
Then the sequences of paint layers follow.
Each the painting sequence is usually finished
by varnish based e.g. on egg white, natural oils
and resins and, later on, on synthetic acrylates. Original painting sequence can very frequently be over-painted by later re-paints.
Fig. 5. Degradation and color change of minium (Pb3O4). In the environment of dissociated carbonic acid minium disproportionates as
follows: Pb3O4 (orange minium) + 2H2CO3 # PbO2 (brown-black plattnerite) + 2PbCO3 (white cerussite) + 2H2O; this process of darkening
is showed on the example of Pre-Romanesque murals in Slovakia (a),
where some blackened parts of figures (b) were later retouched by carbon black (c) not further respecting the original coloring.
82
Seminario SEM 09
Fig. 6. Grain size and morphology is related to the origin of minerals. Aggregate of small uniform par ticles of synthetic titanium white
(anatase TiO2) used in modern paints since 1920 (a) vs. weathered grain of natural anatase in the same scale as a common admixture in clay-based pigments used since the pre-histor y (b); microfossils indicating a natural origin of the chalk (limestone) used instead of ar tificially prepared calcium carbonate or carbonatizated lime (c); sharp and elongated cr ystals of neo-formed salts in porous
space of color layers as an example of secondar y deterioration process (d).
is another popular field of recent investigations

of works of art (Monico et al. 2011).
Merrifield (1967). Then, further works on painting techniques with a general scope should be
mentioned, e.g. Eastlake (1960), Laurie
(1967), Berger (1973).
3. Microanalysis of pigments
3.1. Mineral and synthetic pigments
To properly interpret the painting technique is

thus not only needed to identify materials but
also to locate them in the layer sequence (Rosi
et al. 2011). Heterogeneity of the source
materials from which the paint layers are made
is further important for understanding their
provenance and/or properties and thus it
should not be lost or overlooked during the
analysis. To properly interpret these source
materials in the context of their use in the history combining knowledge of analytical chemistry and geosciences is needed.
Pigments in color layers of paintings are

either natural (mineral) applied simply after
mere mechanical pre-treatment and separation not-affecting their chemical or phase
composition (e.g. malachite, azurite, celadonite, cinnabar, orpiment etc.), or manufactured - prepared by chemical reactions from
substantially different raw materials (e.g.
smalt, lead white, verdigris).
In a relatively lower extent, also organic pigments are prepared from organic dyes by precipitation on inorganic substrate (e.g. red
organic lakes). Gradually, a lot of mineral pigments have been substituted by their artificial analogues (e.g. artificial ultramarine, artificial orpiment, vermillion etc.), however, on
the other hand, some of them survived until
On the other hand, the description of secondary-developed textures e.g. corrosion and
weathering rims, surface layers etc. is relevant
for better understanding of deterioration processes and virtual reconstruction of original
colors (Fig. 5). A description of zones of degradation and explaining deterioration processes
83

table 1. Comparison of mineralogical composition of five selected red clay-based grounds of paintings from the Czech collections and
their attribution to three different source materials from historical mining deposits Horenec in the Czech Republic (Bk), Kronach in
nor thern Bavaria (C) and yet unknown locality in nor thern Italy (Bs)
3.2. Methodology
the present days (e.g. clay-based pigments

earths). During the 19th century industrial
production of new synthetic pigments (e.g.
zinc white, synthetic alizarine etc.) has started. Fundamental works on pigment origin,
preparation, use and identification are given
e.g. by Feller (1986), Roy (1993), Fitzhugh
(1997) and Berrie (2007).
Complete fingerprint of each painter can be

folded from the material composition of
colors (materials fingerprint), the method of
their preparation, mixing and spreading in
layers (technological fingerprint) and artistic
expression (style fingerprint). The first two fingerprints provide extra information about the
region and the period of artwork origin.
Natural and artificial pigments differ in content

of various admixtures, variable grain size and
crystallinity. These properties affect the opacity and color fastness of the pigment (Fig. 6).
Obtaining a complete fingerprint today

requires costly transpor tation of the painting for a long distances and extensive
sampling - other wise the evaluation is
highly subjective and it results in the growing of the trade with forgeries. The costs
of analyses, the transpor t of works of ar t,
insurance costs, etc., which are usually
too high for regional museums, churches
and other owners, have their share on the
growing interest in non-invasive analytical
techniques. Despite a significant boom in
this field in last years, it must be said
that without sampling the description of
authors fingerprint will always be only
par tial (Fig. 7) .
The knowledge about when and how the historical pigments were being replaced by the
synthetic ones contributes to the dating of
paint layers. Mineralogical analysis describing
the process of the formation of individual
mineral pigments in nature helps to indicate
the regional provenance of painting materials
by comparing them with materials from reference sources (Table 1).
Modifications of the pigments structures,
different admixtures and contaminations of
the product could also be related with different fabrication processes and thus with different workshops. To assign the authorship
of anonymous paintings the materials
analysis should always be combined with
the description of ar tistic style within comparative studies.
Once samples are taken from the prestigious

works of art, they become a part of a physical archive and may not be lost or consumed
during their analysis. Therefore, the main
effort is directed to analyze a small amount
84
Seminario SEM 09
Fig. 7. X-ray fluorescence

spectra (a) obtained by
non-invasive
punctual
measurement by handheld equipment (b). Use
of mixed Pb-Sb-Sn yellow
(i.e. Pb2SbSnO6.5) instead of pure Naples yellow
(i.e.
bindheimite
Pb2Sb2O7) is here indicated by a joint occurrence
of Sb and Sn in yellow
color together with Zn
zinc white (ZnO); use of
this uncommon pigment
is one of authors fingerprint of the 19th century
painter Friedrich von
Amerling.
of a sample by the most methods in a nondestructive way to obtain maximum information without any loss of material. Sample pretreatment has to be minimized and, if
applied, it has to be acceptable for most or,
ideally, all techniques which are necessary
for complete examination of the sample. This
implies testing of particular methods, namely
their detection limits, accuracy, and correctness of measurements because they can differ significantly from those of the standard
procedures.
such as Raman and/or infrared spectroscopy

(Vandenabeele et al. 2007, Bacci et al. 2001).
The main disadvantage of Raman spectroscopy
in the mineralogical analysis of paints is a high
risk of undesirable fluorescence promoted either
by organic stuff (binders, sealing compounds
etc.) and/or other fine-grained materials such
as, for example, clays (Fig. 8).
X-ray diffraction, contrarily to Raman spectroscopy, enables indisputable identification of
crystal phases, including double salts, hydrates, and unstable materials, using a huge number of reference patterns available in an array
of databases. Furthermore, XRD can be used
for quantification of phases in mixtures.
Routinely used laboratory methods for instant investigation of fragments of paints and
their cross-sections are light microscopy (LM)
and scanning electron microscopy coupled
with energy dispersive spectrometry (SEMEDS). They provide preliminary information
about the morphology, stratigraphy, and elemental composition of paints. The semi-quantitative elemental analysis can further be
improved by quantitative and trace elements
analysis via particle induced X-ray emission
(PIXE) and/or scanning electron microscopy
coupled with wavelength dispersive spectrometry SEM-WDS (Schreiner et al., 2007).
Implementation of mono or poly-capillary

systems into the conventional diffractometers enables analysis of small volume samples or even their selected parts without any
destructive pre-treatment (Svarcov et al.
2010). Introduction of X-ray microdiffraction
into material characterization was made possible by synchrotron radiation sources, which
are noted for high intensity X-ray beams enabling collection of diffraction data from small
areas (typically of the order of 0.001 0.1
mm) in a reasonable time (Dooryhe et al.
2005). Laboratory equipments for routine
powder X-ray microdiffraction have become
more frequent in last years and, as we already proved, the resulting data are generally
Focusing on the identification of inorganic crystal

phases, X-ray diffraction-based techniques (XRD)
are very effective tools for their indisputable
determination (Svarcov et al. 2010), besides
more frequently used spectroscopic methods
85

Fig. 8. Raman spectra of

natural
kaolinite
from
Georgia (U.S.A.), where only
the peaks of admixed anatase (A) are clearly distinguishable; without additional
information this spectra
could be misinterpreted as
titanium white (adopted from
Kosarov, 2011).
(Hradil et al. 2003 and 2011).
comparable with those obtained on synchrotron-based microdiffraction (Svarcov et al.

