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Geomaterials in Cultural Heritage

The Geological Society of London


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MAGGETTI, M. & MESSIGA, B. (eds) 2006. Geomaterials in Cultural Heritage. Geological Society, London, Special
Publications, 257.

SHORTLAND, A. J., HOPE, C. A. & TITE, M. S. 2006. Cobalt blue painted pottery from 18th Dynasty Egypt. In:
MAGGETTI, M. & MESSIGA, B. (eds) Geomaterials in Cultural Heritage. Geological Society, London, Special
Publications, 257, 91 - 100.
GEOLOGICAL SOCIETY SPECIAL PUBLICATION NO. 257

Geomaterials in Cultural Heritage

EDITED BY

MARINO MAGGETTI
University of Fribourg, Switzerland

and

BRUNO MESSIGA
Universit~ degli Studi di Pavia, Italy

2006
Published by
The Geological Society
London
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Contents

Preface vii

MAGGETTI, M. Archaeometry: quo vadis?


SMITH, D. C. A review of the non-destructive identification of diverse geomaterials in
the cultural heritage using different configurations of Raman spectroscopy

Pottery (BC)

BASSO, E., BINDER, D., MESSIGA,B. & RICCARDI,M. P. The Neolithic pottery of Abri 33
Pendimoun (Castellar, France): a petro-archaeometric study

LAVIANO,R. & MUNTONI,I. M. Provenance and technology of Apulian Neolithic pottery 49

MAGGETTI, M. & GALETTI,G. Late La Tbne pottery from western Switzerland: one 63
regional or several local workshops?

MOMMSEN, H., BONANNO, A., CHETCUTI BONAVITA, K., KAKOULLI,I., MUSUMECI, M., 81
SAGONA, C., SCHWEDT, A., VELLA, N. C. • ZACHARIAS,N. Characterization of Maltese
pottery of the Late Neolithic, Bronze Age and Punic Period by neutron activation analysis

SHORTLAND,A. J., HOPE, C. A. & TITE, M. S. Cobalt blue painted pottery from 18th 91
Dynasty Egypt

SHOVAL, S., BECK, P. & YADIN,E. The ceramic technology used in the manufacture of 101
Iron Age pottery from Galilee

SMITH, M. S. & TRINKLEY,M. B. Fibre-tempered pottery of the Stallings Island Culture 119
from the Crescent site, Beaufort County, South Carolina: a mineralogical and
petrographical study

Pottery (AD)

BIANCHINI, G., MARROCCHINO,E., MORETTI, A. & VACCARO, C. Chemical- 127


mineralogical characterization of historical bricks from Ferrara: an integrated
bulk and micro-analytical approach

~OLAK, M., MAGGETTI,M. & GALETTI,G. Golden mica cooking pottery from 141
Grkeyfip (Manisa), Turkey
vi CONTENTS

DELL'AQUILA, C., LAVIANO,R. & VURRO, F. Chemical and mineralogical investigations 151
of majolicas (16th-19th centuries) from Laterza, southern Italy

VENDRELL-SAZ, M., MOLERA, J., ROQUI~,J. & PI~REZ-ARANTEGUI,J. Islamic and 163
Hispano-Moresque (mfidejar) lead glazes in Spain: a technical approach

Glass

ARLETTI, R., CIARALLO, A., QUARTIERI, S., SABATINO, G. & VEZZALINI,G. 175
Archaeometric analyses of game counters from Pompeii

ERAMO, G. Pre-industrial glassmaking in the Swiss Jura: the refractory earth for the 187
glassworks of Derriere Sairoche (ct. Bern, 1699-1714)

FREESTONE, I. C. Glass production in Late Antiquity and the Early Islamic period: 201
a geochemical perspective

MARCHESI, V., NEGRI, E., MESSIGA, B. & RICCARDI, M. P. Medieval stained glass 217
windows from Pavia Carthusian monastery (northern Italy)

Stone

ANTONELLI, F., SANTI, P., RENZULLI,A. & BONAZZA, A. Petrographic features and 229
thermal behaviour of the historically known 'pietra ollare' from the Italian Central
Alps (Valchiavenna and Valmalenco)