2011a). In our workplace, for example,
PANalytical XPer t PRO diffractometer is
used, equipped with a conventional X-ray tube
(CoK! radiation, 40 kV, 30 mA, point focus),
a glass collimating mono-capillary with an exit
diameter of 0.1 mm, and a multichannel position-sensitive detector (XCelerator) with an
anti-scatter shield (Fig. 9).
Based on distinguishing of structural modification of bindheimite (Pb2Sb2O7) by Sn and

identification of its accompanying minerals
one can trace back procedures and raw materials to produce various types of lead-based
yellows (Hradil et al. 2007).
Experimental mineralogical research has led
to the novel description of the crystal structure of basic copper acetate (verdigris) a pigment used by painters since the Middle Ages
(Svarcov et al. 2011b).
3.3. Case studies

The authors have been dealing with mineralogical analysis of pigments systematically for
many years and have published its results on
regular basis.
Practically no attention has been paid in literature to description of clay structures in the
traditional painting pigments. Most articles
on analyses of paintings are happy with the
statement that the painting contains an
earthy pigment, iron ochre or red clay, without
fur ther specifying their compositions.
Meanwhile, there is a significant diversity of
such materials in terms of natural processes
of their formation.
European Medieval paintings often contain intensely-colored materials, originally coming from
surface layers of just uncovered polymetallic ore
deposits, where clay minerals were practically
missing and for which the technical term earth
should not be even used. On the other hand,
these raw materials often contained specific
admixtures of metals (e.g. Pb, As or Zn), which
may help to identify their origin.
Fig. 9. Powder X-ray diffraction equipment at the Institute of Inorganic

Chemistry of the AS CR in Rez, Czech Republic.
The mineralogical analysis provides e.g. indicators which make it possible to discern provenance of various earthy pigments (containing clay minerals) found in microsamples
86
Seminario SEM 09
Fig. 10. X-ray intensity maps of selected elements in the original beige layer of the background, toned by red grains (Altarpiece of
Matejovce, right wing); X-ray intensities correspond to relative concentrations of individual elements within the measured area, but the
concentration maxima indicated by the highest intensity are different for each element (Ca maximum 100 wt%, Fe maximum 60 wt%,
Mg maximum 45 wt%, Pb maximum 60 wt%, Zn maximum 5 wt%); grain +1 represents iron oxides with some admixtures of Zn-bearing
minerals, and grain +2 is Zn-dolomite.
sources, differently to other workshops of the

same period and place (Hradil et al. 2008)
(Fig. 10).
Within detailed mineralogical research of

selected Gothic altarpieces in Nor thern
Slovakia and Lesser Poland it was, for example, found that the original iron red contains
goethite, hematite, calcite, and Zn-dolomite.
Zinc containing dolomite represents a fingerprint indicating that the source material was
mined in the oxidation zone of the carbonatehosted ZnPb ore deposit near Cracow,
Poland, which has been active since the 12th
century. Thus one could conclude that works
of the so-called Master of Matejovce altarpiece workshop can be recognized not only by
their conservative style known as the Cracow
school of painting but also by very characteristic materials features indicating the authors preference to use pigments from regional
In the case of mineral pigments, which were

formed by weathering or other alteration of
silicate rocks, the decisive factor is the
correct identification of clay structures and
their closely associated phases, e.g. iron oxides. The main reason why such information
is often missing is particularly the limited
availability of material from the painting,
which reduces the possibility to apply standard procedures for clay investigation separation and orientation of particles, exchange
of interlayer cations etc. (Moore and
Raynolds 1997).
87

Fig. 11. Interstratified

illite / smectite indicated by interplanar distance of ca 1.31 nm at
the diffraction pattern
of reference Italian
17th century painting
by G.B. Langetti and
on one anonymous
painting; this clay fingerprint together with
almost the same mineralogical composition
of the ground helped
to locate the anonymous painting to the
region of nor thern
Italy.
the way to reduce this disparity is the current

development of non-invasive analytical techniques that allow obtaining exact data in situ,
even in distant places - regional galleries,
rural churches, etc.
Completely unaddressed remains the issue of

reaction of expandable clay structures in the painting layer with humidity and organic binders,
which result in organo-clay complexes, both in
painting and preparatory layers. However, their
stability in the painting may be very significant
from the viewpoint of preservation of the paintings. The only organo-clay historical pigment,
which has been carefully investigated, is the socalled Maya blue a very stable complex of palygorskite and natural indigo (Domnech et al.
2009; Giustetto et al. 2011). This pigment, however, has not been found in European paintings.
In the restoration/conservation practice the aimless collection of analytical data still prevails
over the targeted analyses. Each expertise in the
field of cultural heritage requires its make-to
measure methodology reflecting the diversity of
materials as well as variety of tasks. When applying this approach, targeted mineralogical analysis of paint layers could directly lead to dating
and to determining the provenance of anonymous works of art.
Often we also hear the opinion that artworks
must first to be preserved and then (when enough
money is left) discovered and explored. But is it
not rather the opposite? Material properties we do
not keep forever, they decompose sooner or later,
and we can only slow down this process. But they
were created for our inspiration and knowledge,
which is not a subject of any further decay. First of
all, this knowledge itself is a substantial part of
our cultural heritage. And a respect to the knowledge is something what we often lack.
Results of last investigations demonstrated

how a correct description of basal diffractions of clay minerals in the low-angle region
leads to a direct determination of provenance
of anonymous 17th century paintings (Hradil
et al. 2010), or, how the source locality of the
white earth (kaolin) used in the preparatory
layer of Bohemian Gothic murals can be indicated by a calculation of the kaolinite crystallinity index (Svarcov et al. 2011a). Wide
range of other examples could be given.
4. Conclusion
5. Acknowledgement
An estimated 90% of tangible cultural heritage is not studied by modern scientific

methods. Often (and often unnecessarily)
only the famous works of art in famous galleries are subjected to detailed investigations.
The authors are grateful to all their colleagues

from laboratory ALMA as well as to all friendly
collaborating restorers for fruitful cooperation
in this research. Financial supports by the
Ministry of Education of the Czech Republic
Is this correct? As mentioned in this paper,
88
Seminario SEM 09
(RVO 61388980), and Ministry of Culture of

the Czech Republic (DF12P01OVV048) is kindly
acknowledged.
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Palmieri, M., Vagnini, M., Pitzurra, L., Rochci, P.,
90
Binders in historical buildings:

Traditional lime in conservation
/ Carlos Rodrguez-Navarro
Dpto. Mineraloga y Petrologa, Universidad de Granada, Fuentenueva s/n, 18002 Granada
Abstract
Mankind has used many types of binders throughout history: from mud in vernacular earthen architecture to current high-performance cement. However, gypsum and lime have been by far the most
common and important binders in historical buildings. Their use expands several millennia and is
represented in the architectural feats of all kind of civilizations. Here, the history, technology and
uses of gypsum- and lime-based binders are reviewed. We focus on the study of the different steps
of the gypsum and lime cycles as a conceptual framework to underline past applications and performance of these binders, and their current use in architectural conservation. Special emphasis is paid
to the technology and uses of lime as a versatile and compatible conservation material.
Resumen
La humanidad ha usado muchos tipos de ligantes a lo largo de la historia: desde el barro en la arquitectura verncula de tierra a los actuales cementos de altas prestaciones. Sin embargo, el yeso y
la cal han sido, con diferencia, los ligantes ms comunes en edificaciones histricas. Su uso se
extiende durante varios milenios y est presente en los hitos arquitectnicos de todo tipo de civilizaciones. Se revisan aqu la historia, tecnologa y usos de los ligantes basados en el yeso y la cal.
Nos centramos en el estudio de las diferentes etapas en los ciclos del yeso y la cal, como un entramado conceptual para destacar las aplicaciones y comportamientos de estos ligantes en el pasado
y su actual uso en la restauracin arquitectnica. Se hace un especial nfasis en la tecnologa y los
usos de la cal como un material de restauracin verstil y compatible.
Key-words: Binders, lime, portlandite, gypsum, calcite, mortars, plasters, historical buildings, carbonation, hydration, topotactic.
1. Introduction
A binder is defined as a material which acts as a glue or cement when mixed with an aggregate (e.g., sand) and water to form a fresh plaster, render, mortar or concrete. Following setting and hardening, such composite materials play a structural and/or decorative role in a building (Lea 1970). Since the advent of sedentism and building technology, which could be traced back to the Pre-Pottery Neolithic A in South-West Asia (e.g., Jordan river valley), ca.
11,700 to 10,500 years ago (Finlayson et al. 2011), mankind has used many different binders. Mud (clay-rich earth) was among the first binders used (Houben and Guillaud 1994) as
exemplified by the adobe walls of Jericho (Israel) dated to 8300 BC (Allen and Tallon 2011) or
the earthen structures (rammed earth) in atalhyk (Anatolia, Turkey) dated to 6000-7500
BC (Mellaart 1967).
However, the use of this type of binder does not involve pyrotechnology (i.e., no heat treatment was required). As a result, ear then structures display a low strength and are
prone to weathering and damage. With the advent of pyrotechnology ca. 12000 years
ago (Kinger y et al. 1988) , a new class of binders emerged with superior proper ties in
terms of strength and durability, as well as versatility and applicability. Among them,
gypsum and lime have played an outstanding role in building histor y from the Neolithic
until nowadays.
91
Binders in historical buildings: Traditional lime in conservation

Carlos Rodrguez-Navarro
Here, the history, technology and uses of

gypsum and lime binders will be reviewed.
Special emphasis will be paid to the case of
lime, as this has been the binder most profusely and ubiquitously used by mankind.
Furthermore, lime has recently emerged as
the binder of choice for architectural conservation. Therefore, its current use in heritage
conservation will also be outlined.
Gypsum was the most common binder in

Ancient Egypt both for masonry and decorative
purposes since Pharaonic times (Lea 1970;
Lucas and Harris 1962). Lucas and Harris
(1962) report the use of gypsum in several
tombs and as mortar and plaster in the Giza
pyramid. Other studies have confirmed its presence in mortars from the pyramids of Medium
(2600 BC), Cheops (2500 BC) and Unas
(2250 BC) (Regourd et al. 1988).
2. Gypsum binders
Gypsum plasters were commonly used in the