BELLELLI, C., PEREYRA, F. X. & CARBALLIDO,M. Obsidian localization and circulation 241
in northwestern Patagonia (Argentina): sources and archaeological record

D'AMIco, C. & STARNINI,E. Prehistoric polished stone artefacts in Italy: a petrographic 257
and archaeological assessment

GANDIN, A., CAPEZZUOLI,E. & CIACCI,A. The stone of the inscribed Etruscan stelae 273
from the Valdelsa area (Siena, Italy)

MILLER, S., MCGIBBON, F. M., CALDWELL, D. H. & RUCKLEY, N. A. Geological tools 283
to interpret Scottish medieval carved sculpture: combined petrological and magnetic
susceptibility analysis

MORGENSTEIN, M. Geochemical and petrographic approaches to chert tool 307


provenance studies: evidence from two western USA Holocene archaeological sites

QUARESIMA, R., GIAMPAOLO,C. SPERNANZONI, F. & VOLPE, R. Identification, 323


characterization and weathering of the stones used in medieval religious architecture
in L'Aquila (Italy)

Mortar

CARO, F., DI GIULIO, A. & MARMO, R. Textural analysis of ancient plasters and mortars: 337
reliability of image analysis approaches

Index 347
Preface

The scientific study of monuments, as well as is dedicated to all scholars eager to undertake or
objects from excavations and museums, deals to continue an exciting research activity.
with their origin, technique, age and conser- Many colleagues helped us in the review
vation. Such topics were addressed during the process and we thank C. D'Amico, F. Antonelli,
one-day topical symposium 'Geomaterials M. Baxter, C. Belelli-Pereyra, G. Bianchini,
in Cultural Heritage' of the 32nd International G. Bigazzi, F. Car6, G. Eramo, I. Freestone,
Geological Congress held in Florence on 20-28 A. Gandin, K. Gherdan, B. Grob6ty,
August 2005. We have edited this volume by R. Heimann, A. Jornet, R. Laviano,
assembling papers of participants of the Florence L. Lazzarini, S. Miller, H. Mommsen,
meeting, as well as invited contributions, to R. Quaresima, M. P. Riccardi, G. Schneider,
present a wide view of the interdisciplinary V. Serneels, A. Shortland, S. Shoval, D. C.
application of geoscience disciplines, and to Smith, S. Smith, G. Thierrin-Michael, M. Tite,
reaffirm the important contribution of geo- S. Trfimpler, M. Vendrell-Saz, G. Wagner and
sciences to solve problems concerning the S. Wolf for their goodwill and rigorous review
study of complex materials such as minerals, of the submissions. We acknowledge the
rocks, glass, metals, mortar, plaster, slags and efficient assistance and the exemplary editorial
pottery. This interdisciplinary application of support of the Geological Society publishing
geosciences includes field geology, geophysics, staff (particularly Angharad Hills and Sally
microscopy, textural analysis, physical methods Oberst) and the remarkable technical help from
and geochemistry as fundamental support to Nicole Bruegger.
disclose hidden information, retained by the
ancient materials, such as the raw materials
provenance, the firing technology, the ancient Marino Maggetti
recipes and the alteration pathway. The volume Bruno Messiga
Archaeometry: quo vadis?

MARINO MAGGETTI
University of Fribourg, Department of Geosciences, Mineralogy and Petrography, Chemin du
Musde 6, CH-1700 Fribourg, Switzerland (e-mail: marino.maggetti@unifr.ch)

Abstract: First, a brief overview of the tasks and the historical development of archaeo-
metry will be given. Although archaeometry is generally doing well, a few issues currently
faced by this discipline will be outlined. These include: (1) funding for projects and research
positions; (2) the appeal of archaeometry to a new generation of academics; (3) the standard
of publications; (4) the safeguarding of and the immediate access to scientific data.

Scientific study of raw materials and products Tite 1972; Fleming 1976; Hrouda 1978; Goffer
used in prehistoric and historical time involves 1980; Riederer 1981a, 1987; Matteini & Moles
an interdisciplinary collaboration between 1984; Cuomo di Caprio 1985; Mommsen 1986;
archaeology, art history, preservation of the cul- Parks 1986; Wagner & Van den Haute 1992;
tural heritage, ethnography and science. This Taylor & Aitken 1997; Wagner 1998; Ciliberto
area of research, in which these disciplines & Spoto 2000; Barclay 2001; Brothwell &
overlap, is known as archaeometry or archaeolo- Pollard 2001; Martini et al. 2004).
gical sciences. The term geomaterials includes Apart from a multitude of papers published in
rocks, soils, mortars, pigments, ceramics, glass journals or books, there are many specifically
and slags. Scientific analysis of these objects geomaterial-related monographs, as well as pro-
aims at answering the following questions: ceedings from conferences. We shall name only
(1) Where does the raw material come from? a few of these and limit them to three domains
(2) Where was the object manufactured? (3) How as examples, because a complete listing would
was it manufactured (technique)? (4) What was go beyond the scope of this Introduction.
its purpose (function)? (5) When was it manufac-
tured (dating)? Scientific analysis should not Ceramics. Shepard 1956; Matson 1965; Brill
limit itself to the qualitative and quantitative 1971; Picon 1973; Rye & Evans 1976; Peacock
description of the 'chai'ne oprratoire'. Rather, it 1977, 1982; Winter 1978; Drmians
should approach these questions in a holistic d'Archimbaud & Picon 1980; Arnold 1981,
manner. This involves the socio-cultural environ- 1985, 1993; Howard & Morris 1981; Hughes
ment in which the artefact was manufactured 1981; Thompson 1982; Rice 1984, 1987, 1997;
(household, workshop, etc.), distributed and Kingery 1985, 1986a, b; Laubenheimer 1985,
used. Collaboration with archaeologists and art 1992, 1998; Empereur & Garlan 1986; Jones
historians needs to show how and why a particu- 1986; Kingery & Vandiver 1986; Riederer
lar technique was introduced or a specific manu- 1987; Atasoy & Raby 1989; Lenoir et al. 1989;
facturing process used. It also needs to clarify the McGovern & Notis 1989; Middleton & Freestone
intention behind a certain function and the choice 1991 ; Noll 1991; Wilson 1991; Li Jiazhi & Chen
of a particular trading structure. Xianqiu 1992; Mrry 1992; Neff 1992; Pollard
In the field of preservation, material-specific 1992; Failla 1993; Burragato et al. 1994;
properties of unweathered objects must be com- Guo Jinkum 1995; Lindahl & Stilborg 1995;
pared with their decay products so as to work Vendrell-Saz et aL 1995; Vicenzini 1995; Whit-
out restoration concepts within a framework of bread 1995; Frontini & Grassi 1996; Cumberpatch
interdisciplinary collaboration. & Blinkhorn 1997; Drmians d'Archimbaud 1997;
Freestone & Gaimster 1997; Gaimster 1997;
Gibson & Woods 1997; Lang & Middleton
Methods and history 1997; Santoro Bianchi & Fabbri 1997; Druc
Experimental methods used in the field of 1998; Fabbri & Lega 1999; Levi 1999;
archaeometry have been described in a number Ruf et al. 1999; Velde & Druc 1999; Wood
of papers (Aitken 1961, 1985, 1990, 1998; 1999; Henderson 2000; Rosen 2000; Shortland
Brothwell & Higgs 1968; Berger 1970; 2001; Veeckman et al. 2002; D'Albis 2003;

From: MAGGETTI,M. & MESSIGA,B. (eds) 2006. Geomaterials in Cultural Heritage.


Geological Society, London, Special Publications,257, 1-8.
0305-8719/06/$15.00 (c) The Geological Society of London 2006.
2 M. MAGGETI'I