Middle East and in countries around the
Mediterranean basin, especially during the
Middle Ages (e.g., Islamic Architecture) (Elsen
2006). In the area around Paris, gypsum mortars were thoroughly used in gothic buildings
such as the Cathedrals of Chartres and
Bourgues (Adams et al. 1992), which may
explain why gypsum-based binders are known
as Plaster of Paris. Despite its low strength
and poor durability in humid environments,
examples of gypsum mortar applications in
northern Europe are numerous. For instance,
2.1. Gypsum as a building and decorative

material
Gypsum-based mor tars and plasters have
been used since ancient times, especially
to cover masonr y, as decorations, or as a
suppor t for mural paintings (Elsen 2006).
Due to their setting upon addition of water,
gypsum-based binders could be considered
the first hydraulic binder used by mankind
since ca. 9000 years before present
(Gar tner 2009).
Fig. 1. Gypsum-based mocrabes in the Corral del Carbn, a XIV c. Islamic building in Granada (Spain).
92
Seminario SEM 09
Kawiak (1991) describes the use of gypsum

mortars in a XII c. church in Wislica, Poland.
gypsum, although in some ancient mortars

and plasters, anhydrite has been also found
(Regourd et al. 1988) along with calcite
(Kawiak 1991). The presence of anhydrite
poses the question about the possible origin
of anhydrous calcium sulfate after dehydration of gypsum at relatively low T (< 30 C)
and RH (<< 70 %) (Charola et al. 2008).
Conversely, it could be argued that anhydrite
crystals are unhydrated relicts of the original
binder prepared following calcination at high
T (> 350 C) of gypsum mixed with calcite,
what is known as Keenes cement or
Estrich Gips (Sayre 1976; Kawiak 1991).
Up until nowadays gypsum has been applied

either as mortar and plaster for surface finishing, or as cast and/or carved decorations
(Arredondo 1991 Luxn et al. 1995). A significant example of this latter application is the
case of the mocrabes and decorated plasters (yeseras) from the Alhambra and other
Islamic buildings in Granada (Spain) (Fig. 1).
At the Alhambra (and by extension in most
Medieval Islamic architecture) two main
gypsum-types were used:
A variation of plaster of Paris is the so-called

scagliola which is a composite material prepared by mixing soft-burned gypsum (hemihydrate or bassanite, see section 2.2), glue
and pigments with water. Such a composite
material has been used as an imitation of
marble, thereby its name stucco marble. To
some authors, however, scagliola is a
gypsum-based plaster made of purer and
finer hemihydrate particles, which typically
makes the set material whiter than normal
gypsum plasters (Rubio-Domene 2006).
Rubio-Domene (2006) indicates that the so-
black gypsum (yeso negro), made of

highly impure hemihydrate (50-60 wt %)
containing significant amounts of ashes
produced during calcination, and
white gypsum (yeso blanco) a purer material made of > 66 wt % hemihydrate
(Rubio-Domene 2006).
Gypsum renderings were extensively applied
as a base for mural painting. In all these
cases the major component after setting was
Fig. 2. The gypsum cycle. Scanning electron microscopy (SEM) images show examples of lens-shaped gypsum prior to dehydration, bassanite phases formed after dehydration (modified from Singh and Middendor f, 2007) and gypsum in a set plaster.
93

called stucco is made by mixing inert anhydrite with glue.
equilibrium transition T between bassanite

and gypsum) at standard atmospheric pressure (Charola et al. 2007). Because at this T
the reaction is extremely slow, T > 373 K is
normally required in order to accelerate the
dehydration kinetics. Industrial plaster of
Paris is produced under humid conditions at
ca. 413 K (Charola et al. 2007). Depending
on the dehydration procedure, two hemihydrate varieties are obtained, !- or $CaSO40.5H2O. Heating gypsum in a humid
atmosphere produces the first variety, while
heating in a dry atmosphere results in the
second variety (Freyer and Voigt 2003; Singh
and Middendorf 2007).
2.2. Calcium sulfate phases

The common calcium sulfate minerals are
gypsum (CaSO42H2O, monoclinic, I2/c),
bassanite (CaSO40.5H2O, trigonal, P312),
and anhydrite (CaSO4, orthorhombic, Amma).
Here we report the space groups compiled in
Hawthorne et al. (2000); note however that
hemihydrate and anhydrite form different
polymorphs (see below).
Gypsum is the most abundant sulfate mineral
on the Earth surface and has a very widespread occurrence in evaporite deposits and other
sediments, in fumaroles, and in ore deposits
(Vaniman and Chipera 2006). Evaporation of
sea water initially leads to gypsum precipitation, followed by the crystallization of anhydrite (CaSO4) in the residual brine due to a reduction in water activity. Anhydrite and bassanite
also occur in situations where thermal activity
has naturally dehydrated precursor gypsum, or
in acid alteration environments (see review by
Charola et al. 2007).
Under near-equilibrium conditions, heating to

~373-473 K (dehydration T depends on the
type of precursor bassanite: Freyer and Voigt
2003) produces %-CaSO4 (also known as
CaSO4(I)), according to:
CaSO40.5H2O # CaSO4 + 0.5 H2O (2)
The anhydrous product is called soluble anhydrite, a metastable phase which rapidly rehydrates under normal atmospheric conditions.
As in the previous step, some overstepping (T
higher than the equilibrium decomposition T)
is required to speed up the reaction.
2.3. The gypsum cycle

The use of calcium sulfate as a binder involves a series of steps which form the so-called
gypsum cycle or calcium sulfate cycle
(Fig. 2).
Further heating at 633 K leads to the formation of anhydrite ($&CaSO4 or CaSO4(II))

which does not react with water (Prasad et al.
2005). Heating of anhydrite at 1453 K
results in the formation of !&CaSO4
(CaSO4(I)) (Charola et al. 2008).
The first step consists in the thermal dehydration of gypsum to form a hemihydrate (the
mineral bassanite). The second and final step
of this cycle involves the hydration and setting of bassanite to form gypsum which acts
as a binder. Below we will study these two
steps separately.
Le Chatelier (1887) was the first to show the

two steps dehydration of gypsum. Since his
pioneering work, much has been published
on the mechanisms and kinetics of gypsum
thermal decomposition (see reviews by Freyer
and Voigt 2003; Charola et al. 2008).
2.3.1. The dehydration of gypsum
There is however no consensus on the actual

mechanism of thermal decomposition of
gypsum. For instance, the two-step dehydration process has been challenged by Prasad
et al. (2005) that reported direct dehydration
of gypsum to form %&CaSO4, followed by its
rapid hydration to yield bassanite. There is
also a persisting controversy regarding the
The use of gypsum as a binder involves its

thermal treatment to form the hemihydrate
(plaster of Paris), according to the dehydration reaction:
CaSO42H2O # CaSO40.5H2O + 1.5H2O (1)
This reaction starts at 42C (315 K) (i.e.,
94
Seminario SEM 09
promotes the dissolution of the remaining bassanite and the precipitation of more gypsum.
Typically, newly formed gypsum appears as
m-sized acicular crystals which form a highly
porous, yet strong, 3D-mesh structure (Singh
and Middlendorf 2007). Both the morphology/size of gypsum crystals and the kinetic of
the hydration reaction can be modified by the
addition of different inorganic and organic
compounds (Solberg and Hansen 2001). For
instance, addition of Ca(OH)2 accelerates setting (Ridge and King 1976) whereas addition
of carboxylic acids (and their salts) have been
shown to delay hemihydrate setting, leading to
the formation of larger equant gypsum crystals
as opposed to the fibrous interlocking crystals
in additive-free set pastes (Singh and
Middlendorf 2007; Gartner 2009). As a
result, the flexural and compressive strength
of gypsum plaster is significantly reduced
(Lanzn and Garca-Ruiz 2012).
existence of several hydrated (metastable)

phases with formula CaSO4nH2O, where the
actual value of n is not well established for
some of these phases (see Adam 2003).
Crystallographic studies (using XRD and/or
neutron diffraction) show that the thermal
decomposition of gypsum crystals most probably follows a topotactic mechanism (Abriel et
al. 1990). Topotaxy can be defined as a solidstate chemical change in which the reactant
provides a template for product phase generation (Galwey 2000). This means that there is a
clear structural relationship between precursor
and product phases due to a good matching
between their crystallographic structures. In
situ TEM-SEAD analyses have confirmed that
the dehydration reaction is in fact topotactic
(Sipple et al. 2001).
2.3.2. The hydration of bassanite

The setting and hardening of plaster of Paris
has been the subject of extensive research
over the last 100 years, although it is a process not fully understood (Singh and
Middendorf 2007). Hemihydrate hydration
follows the overall (exothermic) reaction:
In addition to precipitation in solution, Melikhov

et al. (1991) indicate that a topochemical reaction is responsible for the formation of gypsum
pseudomorphs after bassanite. This is consistent with the reported pseudomorphic transformation of hemihydrate into gypsum in a water
vapor atmosphere (Triollier and Guilhot 1976), a
process which appears to be topotactic. Note
however that a tightly interface-coupled dissolution-precipitation reaction could also explain the
formation of gypsum after a pseudomorphic
replacement of bassanite. For details on such a
replacement process see the recent review by
Putnis (2009). Overall, these observations suggest that the mechanical properties of the set
material may strongly depend on the textural properties of the precursor bassanite (in addition to
the curing and setting conditions, as well as the
absence/presence of additives and impurities).
CaSO40.5H2O + 1.5H2O # CaSO42H20 (3)