D'Anna et al. 2003; Di Pierro et al. 2003; However, it appears appropriate to take on
Keblow Bernsted 2003; Bargossi et al. 2004; some of the points raised by Widemann (1982),
Gurt i Esparraguera et al. 2005; Livingstone Fabbri (1992), Vidale (1992) and Maggetti
Smith et al. 2005. (1994b). They deal with the funding of projects
and research positions, the appeal of archaeo-
Glass. Lucas 1921; Caley 1962; Sayre 1964; metry to young scientists, the quality of scientific
Ankner 1965; Berger 1970; Oppenheim et al. publications and the immediate and efficient
1970; Besborodov 1975; Newton & Davison access to research data.
1978; Frank 1982; Olin & Franklin 1982;
Wertime & Wertime 1982; Kazmarzyck &
Hedges 1983; Lambert 1984; Bhardwaj 1987; Funding
Bimson & Freestone 1987; Riederer 1987; Although interdisciplinary research is up-to-date
Henderson 1989, 2000; Brill & Martin 1991; and highly praised by all entities, people working
Foy & Sennequier 1991; Mendera 1991; Tait in this sector do indeed face difficulties. For
1991; Vandiver et al. 1992; Lilyquist & Brill instance, it is not easy to obtain funding,
1993; Foy 1995, 2001; Hook & Gaimster 1995; because problems concern historical disciplines,
Pollard & Heron 1996; Kingery & McCray whereas answers and methods pertain to the
1998; Seibel 1998; Nenna 2002; Veeckman sciences. In the quest for funds, one may find
et al. 2002; Foy & Nenna 2003; Steppuhn that a scientific body either rejects a project
2003; Wedepohl 2003; Bargossi et al. 2004. because questions are regarded as of historical
nature, or it may pass it on to an arts or humanis-
Stone. Gnoli 1971; Young 1973; Winkler tic body, which in turn also declines the project,
1973; Pensabene 1985, 1994, 1998; Sieveking considering it to be of scientific nature.
& Hart 1986; Torrence 1986; Riederer 1987;
Fant 1988; Herz & Waelkens 1988; Trou &
Podany 1990; Borghini 1992; Moens et al. Citation index
1992; Bradley 1993; Klemm & Klemm 1993; It is becoming more and more common for
Moorey 1994; Maniatis et al. 1995; Cunliff & universities, departments and scientists to be
Renfrew 1997; Shackley 1997; Schvoerer 1999; judged by the number of scientific papers being
Henderson 2000; Roux 2000; De Nuccio & published in journals belonging to the citation
Ungaro 2002; Herrmann et al. 2002; Lazzarini index. Many archaeometric publications,
2002, 2004; Kardulias & Yerkes 2003; Poupard however, do not appear in such journals, a fact
& Richard 2003; Bargossi et al. 2004. that must have a detrimental effect on the career
The first scientific analyses of ceramics, and reputation of the scientist concerned, if they
metals and pigments started early; that is, at the do not already hold a position in archaeometry.
beginning of the 19th century (Riederer 198 lb, On the other hand, the archaeometric results
1987; Maggetti 1990, 1994a). The foundation should also be published in archaeologically
of specialist laboratories at museums and univer- relevant journals or books, to strengthen interdis-
sities, such as the Chemisches Laboratorium der ciplinary collaboration. As a result, young,
k6niglichen Museen zu Berlin (Rathgen- enthusiastic scientists will be discouraged from
Forschungslabor, 1888), as well as the Research pursuing a career in archaeometry.
Laboratory for Archaeology and the History of
Arts (1955) at the University of Oxford, were
milestones in the development of archaeometry. Stable research p o s i t i o n s
The number of similar institutions, active In addition to the problem mentioned above,
working groups and professional societies has there are far too few permanent posts for
increased ever since. The publication of several trained archaeometrists. It is understandable
archaeometric journals was initiated, along that in times when jobs are cut everywhere,
with a great number of conferences. Obviously, scientific disciplines do not appear willing to
archaeometry is an encouragingly vital disci- redefine a vacancy as an interdisciplinary lectur-
pline, but is it free of problems? ing and research position. Because the questions
pertain to the field of archaeology, art history and
the preservation of ancient monuments, it should
Problems faced by archaeometry be up to these disciplines to safeguard or create
Fundamental aspects of the status of archaeo- the appropriate posts. Without such new pos-
metry have been discussed extensively by Tite itions it is impossible to retain the interest of
(1991, 2004) and Jones (2004). It is therefore young scientists or to motivate them to undertake
unnecessary to further comment on them here. research in archaeometry.
ARCHAEOMETRY: QUO VADIS? 3