Both the kinetics and properties of set
gypsum are dependent on the type of bassanite
precursor
phase
(!& or
$&
CaSO40.5H2O). The !&phase shows a shorter induction period and produces a set plaster with higher strength than the $&phase
(Singh and Middendorf 2007).
Most researchers agree that the hydration of
bassanite is a solution mediated process (Singh
and Middledorf 2007). In contact with water,
bassanite crystals start to dissolve generating a
saturated solution with respect to this phase.
Bassanite is more soluble than gypsum: 0.65 wt
% calcium sulfate hemihydrate dissolves in water
at room T, against 0.2 wt % in the case of
gypsum. The resulting solution rapidly reaches
supersaturated with respect to gypsum leading
to its crystallization.
2.4. Deterioration and conservation of

gypsum mortars and plasters
Gypsum plasters and mortars are prone to
decay (Cotrim et al. 2008). This is primarily due
to the low strength of gypsum, which has a hardness of 2 in the Mohs scale, and its relatively
high solubility (2.1 g/L at 20C). Gypsum plasters and mortars are therefore highly susceptible to chemical weathering (dissolution) and
loss of structural stability, particularly in humid
Precipitation of gypsum reduces the activity of

both Ca2+ and SO42- in solution, which further
95

environments and outdoors exposure. Although

they undergo very similar decay problems as
those of lime mortars, they are however less
sensitive to air pollutants (Sayre 1976).
de (Ca(OH)2), the mineral portlandite, also

known as slaked lime or hydrated lime
(Boynton 1980; Grate Rojas 1994). This term
also applies to the products of the hydration of
Ca and Mg oxides formed after the calcination
of magnesium limestone and, in particular,
dolomite (CaMg(CO3)2). Calcitic lime is commonly known as fat lime, while dolomitic or
magnesian limes are commonly called magre
limes (Cowper 1927; Grate Rojas 1994).
Gypsum can undergo deliquescence and reprecipitation under fluctuating relative humidity
(RH) conditions. Its equilibrium relative humidity
(RHeq) at 25C is 99.9 %, so when the RH is
higher than its RHeq, gypsum crystals dissolve.
When the RH drops, crystals reprecipitate as a
non-coherent powder, and may even induce
crystallization damage (salt weathering) when
they grow within the pores of adjacent building
materials (mortar, bricks or stone) (Charola et
al. 2007). At T > 42C, transition to anhydrite
can take place, thereby resulting in a significant
weakening of the material. Such a transition can
also occur at lower T if RH < RHeq (Charola et
al. 2007).
Archaeological evidence shows that lime was

used in the construction of some of the floors
and paving of the ruins excavated in
atalhyck (Mellaart 1967), dated between
10000 and 5000 BC (Von Landsberg 1992;
Kingery et al. 1998). These archaeological findings, along with the remains of 4500 years old
lime kilns found in Khafaje, Mesopotamia, confirm that lime was a common building material
in the Levant during the Neolithic (Davey 1961).
Little has been published on the conservation of

gypsum plasters and mortars. In general, lost
material tends to be replaced with new gypsumbased materials. Consolidation and protection
of this type of building and decorative material
has been performed using the same approaches used for other materials such as stone or
lime mortars (Sayre 1976; Ashthur 1990;
Cotrim et al. 2008). Much research is needed
to develop and apply specific conservation treatments for gypsum-based materials. Van
Driessche et al. (2012) recently reported the
direct precipitation of nanosized bassanite
which eventually transforms into gypsum at
room T. This technology offers a new, potentially
effective way to consolidate gypsum-based building materials via the application of a suspension of nanosized bassanite. When transformed
into gypsum, it could act as a consolidant in a
similar manner as nanolimes applied on porous
building materials (see section 3.5).
The Egyptians also used lime as a binder.

Some coatings of lime in different pyramids
have been dated ca. 4000 BC (Boynton 1980).
However this is challenged by Lucas and Harris
(1962) and Ghorab et al. (1986) who indicate
that the Egyptians did not use lime in construction (they used gypsum) until Roman times.
Other ancient civilizations, like India, China and
the different cultures of pre-Columbian America
(e.g., Mayans and Aztecs) systematically used
lime as a building material (Grate Rojas
1994).
The type of lime first used hardened when exposed to air, and was called air lime. The Greek
and Roman civilizations discovered that calcination of marly limestones, i.e., with a concentration of aluminosilicates (clays) > 10 wt %,
yielded a binding material that hardened underwater (hydraulic setting) and had improved
mechanical properties (Malinowski 1981).
3. Lime binders
Upon calcination of impure limestones, clays

dehydroxylate at 400 to 600C. The resulting
silica and alumina combine with CaO formed
after the decomposition of CaCO3 at 950 to
1250 C, to produce calcium aluminates and
silicates (Callebaut et al. 2001). These limes
are called natural hydraulic limes. Dicalcium
silicate (C2S) is the main phase that reacts with
water causing their hydraulic setting, unlike in
3.1. Lime-based building materials: definitions, history and uses

The term lime s.l. refers both to calcium oxide
(CaO) or quicklime, the product of the calcination of calcium carbonate (calcite or aragonite:
CaCO3), and to the compound obtained after
the hydration of the oxide, i.e. calcium hydroxi-
96
Seminario SEM 09
(hydraulic setting) and acquired the strength of

Portland limestone, one of the most resistant
stoned used in British architecture, hence the
name "Portland cement". See details on such
pioneering works in the report by Haswell
(1865). The homogeneity and uniform properties, easy of application and high mechanical
strength after a rapid setting explains the
immediate success and massive use of
Portland cement until present day.
the case of cement where tricalcium silicate

(C3S) is the main hydraulic phase (Callebout et
al., 2001).
In addition to natural hydraulic lime, the socalled artificial hydraulic limes have been also
used. They were discovered by the Phoenicians
and perfected by the Greeks and the Romans.
Artificial hydraulic limes were obtained by
mixing lime with a pozzolanic material, name
taken from the town of Puzzoli, located nearby
the Vesuvius in Italy, where a tuff with high
hydraulic capacity was extracted. A pozzolanic
material contains highly reactive silica and alumina. When combined with Ca(OH)2 in the presence of water generates new products, mainly
hydrated calcium silicates and aluminates, with
superior binding or cementing properties
(Mertens et al. 2009).
However, in recent decades, lime has reemerged as the optimal material for the conservation of historic structures and buildings
(Teutonico et al. 1994), replacing cement in
such interventions. There are several reasons for the revival of lime (Elert et al. 2002).
Compared with cement, lime is more compatible from a mechanical, physical and chemical point of view when applied in historical
structures (brickworks and/or stone) (Elert et
al. 2002; Lanas and Alvarez 2003; Hansen et
The Greeks used the so-called "Santorini

earth, a tuff, as a puzolanic additive mixed
with lime for the manufacture of hydraulic lime
mortars as those found in Thera (Santorini,
Greece) (Alejandre Snchez 2002). The
Greeks also used a technique called "polishing" consisting in the application of coatings
made of lime and crushed limestone mixed
with pozzolana (Malinowski 1981; Alejandre
Snchez 2002). The Romans used lime in
construction since the last two centuries of the
Republic (200-100 BC). In addition to air lime,
they routinely used lime mixed with either natural (pozzolana s.s.) or artificial (brick powder)
pozzolanic materials, thus obtaining the wellknown opus ceamentitious and the cocciopesto described by Vitruvius (30 BC).
After the fall of the Roman Empire, natural and
artificial hydraulic limes, including Roman
cement, together with traditional air lime were
the most common binders in construction
since Byzantine time, though the Middle ages,
Renaissance and Baroque, until the discovery
of Portland cement in the early 19th century by
Aspdin (Lea 1970).
However, since mid-18th century, traditional
limes began to be replaced by high performance artificial hydraulic limes, made by researchers such as Smeaton (1791) or Vicat (1837).
In 1824 Aspdin patented a process for obtaining a cement which hardened under water
Fig. 3. Examples of the high incompatibility between Portland cement

and historic structures: a) Portland cement applied on serpentine and
marble at the Chancilleria (Granada, Spain); b) salt efflorescence and
detachments associated to Portland cement applied on limestone
ashlars (Granada Cathedral, Spain).
97

Fig. 4. The lime cycle: Electron microscopy images show reactant and products of the different stages of the cycle. ACC: Amorphous
Calcium Carbonate.
3.2. The lime cycle
al. 2008). For instance, the absence of alkalis and sulfates in lime prevents salt weathering due to the formation of deleterious carbonates and sulfates of Na/Ca or Mg, as can
be seen after the application of Portland
cement (i.e., Rodrguez-Navarro et al. 1998;
Maravelaki-Kalitzaki et al. 2003; Hansen et
al. 2008). Crystallization of such salts causes extensive damage in both new construction and historic structures (Fig. 3).
The lime cycle consists of three stages (Fig. 4):

calcination;
hydration or slaking; and
carbonation (or air setting).
Below we will present a detailed description of
each stage of this cycle.
3.2.1. Calcination
In successive sections recent advances in

the study of air limes are presented. We will
focus on the case of high calcium or calcitic
limes as these have been the most profusely
used by mankind and tend to be preferably
applied in architectural conservation (Hansen
et al. 2008).
The first stage of the lime cycle involves the

calcination of limestone at a sufficiently high
temperature as to cause the decomposition of
calcite according to the reaction:
CaCO3 # CaO + CO2' (4)
The most impor tant aspects that determine

lime proper ties, reactivity, applicability and
suitability as a binder in conser vation will be
studied within the framework of the "lime
cycle". Finally we will discuss aspects related to recent studies on the characteristics
of historic lime mor tars, and the design and
testing of conser vation mor tars as well as
methods for their actual consolidation and
protection.
This reaction is strongly endothermic, so the

production of calcium oxide requires high
energy consumption and the use of suitable
kilns. Traditional lime kilns involved the firing
of wood or coal along with limestone blocks,
resulting in lime mortars with a high content
of ash (Luxn and Dorrego 1996). Kilns used
since the industrial revolution placed the fuel
and the limestone in separate compartments
(Boynton 1980). Thus, the resulting limes do
98
Seminario SEM 09
sition process and reduce calcination T (Beruto

et al. 2003). The characteristics of the oxide
product are strongly dependent on T and duration of the calcination process (Boynton 1980).
CaO crystals formed a low T, and/or after a
relatively short period of calcination, are nanosized, show a very porous structure and are
highly reactive (Fig. 5a).
not present any ashes and have homogeneous characteristics, something difficult to
achieve through the use of traditional kilns.
The temperature of dissociation of CaCO3 is
898C at pCO2 = 1 atm. This T is reduced the
lower the pCO2 is, and increases as pCO2 increases (Boynton 1980). CO2 released by carbonate decomposition (plus CO2 generated by the
combustion of wood or coal in traditional kilns)
must be evacuated to avoid the re-carbonation
of CaO, or to hinder carbonate decarbonation.
Calcination in air at T above 900C and/or

during long periods of time favors the oriented
aggregation of CaO nanocrystals and the subsequent
sintering
and
densification
(Rodrguez-Navarro et al. 2009). These phenomena can lead to the formation of completely
inert or "dead burnt" CaO at T ca. 1400C. In
The presence of other gases, e.g. water vapor

released during the combustion of wood in traditional lime kilns, may speed up the decompo-
Fig. 5. The thermal decomposition of calcte: a) SEM image of the porous structure of CaO cr ystals formed after calcite (see pseudomorph in inset). Preferred orientations of CaO cr ystals are indicated with arrows. The left inset shows the (100) pole figure of CaO
cr ystals with a preferred orientation with respect to the parent calcite (the projection plane is parallel to the cleavage plane of calcite);
b) TEM photomicrographs of oriented CaO nanocr ystals formed upon calcite decomposition following e-beam irradiation in the TEM
chamber. Insets show the corresponding SAED pattern of precursor (calcite) and product (CaO) phases. Four sets of product CaO
cr ystals with preferred cr ystallographic orientation are identified in the SAED as shown by the orientation of their reciprocal lattice vectors (1 to 4); c) projection of the calcite structure on the cleavage plane; d) loss of CO2 from former CO32- groups in the calcite (10.4)
planes; and e) final transformation (via a topotactic mechanism) into oriented CaO cr ystals. Modified from Rodrguez-Navarro et al.
(2009).
99

general, the most reactive limes are those

subjected to a relatively "soft" calcination process ("soft burning") (Boynton 1980).
An adequate knowledge of the mechanism of
CaCO3 calcination is crucial to optimize this
process and to obtain oxides with desired properties. Despite many studies, there is no
consensus on how such a reaction occurs
(Rodrguez-Navarro et al. 2009). We recently
investigated the thermal decomposition of calcite, both studying the kinetics of the reaction
and its textural and microstructural aspects
(Rodrguez-Navarro et al. 2009). X-ray diffraction (XRD), two-dimensional XRD (2D-XRD),
scanning (FESEM) and transmission electron
microscopy (TEM-SAED) allowed us to determine that the calcination of calcite is pseudomorphic and topotactic (Figure 5b).
The release of CO2 from CO32- groups existing
along the (10.4) planes of calcite, results in a
realignment of oxygen and Ca atoms to form
CaO nanocrystals that preserve a close
crystallographic relationship with the parent
calcite crystal (Figure 5c-e). Pseudomorphs
are highly porous (up to 54% porosity) due to
the molar volume difference between calcite
and calcium oxide. CaO nanocrystals (initially
with size ca. 5 nm and with surface area of up
to 80 m2/g) show the following crystallographic relationships with the precursor calcite:
{10.4}calcite//{110}CaO
and
<4- 41>calcite//<110>CaO. These results enabled us to
propose a new model for the thermal decomposition of calcite, which is schematically
shown in Fig. 5.
The nanosized character of CaO crystals formed topotactically pre-determines the kinetics
of the following stage of the lime cycle,
namely, the hydration step, as well as the properties of the resulting hydroxides. On the
other hand, the close textural and crystallographic relationship between carbonate and
oxide crystals means that the textural and
microstructural characteristics of the carbonate will largely determine the properties of the
resulting oxides. This assertion is corroborated by various studies showing that the surface area, porosity, pore size and crystal size
distribution of the carbonate rock, in addition
to the presence of impurities, determine the
properties, in particular the reactivity, of product calcium oxide (Elert et al. 2002).
Depending on the composition and textural
characteristics of carbonate rocks, it will be
therefore necessary to establish the optimal
parameters for calcination (temperature and
duration) (Boynton 1980).
3.2.2. Hydration
In contact with water calcium oxide reacts forming calcium hydroxide (Ca(OH)2), the mineral
portlandite, according to the reaction:
CaO + H2O # Ca(OH)2
(5)
Reaction (5) is highly exothermic. Thus, safety

precautions have to be taken during traditional
lime slaking, both due to possible burns and to
the corrosive effect of splashes (pH 12.4). If the
hydration occurs with the stoichiometric amount
of water, a dry powdered precipitate is formed.
Dry hydrate is the standard industrial product
nowadays. If excess water is added, the final
product is an aqueous dispersion of hydroxide
crystals. This way a lime paste (or lime putty) is
formed.
There are numerous studies on the effect of
oxide/water ratio, oxide grain size, temperature
of water, presence of alcohol or additives in the
slaking water, and agitation in the properties of
the hydroxide formed after slaking (see review
by Elert et al. 2002).
Various mechanisms for the transformation of
calcium oxide into portlandite have been proposed (Ramachandran et al. 1964; Beruto et al.
1981; Wolter et al. 2004; Sato et al. 2007). It
appears that a part of Ca(OH)2 directly precipitates from the supersaturated solution formed
upon dissolution of CaO in the slaking water.
However, there is evidence suggesting that the
hydration of a considerable amount of CaO
occurs as a solid state reaction between the
oxide and water vapor generated as a result of
the increase in temperature experienced during
hydration (Wolter et al. 2004).
Yet, it is not clear how these two processes
occur and what their relative merit is in the overall slaking process. Beruto et al. (1981) propo-
100
Seminario SEM 09
se that vapor phase hydration of CaO is controlled by the structure of the reactant and product,
being a pseudomorphic reaction that generates
nanometric Ca(OH)2 crystals. It could be hypothesized that given the structural similarity between (111)CaO and (001)Ca(OH)2 planes, the
replacement of O= in the oxide by OH- groups
could easily result in the topotactic formation of
portlandite. This would imply that the microstructural characteristics of the oxide would be
(at least partially) inherited by the hydroxide.
This mechanism could help to explain why
depending on the characteristics of the oxide
(e.g., surface area, porosity and particle size)
hydrated limes with different properties are
generated, even when slaking is performed
under identical conditions (Elert et al. 2002).
Rodrguez-Navarro et al. (2005) have shown

that there are significant microtextural differences between traditional slaked limes (lime putties) and commercial (powder) hydrated limes.
The formers have a greater proportion of particles with size < 1 m. Apparently, the drying process undergone by dry hydrated limes results in
both reversible (non-oriented) and irreversible
(oriented) aggregation of portlandite crystals.
Oriented aggregation results in an increase of
the effective size of Ca(OH)2 particles (aggregates), which results in a significant reduction of
surface area and reactivity, and a worsening of
rheological properties (viscosity, plasticity and
workability) (Ruiz-Agudo and Rodrguez-Navarro
2010). This is consistent with studies carried
out at the beginning of the 20th century which
concluded that slaked lime behaved as an irreversible colloid once dried (Ray and Mathers
1928).
In the case of lime putties, there is a range of
phenomena that occur after slaking if the paste
is kept underwater during long periods of time
(months or years). This is the so-called
ageing, which was used since Roman times to
improve the properties of slaked lime (Cowper
1927; Ashurst 1990). Pliny indicates that there
was a law in ancient Rome which established
that lime putties should be "aged" for at least
three years prior to their application (RodrguezNavarro et al. 1998).
This tradition, based on empirical observations,
has survived to our day. However, until relatively