'Hobby' such as precise dating, is indispensable to the


Unfortunately, there are far too many people fields of archaeology and art history. Also, it is
impossible to make restorations without the
doing archaeometric research as a 'hobby'.
Many of these part-time archaeometrists are not appropriate and relevant research being done.
familiar with archaeometric literature and rein- This presents a huge opportunity for archaeo-
vent the wheel, so to speak, i.e. they tackle ques- metry, because, owing to its impact on tourism,
tions that have been solved a long time ago. the study and preservation of our cultural heri-
tage is likely to receive sufficient financial
Often archaeologically irrelevant questions are
investigated, insufficient numbers of samples support from governments. However, it is
are analysed and it can happen that 'poverty of necessary for research in all archaeometric
sectors to focus on archaeometric competence
measurements are covered up with sophisticated
data processing' (Widemann 1982). Many such centres that provide sufficient long-term employ-
ment, knowledge and sound technical apparatus.
papers appear in unrefereed journals or books
and escape the quality filter. This is the only way in which young, well-trained
scientists will be willing to commit themselves to
the fascinating field of interdisciplinary research.
Databases
Often, results of archaeometric studies will not
be found in relevant journals, such as Archaeo-
metry, Geoarchaeology, Journal of Archaeologi-
cal Sciences, Revue d'Arch¢ombtrie, Journal o f References
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A review of the non-destructive identification of diverse geomaterials
in the cultural heritage using different configurations of
Raman spectroscopy
D A V I D C. SMITH
Museum National d'Histoire Naturelle, Laboratoire LEME, USM0205, 61 Rue Buffon,
75005 Paris, France (e-mail: davsmith@mnhn.fr)

Abstract: Non-destructive Raman microscopy (RM) applied to geomaterials in the cultural


heritage is reviewed by means of explaining selected examples representative of the differ-
ent kinds of geomaterials that can be characterized and of the different kinds of analytical
configuration that can be employed. To explain the versatility and considerable analytical
potential of RM that result from its unique combination of capabilities, the first sections
summarize the theory and practice of the method and its advantages and disadvantages.
The most modern configurations (mobile RM (MRM) and ultra-mobile RM; micro-
mapping and imaging; telescopy) are described. Applications in the new age of 'don't
move it, don't even touch it' archaeometry have previously been classified into 10
domains, seven of which concern geomaterials: gems; rocks; ceramics; corroded metals;
coloured vitreous materials; and mineral pigments on an inorganic or organic substrate.
The representative examples here include all these domains and cover the time range
from Prehistoric through Egyptian, Roman, Meso-American, Medieval, Chinese, Renais-
sance and Mogul cultures to modern colouring of glass and a contemporaneous simulation
of submarine archaeology.

The analysis of geomaterials in the cultural for very remote studies (such as planetology); this
heritage, to clarify the nature of the material approach has not yet been applied to archaeo-
employed, evaluate possible provenances, logy, but it could be useful for analysing gem-
detect treatments or to recognize fakes, calls stones in shop windows from across the street,
for a variety of techniques, depending upon the which brings us into the domain of 'Raman
type of material available and the kind of infor- spying' (Smith 2005a), and 21st-century social
mation sought. Raman microscopy (RM) (one science, which will not be pursued here. Future
kind of Raman spectroscopy (RS)) has become developments will no doubt soon include syn-
an important technique in archaeometric studies thetic vocal replies for automated analysis
in archaeology and art history since about (Smith 2005a).
1996, and the pseudo-acronym 'ARCHAEORA- In 1986, during a review of RM applications to
MAN' was coined by Smith & Edwards (1998) mineralogy in general, Smith (1987) argued that
to summarize this wide field of research activity. RM should be of great value to archaeometry, but
More recently the term 'mobile Raman no significant studies were known to the geologi-
microscopy' (MRM) (Smith 1999) was cal community at that time, except for some
employed to analyse art works in situ inside pioneering studies on gemstones and their
museums by taking the laboratory to the object, microinclusions (Drlr-Dubois et al. 1981a,b,
rather than the object to the laboratory as in con- 1986a,b). In fact, some chemists and physicists
ventional 'immobile Raman microscopy' (IRM). had already begun analysing artworks (Delhaye
Subsequently, the possibility of using MRM for et al. 1985; Guineau 1987), but only pigments,
subaquatic archaeology was evaluated positively and only publishing in journals in fields other
(Smith 2003), and more recently Raman micro- than geology or mineralogy, especially chem-
mapping has been used to clarify the microstruc- istry or art history; furthermore, they generally
tural mineralogy of artworks (Smith 2004a) or of avoided mineralogical terminology by using
rocks susceptible to be the provenance thereof chemical names such as mercury sulphide or
(Smith 2004b,c). The most recent development colour names such as vermilion instead of
in RS is telescopy (Sharma et al. 2002, 2003) mineral names such as cinnabar. At the