recently, there were doubts about whether or
not ageing produced any improvement in the
properties of lime paste, and if this was the
case, it was not known which was the cause
and/or mechanism of such improvement.
Rodrguez-Navarro et al. (1998) showed that
after ageing of lime pastes for 2 to 10 months,
there was a reduction in the size of portlandite
crystals and an increase in their surface area.
Planar (hexagonal platelets) with overdeveloped
{0001} forms appeared in parallel with the
disappearance of larger prismatic crystals.
Preferential dissolution of the prism faces along
(0001) planes resulted in an overall increase in
the amount of plate-like portlandite crystals. In
addition, secondary precipitation of sub-micrometric, planar portlandite crystals also occurred
during ageing. All these smaller planar crystals
led to an overall increase in surface area, reactivity, dynamic viscosity and plasticity
(Rodrguez-Navarro et al. 2009; Atzeni et al.
2004; Ruiz-Agudo and Rodrguez-Navarro
2010).
However, Ruiz-Agudo and Rodrguez-Navarro
(2010) indicate that depending on the characteristics of the oxide (hard vs. soft burnt lime), the
rheological evolution of slaked lime putties was
different, although in all studied cases a general improvement was observed after long
periods (several months) of ageing.
3.2.3. Carbonation
Carbonation of calcium hydroxide in the presence of atmospheric CO2 occurs according to the
overall reaction:
Ca(OH)2 + CO2 # CaCO3 + H2O
(6)
The resulting CaCO3 crystals act as a binder or

cement due to their interconnected microstructure (Beruto et al. 2005) joining the rest of the
elements in the mix (aggregate).
The setting of air lime mortars and plasters
begins with an initial period of drying and shrinkage and is followed by the carbonation reaction. The reaction interface advances through
the porous system from the surface towards
the unreacted core. This process consists of
several steps:
101

(i) diffusion of CO2 (gas) through the open

pores,
(ii) dissolution of Ca(OH)2 in the pore water,
(iii) absorption and dissolution of CO2 in the
alkaline pore water forming carbonic acid
H2CO3;
(iv) its immediate dissociation into bicarbonate and carbonate ions,
(v) reaction between Ca2+ and CO32 ions forming CaCO3 through nucleation and growth.
All these processes are interrelated and altering
the kinetics of one process influences the
others (Van Balen and Van Gemert 1994;
Cultrone et al. 2005; Cizer et al. 2012).
The volume, geometry and size of the pores, as
well as the water content, play an important
role in the progress of carbonation. This is primarily due to the fact that water largely controls
the rate of CO2 diffusion, which along with CO2
dissolution (forming carbonic acid) are rate
determining steps for carbonation. As water
evaporates during drying, an effect which is
promoted by the exothermic nature of carbonation (Moorehead, 1986) and the less hydrophilic character of newly-formed CaCO3 if compared with Ca(OH)2 (Beruto and Botter 2000;
Beruto et al. 2005), pores tend to stay open.
This accelerates CO2 diffusion towards the
interior of the material which is carbonating.
However, the porosity is slightly reduced due to
the precipitation of CaCO3 crystals, which have
a molar volume 11.7% higher than that of
Ca(OH)2 (Moorehead 1986). Overall the kinetics
of carbonation is very slow, an the reduction in
pore size (Lawrence et al. 2007) could further
contribute to a reduction in carbonation rate
over time. This may help explaining why uncarbonated portlandite has been found in lime mortars several centuries old (Marchese 1980),
although this is a matter of controversy (Adams
et al. 1998).
CaCO3 formed after carbonation may appear
as three anhydrous polymorphs, calcite, aragonite and vaterite, depending on the conditions of the reaction, (i.e. pH, T, supersaturation) and the presence of impurities or additives. Calcium carbonate may also precipitate
as an amorphous phase (Amorphous Calcium
Carbonate, ACC), which is hydrated and
metastable. ACC, which usually precipitates

as small spheres of less than 1m in diameter, turns into calcite as the reaction progresses. As we will see later, this phase seems to
play a key role in the process of carbonation
of Ca(OH)2 (Cizer et al. 2012).
The textural characteristics of CaCO3, as well
as the cementing structure formed after carbonation, appear to depend on the properties
and characteristics of precursor portlandite
crystals and on the conditions of carbonation
(i.e., water content, T and RH, pCO2, pH, and
ionic activity). There are studies on the
effects of the size, surface area, and habit of
portlandite crystal on the kinetics of carbonation. In general, the smaller the portlandite
crystals are, the higher their reactivity during
carbonation is (Van Balen 2005). In turn, the
textural features of the portlandite precursor
and the kinetics of carbonation determine the
physical and mechanical properties of limebased materials (Cizer et al. 2012).
Regarding the mechanisms of Ca(OH)2 carbonation, two possible routes exist: a) precipitation in solution and b) replacement of portlandite by calcium carbonate. The latter can
occur either via a solid state reaction (Gillott
1967; Matsuda and Yamada 1973;
Moorehead 1986) or through a tightly coupled process of dissolution/precipitation
(Putnis 2009).
Carbonation in solution has been thoroughly
studied because it is important in the industrial precipitation of calcium carbonate used
in paper, paint, plastic and pharmaceutical
industries (see overview by Cizer et al.
2012).
This reaction takes place according to the
Ostwald rule of stages following the precipitation sequence:
ACC # vaterite # (aragonite) # calcite
(Ogino et al. 1987). Some studies show the
initial precipitation of ACC nanoparticles in
lime mor tars subjected to carbonation
(Rodrguez-Navarro et al. 2002; Cizer et al.
2012), which is followed by the formation of
scalenohedral and, finally, rhombohedral cal-
102
Seminario SEM 09
cite crystals (Cultrone et al. 2005; Cizer et al.

2012) (Fig. 4).
Occasionally, the formation of aragonite or
vaterite has been observed (Zanco 1994). It
should be noted that the use of a calcitic
aggregate may promote the direct epitaxial
(homoepitaxial) precipitation of calcite, i.e.,
not following the Ostwalds rule. Such a
regrowth should generate a coherent interface between the aggregate and the binder.
This could help to explain why conservation
lime mortars prepared with calcitic aggregates tend to show a higher strength than those
prepared using dolomitic or siliceous aggregates (Lanas and Alvarez 2003).
With respect to the second mode of carbonation, that is, the transformation in solid state
or via coupled dissolution/precipitation, there
is no consensus on what is the actual mechanism of reaction. Gillott (1967) and Matsuda
and Yamada (1973) indicate that in the presence of low amounts of water, portlandite
crystals transform into calcite through a solid
state reaction controlled by the structure,
i.e., topotactic transformation. In his classic
study, Moorehead (1986) indicates that in
addition to the precipitation of calcium carbonate in solution, which he considered a
secondar y process, carbonation occurred
following a solid state replacement.
Nonetheless, he noted that water was necessary for the reaction to progress. This casts
some doubts about the solid state nature of
the carbonation process. Beruto and Botter
(2000) and Beruto et al. (2005) show that
carbonation was significantly accelerated for
RH values > 75%, when more than 4 H2O
monolayers were adsorbed onto portlandite
crystals. Ca(OH)2 dissolution into the adsorbed water enabled the carbonation to progress at a sufficiently high speed. This
implies a pseudomorphic replacement via
coupled dissolution/precipitation, which
should be much faster than a solid state
reaction (Putnis, 2009).
Beruto et al. (2005) called attention to the fact

that the direct precipitation of calcite from a saturated Ca(OH)2 solution generates dispersed particles, without any degree of cohesion or mechanical resistance, while through a mechanism of
pseudomorphic replacement, as described

above, a very cohesive and mechanically resistant paste of calcium carbonate is obtained.
Although the mechanism of carbonation via this
pseudomorphic replacement is not yet fully
understood, it has very important implications.
Amongst them are the following: the size, morphology and level/type of aggregation of calcium
hydroxide crystals determine how it will be the
texture and microstructure of calcite crystals formed after carbonation. This may help explaining
why depending on the type of calcitic slaked lime,
mortars with different properties and durability
are obtained after carbonation.
For instance, mortars prepared with aged
lime putties show faster carbonation and a
higher mechanical strength than mortars prepared with fresh lime putties or with dry
hydrate (Cazalla et al., 2000). RodrguezNavarro et al. (2002) show that mortars prepared using aged lime putty (16 y old) display
a carbonated structure which resembles
Liesegang patterns, which is also observed
in historical buildings (Fig. 6). The authors linked the formation of the Liesegang pattern
with the microtextural characteristics of aged
portlandite crystals.
3.3. Historic lime mortars and plasters

The study of lime mortars and plaster collec-
Fig. 6. Formation of a Liesegang pattern in carbonated lime mortars

prepared with 16 y old lime putty: a) scheme of a mortar prism; b) section of the prism after 1 y carbonation following phenolphthalein
impregnation. The red rings correspond to uncarbonated parts, while
the whiter rings are fully carbonated (modified from Rodrguez-Navarro
et al., 2002); c) example of Liesegang pattern following differential
weathering in lime plasters in a historical building (Saint Maria Church,
Utrera, Spain) (modified from Hansen et al., 2008).
103

ted from historical buildings has been a constant in recent decades, highlighting their tremendous compositional variety, both depending on location and age (Elsen 2006).
et al. 1995; Bakolas et al. 1995a,b, 1998;