From: MAGGETTI,M. & MESSlOA,B. (eds) 2006. Geomaterials in Cultural Heritage.


Geological Society, London, Special Publications, 257, 9-32.
0305-8719/06/$15.00 ~:) The Geological Society of London 2006.
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Illl
micro-extraction yes yes x x x x x x x x x x x x x x x x r r i ~
macro/micro micro micro micro micro micro micro micro micro micro nlcro moo rricro x x x x x x macro/rricro
horizontal/vertical vertical vertical vertical vertical vertical vertical vertical vertical vertical ~ ~ ~ x x x x x x ~ ~
mobile/immobile immobile immobile immobile immobile immobile immobile immobile immobile immobile imTdoite irm'ebile m3bile mobile mobile rrd)ile m:3bile rn:Yoile u/~ra-].l~l,f rn~nn'doile
in situ/in lab in lab in lab in lab in lab in lab in lab in lab in lab in lab in lab in lab in situ in situ in situ in situ in situ in situ in situ in situ/in lab
optical fibre head x x x x x x x x x x x fibres til~'es fibres fibres fit:~es fibres all in one opticalfibrelead
under air air air water air air air air air air air ar air air air gl~ss air air under
micro-mapping x x x x trap trap x x x x x nicro-map~ng
iFRESCO- [pigments
in !pigmantsin i ~ , __ ' ~ i i I:~ristmc i
i RAMAN !Roman iPrehistoric i r/"c3 | iPg~ , ~
i~s, Ro~, i ~ Ii~a i
Ukraine i cave, i
..........................................................................................
i.....................................
I. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ~.................................
}.............................................
i lCONO- blue
, !i i a ~oodm -
i slalue,

!GEMI~ iRoman ievaluation i L ~'-- .......................


~ ........................~ '~ ........................
RAI~N iintaglios' IofRMo n i n c ~ i n irnarl~ JR/IM~
.France igemstones ~ ~ . ~ MIdl:le/~ , . ,
~underwater i ~ i s o r ~ i stone J

'PETRO. i ! Meso-
',~A~N i iA~ncan 'in am~c~
....................................................... ! ..... i axehead, ia o ~ !l~ished i i~"Y ' , '
_ !

',METALLO- i icorr~ed
IRAMAN i ~ / ic°ins (Fe' i& °ther
i i !Cu' Zn Pb iartefacts in ;i i

ivrmo, i i
iI~ .... - - ipgrnentson i ! ~
i ! or n stained! i
i i . iglass I I ! . . . . . .- _

references (1°J99a); Robin Barbet


(2001b, Gendron Vemioles Smith (2001), (1999b); (2004b); (2004a) (1999, (2001a, Snith (2003b); F~ndeau (2001a,b) S r ~ & references
Smith & (1997) (1999)
2003) (1997a), (1997) (2001, Bouchard & Bouchard & Smth 2900); 2005a); (2002); ~?th (2001); Lmblanchel
Bouchard Smith 2005b) Sn~th Smith (2005c) Smth Srffth elal, Srffth (2005a) Srdth (unpub.
/2000al /2005cl /2005b) /2002/ /2005at /2003a/ t2005a/ /20(35a/ data/
Notes to tabular part: x denotes "no"; bold type in the configurations highlights unusual features.
NON-DESTRUCTIVE RAMAN SPECTROSCOPY 11

international GEORAMAN-1996 conference in (e.g. Smith & Carabatos-Nrdelec 2001;