Riccardi et al. 1998; Franzini et al. 1999;
Maravelaki-Kalaitzaki et al. 2003; Elsen 2006;
Edwards and Farwell 2008).
The study of such materials, which in many

cases present major alteration problems, is
justified for several reasons. First, the study of
lime-based materials with different age, provenance and uses is of importance from a historical and architectural point of view. On the
other hand, their analysis can help identify what
components were historically used in the production of lime mortars and plasters, and shed
light on the manufacturing technology.
Goins (2000) proposed a complete analytical

protocol for the study of both modern and
ancient lime mortars. It is not our intention to
make an extensive review of these publications. The interested reader is refereed to the
Getty Conser vation Project Bibliography
Series Preservation of Lime mortars and
plaster (http://www.getty.edu/conser vation/publications_resources) and the review
by Elsen (2006). Here, however, a few
aspects of the study of old lime mortars will
be reviewed to get an insight into the importance of this field.
This information is critical if we are to reproduce such materials with a view to their application in architectural conservation interventions.
In this respect, the Venice Charter (1964)
recommends the use of materials and technologies the closest to those originally used in the
making of the element to be conserved.
The number of published studies on limebased materials, mostly mortars, used in historical buildings from prehistory to practically
our days, is large, and has steadily increased
over the last two decades.
Analytical techniques such as polarized light
microscopy (see an example in Fig. 7), scanning
and transmission electron microscopy, x-ray diffraction, termogravimetry, differential thermal
analysis, infrared (FTIR) and Raman spectroscopy, x-ray fluorescence, atomic absorption
spectrometry, and calcimetry, among others,
have been used to study the composition and
microstructure of old lime mortars (Moropoulou
Fig. 7. Optical microscopy photomicrograph of a lime mortar from the

walls of the IX c. Castle of Caete la Real (Malaga, Spain). Plane light.
An interesting aspect of ancient lime technology refers to the slaking of quicklime mixed
with the aggregate before adding water. This is
the so-called "hot lime" technology
(Moropoulou et al. 1996). A variation is called
dry slaking, which involved the mixing of
quicklime with a wet aggregate (Elsen 2006).
Apparently it was a common slaking method
and generated mortars of excellent quality and
durability (Moropoulou et al. 1996). Such a
slaking process could have produced alkaliaggregate reactions between lime and siliceous sand (Armelao et al. 2000), favored by the
high temperature reached. Margalha et al
(2011) have carried out laboratory studies on
the potential benefits "hot lime" technology
can have in the case of air lime mortar mixed
with siliceous sand. Their results, however, do
not show that this technology impart any clear
advantage to these mortars. In contrast,
Malinovski and Hansen (2011) conclude
recommending the use of hot lime technology
for conservation lime mortars.
A large number of studies, such as those of
Bakolas et al. (1995a, 1995b, 1998) on
Byzantine and post-Bizantine lime mortars, or
Moropoulou et al. (1996) show that, in addition to air lime mortar, many of the mortars
of such times included lime mixed with ceramics, crushed or powdered. In general, it
appears that the use of artificial hydraulic
lime mortars was much more common after
the fall of the Roman Empire than previously
104
Seminario SEM 09
thought (Elsen 2006).
Bakolas et al. (1995b) studied 14th to 18th c.

Venetian mortars, and concluded that one of
the most distinctive features in historic lime
mortars is the presence of whitish nodules
(lumps) with dimensions ranging between a
few mm and 1 or 2 cm. These nodules are
composed of calcite, so they could either
correspond to fully carbonated slake lime
lumps, or uncalcined limestone chips.
The presence of traces of silicates (hydraulic
phases), a high porosity and numerous fractures
suggest that these nodules correspond to slaked lime lumps that did not dissagregate upon
mixing with sand and water (Franzini et al. 1999),
possibly due to the lack of aging of the original
lime which displayed a low plasticity (Tuncoku
and Caner-Saltik 2006). Alternatively, they could
be the result of the hot lime or dry slaking technology (Bakolas et al. 1995a, 1998). Local overheating during dry slaking could provoke an
agglomeration of the hydrated lime particles,
causing the formation of such nodules.
Regarding the formulation of historical lime
mortars, classic treaties such as those of
Vitruvius (30 BC) and Alberti (1452), established that 1:3 was the optimal binder to aggregate ratio. However, many researchers have
found that, in general, Roman and Greek lime
mortars with considerable age difference had
very similar textural and compositional characteristics, among which it is highlighted that the
binder/aggregate ratio was higher than 1:3,
typically 1:2 (Foster 1934; Elsen 2006).
Another important aspect of old lime mortar
technology refers to the use of additives (we
do not consider here those imparting hydraulic character). Typically, organic additives
were dosed in the lime mix to improve the
mortar properties both in the fresh and hardened state. Examples of such additives are:
egg white, blood of ox, juices of various fruits
such as figs, keratin and casein, oils from
plants (e.g, linseed oil), and animal fats,
among others (Moropoulou et al. 2005).
For instance, both Aztecs and Mayans used
nopal juice (Oppunctia ficus indica), which is
very rich in pectin, as an additive in preparing
lime mortars and plasters of high plasticity

and capacity to avoid cracking during drying,
tradition which is currently preserved in different parts of Mexico and the United States
(Crdenas et al. 1998).
Researchers have attempted to reproduce
traditional building practices using natural
additives to improve the performance of lime
used in architectural conservation. For example, Yang et al. (2010) used the ancient
China vernacular sticky rice technology for
improving the performance of new conservation lime-based mortars. The presence of
amylopectin in the rice caused the formation
of a matrix of calcite nanocrystals which granted an enormous strength and durability to
such conservation mortars.
Modern, both natural and artificial, organic
additives have been also tested for improving
the performance and properties of limebased conservation mortars. For instance,
Izaguirre et al (2010) noted an increase in
plasticity, adhesion, durability and mechanical strength of lime mortar dosed with potato
starch, plasticizers, air-entraining agents and
water repellents.
3.4. Lime-based conservation mortars

The study of old lime mortars have yielded a
significant amount of information which has
been applied for the design of new lime-based
conservation mortars.
To be compatible with old masonry and to play
a proper role, restoration mortars must meet
a series of requirements, among which the
following can be highlighted (Maurenbrecher
2004):
(a) the mortar should not have a higher
strength than stone or brick: a conservation mortar is not "better" the stronger it
is;
(b) the water absorption and water vapor
permeability of the mortar must be of the
same order of magnitude or greater than
that of the other masonry elements. This
favors the accumulation of water (and
salts) in the mortar which may act as a
sacrificial material;
105

(c) mortars must have a minimum retraction

to prevent crack development;
(d) should ensure a good contact with bricks
or stone. This is favored by a high plasticity
and workability;
(e) in general, its physical properties (thermal expansion, color, etc) should ensure a
high compatibility with the different elements in the old masonry structure, while
ensuring that the mortars is sufficiently
durable. This is particularly relevant in
cases where loss of mortar is so general
that the survival of the whole masonry
structure is in jeopardy (Fig. 8).
the mechanical behavior of air lime mortars

(Lawrence and Walter 2008). Nonetheless,
Arandigoyen et al. (2005) show that increased
water/lime ratios increase the mortars porosity, an effect which could be detrimental in
the presence of ice or soluble salts. It seems
that depending on the type of lime, water requirements vary. A method to overcome such an
effect is to prepare mortars with a standard
consistency (Hansen et al. 2008). A precaution to consider is the purity of the water used.
Vitruvius recommended the use of high purity
sand without fines, discarding the use of sea
water due to the harmful effect of salts.
A consensus exists on the need of using conservation lime mortars with formulations and
manufacturing / application techniques as
similar as possible to the traditional ones. For
example, it is generally recommended the use
of calcitic lime pastes, especially those that
have undergone aging. Faria et al. (2008) note
that resistance to salt crystallization damage
is significantly higher in mortars prepared with
lime pastes aged for 10 to 16 months if compared with mortars prepared with commercial
dry hydrate. There is however no consensus
on what is the optimal aging time. The golden
rule should be the longer the better. However,
from a practical point of view, a period between 2 and 10 months aging brings about a significant improvement (Rodrguez-Navarro et al.
1998). Ashurst (1980) recommends a minimum of three months ageing period.
With regards to the most appropriate binder/aggregate ratio in conservation mortars

and how it affects the mortar properties,
there are mixed results. Classically, the use
of a 1/3 (lime/sand) ratio was recommended
as indicated by Vitruvius and Alber ti.
However, Lanas and Alvarez (2003) demonstrate that the best physical-mechanical properties are achieved when a binder/aggregate ratio of 1:1, or even 2:1, is used. However,
other authors such as Cazalla et al. (2002)
note that the best mortars (in terms of speed
of carbonation and mechanical properties)
are those with a 1:4 ratio. Note that Lanas
and Alvarez (2003) used hydrated lime powder, while Cazalla et al. (2002) got the best
mortars using lime putty aged for 14 years. It
follows that depending on the type of lime
used, and the final application of the conservation mortar (joint mortar, repointing, sacrificial layer, or plaster), the binder/aggregate
ratio has to be gouged.
In addition to slaked lime, conservation mortars and plasters include water and aggregate.
Unlike in the case of Portland cement, water
content does not appear to appreciably affect
The aggregate is another important component of a conservation lime mortar. The aggregate is added to reduce costs, to minimize the
formation of drying cracks, and to provide proper consistency in the fresh state, and adequate strength and permeability (porosity) after
setting. The type of sand is highly variable.
Cowper (1927) in his classic report provides
some general rules for the selection of proper
sand (see also Elert et al. 2000).
3.5. Decay and conservation of lime mortars

and plasters
Fig. 8. Ruins of the Castle of Caete la Real (Malaga, Spain). The
piece of wall shows extensive loss of joint mortar linking the stone
blocks.
Lime mortars and plasters suffer different
106
Seminario SEM 09
damaging processes when exposed both outdoors and indoors. These include chemical
(dissolution, sulfation in polluted environments),
physical
(thermal
changes,
freeze/thaw, salt crystallization) and biological (mechanical action of roots, degradation
by bacterial action) weathering processes
(Ashurst 1990; Furlan 1991; Doehne and
Price 2010). They cause loss of cohesion,
increase in porosity, and granular disintegration, among other phenomena.
Such a damage often entails the loss of
material, as it is shown in Fig. 8, so the more
common type of conservation intervention is
to reapply a new mortar or rendering prepared according to the guidelines referred to in
the previous section.
However, there are situations in which it is
necessary to consolidate the lime-based historical material. Studies dedicated to the consolidation and/or protection of lime mortars are
fairly limited when compared with studies dedicated to the design and testing of restoration
mortars. There are however some studies that
compare various types of products for the consolidation of historic lime mortar following an
approach very similar to that followed during
the consolidation of stone.
For example, Toniolo et al. (2011) have studied the effectiveness of different consolidants applied on lime mortars. The tested
consolidants were:
polyethylmetacrylate-methylacrylate copolymer (Erabiliz B72);
tetraethyl orthosilicate (RC 70 - TEOS);
saturated barium hydroxide solution.
Changes in color and mechanical properties
were evaluated after consolidation. With regard
to the appearance of the treated materials, the
best behavior was observed after the application of barium hydroxide. The highest increase
in strength was observed after the application
of TEOS, while the worst behavior was observed in the case of the barium hydroxide.
Inorganic consolidants such as lime water or
barium hydroxide have been thoroughly applied
on lime plasters. While the classic lime water
treatment seems to be highly ineffective, the

Ba(OH)2 treatment appears to be very promising (Doehne and Price, 2010). Carbonation of
this hydroxide leads to the precipitation of
cementing BaCO3. In the presence of sulfates,
highly insoluble BaSO4 is also formed which
contributes to the strengthening of the limebased material and limits salt damage.
Izaguirre et al. (2009) studied the effects of
some protective treatments (water repellants) applied to air lime mortars, observing
a significant improvement of the mortars
resistance to freeze/thaw cycles.
Treatment based on the application of alcoholic dispersions of Ca(OH)2 nanoparticles, the
so-called nanolimes, show some promising
results as a novel and effective consolidation
method for lime-based mortars, renderings
and plasters (Baglioni and Giorgi 2006). Yet,
much research has to be dedicated to the
study of novel, effective conservation treatments for the in situ consolidation and protection of lime-base building materials.
4. Concluding remarks
Mankind has used gypsum and lime binders for
decorative and structural purposes in historical
buildings since prehistory. Both binders share
some interesting features in their processing and
setting (e.g., the gypsum and the lime cycles). In
particular, their activation and settings show
some mechanistic similarities:
(a) their calcinations/dehydration is a solid
state process which follows a topotactic
mechanism, and
(b) their setting involves two different mechanisms, namely
(i) crystallization in solution, and
(ii) either a solid state reaction or a coupled
dissolution/precipitation process.
Lime is somehow different in that its cycle shows
an additional step of hydration, which from a
mechanistic point of view also involves precipitation in solution and another process which may
be either a solid state reaction or a pseudomorphic tightly coupled dissolution/precipitation.
Research should focus on elucidating which
107

one of the process already mentioned, i.e.,

solid state or dissolution/precipitation,
actually takes place, and how is the atomic
scale mechanism involved in such a process.
It is shown that due to the structural relationships between parent and product phases in
both gypsum and lime cycles, the properties of
the parent phases predetermine the properties
of the product phases. This has profound consequences on the performance of both ancient
and modern (conservation) gypsum- and limebased materials, and emphasizes the fact that
each stage of the two cycles has an effect on
the properties of the final set material.
An overview of the uses of both gypsum and
lime as binders in historical buildings, their use
in conservation interventions, and their actual
decay and conservation, shows that despite
the numerous research efforts that have taken
place over the last few decades, much is still to
be investigated. For instance, the development
of novel effective conservation methods for in
situ consolidation of both gypsum and lime building materials is still a challenge.
The study and testing of nanosized crystalline, or
even amorphous, precursors (bassanite, nanolimes) for the consolidation of gypsum and lime
mortars and plasters could be an interesting and
potentially fruitful research path worth to explore.
5. Acknowledgement
This research was financed by the EU Initial
Training Network Delta-Min (Mechanisms of
Mineral Replacement Reactions) grant PITNGA-2008-215360, the Spanish Government
(grant MAT2009-11332) and the Junta de
Andaluca (research group RNM-179).
Some of the results here presented were
obtained during the development of the Lime
Mortars and Plasters project, a joint collaboration between the Getty Conser vation
Institute, the Catholic University of Leuven
and the University of Granada.
Contributions by K. Elert, E. Hansen, K. Van Balen,
O. Cizer, E. Ruiz-Agudo, O. Cazalla, E. Sebastian
Pardo and K. Kudlacz are acknowledged.
6. References
Abriel, W., Reisdorf, K. and Pannetier, J. (1990)
Dehydration reactions of gypsum: A neutron and X-ray
diffraction study. J. Solid State Chem. 85, 23-30.
Adam, C.D. (2003) Atomistic modelling of the hydration of CaSO4. J. Solid State Chem. 174, 141-151.
Adams, J. Kneller, W. and Dollimore, D. (1992)
Thermal analysis (TA) of lime- and gypsum-based
medieval mortars. Thermochim. Acta 211, 93-106.
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Seminarios de la Sociedad Espaola de

Jos Miguel Herrero

Seminarios de la Sociedad de Espaola

Jos Miguel Herrero

Archaeomineralogy of prehistoric artifacts and gemstones.

Trace element geochemistry and mineralogy for solving problems in

Technology and Provenancing of French faience.

Archaeometallurgy: the contribution of mineralogy.

Microanalysis of pigments in art works.

Binders in historical buildings: traditional lime in conservation.

Archaeomineralogy of prehistoric artifacts and gemstones

ground in geology and mineralogy should

Besides it is particularly important that there

In recent years archaeomineralogy studies

Recent contributions as book edition of Rap

Increased interest from the field of

2. Application of mineralogical studies in

Mineralogical disciplines provide valuable

Ver y dif ferent mineralogical techniques

From the mineralogy and geology in general, it is possible to have a perception of

Depsito legal: CA-602-2004 / ISSN: 1698-5478

3. Analytical techniques at the

Fig. 2. Sample-holder for direct and non-destructive WDXRF analysis of

instruments in order to per form in-situ

Today a great effor t is being focused in the

We currently have a wide range of analytical

Fig. 1. Direct XRD analysis of archaeological objects. Sillimanite axe

Archaeomineralogy of prehistoric artifacts and gemstones

Fourier Transform Infrared Spectroscopy

Many examples of minerals and rocks used

Many of these or other qualitative, semiquantitative or quantitative techniques, classified as

There is a extensive bibliography on the characterization and identification of source

An important role is played by isotopic

The bulk of the analytical work on polished

Depsito legal: CA-602-2004 / ISSN: 1698-5478

rocks, has taken place on the most common

which would have given an adjudication of the

In recent years archaeomineralogical studies

To these obstacles we also have to add the fact

The study of the lithic industry has a strong

Mineralogical, petrological and geochemical

4.1. Archaeomineralogy of prehistoric artifacts,

From the end of the XIXth century to the

Archaeomineralogy of prehistoric artifacts and gemstones

al. 2012; Rubalcaba et al. 2008).

The study and determination of mineralogical

The size of the nodules of sillimanite seems

In the studies that we are doing since 1994

We are currently working on the possible

Within the group of analyzed knapped stone

4.2. Metamorphic rocks in the Atlantic Band of

Within these lithologies, generally scarce in the

4.2.1. Sillimanite/fibrolite, amphibolites, marbles

Depsito legal: CA-602-2004 / ISSN: 1698-5478

currently under study geochemical and mineralogical XRD-XRF and MO.

archaeological record of the Atlantic Band of

Regarding the articles made of marble, they

Notable examples in the minerals used in

4.2.2. Serpentinites and peridotites

They highlight examples such as jade in

Archaeomineralogy of prehistoric artifacts and gemstones

different methods of analysis of this mineral

field of mineralogy as OM, XRD, WDFRX,