Nantes an attempt was made to bring ARCHAEO- Nasdala et al. 2004). The modified light is
RAMAN topics to the attention of the geological called Raman diffused light according to the
community and since then contributions on 'Raman effect' discovered by Sir Chandrase-
archaeology and art history became significant khara Venkata Raman in 1928, for which he
at every G E O R A M A N meeting (1999 in received the Nobel Prize for Physics. Thus the
Valladolid; 2002 in Prague; 2004 in Honolulu) technique does not analyse a single atom, as do
(see table 8 of Smith & Carabatos-Nedrlec a great number of chemical analytical techniques
(2001) for a list of archaeological or art historical such as X-ray fluorescence, as at least two atoms
topics presented at these meetings). Another are required. The vibrational energies involved
series of international congresses on non- are the same as those in infrared (IR) spec-
destructive analysis in the cultural heritage troscopy, such that the two techniques are often
brought in RM at Antwerp in 2002, and this con- considered similar. They are indeed complemen-
tinued at Lecce in 2005. The meetings of ICAM tary, but are not really similar, because in IR
(International Congress on Applied Mineralogy), spectroscopy photons are absorbed or reflected
IRUG (InfraRed users Group), GFSV (Groupe according to the various vibrational energies,
Franqais de la Spectroscopie Vibrationelle), and whereas in RS, incoming photons lose some
GMPCA (Groupe des M~thodes Pluridiscipli- energy, which leaves a vibration mode more
naires Contribuant h l'Archrologie), and others, excited, and hence the outcoming photons
have started to include RM, as have other more have lost some energy, i.e. they have a higher
archaeological meetings (e.g. Smith et al. wavelength, and hence a lower wavenumber
2000). A separate series of international con- (the reciprocal of wavelength) (Fig. 2). This is
gresses on exclusively 'Raman Spectroscopy called Raman Stokes scattering. Raman Anti-
applied to Archaeology and Art History' Stokes scattering also occurs whereby a vibration
('ArtRaman') was started in London in 2001 mode gives up some energy to become less
and continued in Ghent in 2003 and in Paris in excited and the outcoming photons have gained
2005. The literature on A R C H A E O R A M A N energy, i.e. they have a lower wavelength, and
has thus increased enormously in a decade, but hence a higher wavenumber; this effect is
it is dissipated amongst journals in many disci- weaker and will be ignored here. Thus with
plines. This paper cannot review all the litera- Raman Stokes scattering a single kind of intera-
ture; it thus focuses on explaining why RM is tomic vibration causes a shift of the wavenumber
so useful and describes a series of examples of of the incoming exciting light, usually from a
studies by the author's research group that are laser (although Raman used sunlight) and necess-
in two ways representative: of the different arily monochromatic. The exciting wavelength
kinds of geomaterials that can be analysed, and (e.g. 514.5nm from an Ar + green laser or
of the different kinds of analytical configuration 632.8 nm from a H e - N e red laser) is placed at
that can be employed (Fig. 1). zero cm - l on the relative wavenumber scale
such that the Raman band created occurs at a
characteristic Raman shift (e.g. 465 cm -1 from
What is Raman spectroscopy? the major vibration of quartz). Raman shifts are
RS is an optical, hence physical, technique conventionally plotted as being positive, as a
by which the wavelength of light is modified shift is an amount without direction, but in
by interactions with interatomic vibrations reality it should be plotted as - 4 6 5 cm -1, as

Fig. 1. Representative examples of ARCHAEORAMAN studies on geomaterials: configurations, domains and


images. Tabular part: configurations listed horizontally; domains listed diagonally; examples placed in the appropriate
case. Arrowed superimposed images demonstrate the following selected cases. (a) Raman spectra from the
Meso-American stone axe-head in eclogite; from top to bottom: titanite, garnet, clinoamphibole, clinopyroxene
(modified after Smith & Gendron 1997a). (b) A Domitian denier silver alloy coin with cuprite corrosion (modified after
Bouchard & Smith 2005b). (e) Raman spectra of microcline under air, distilled water and water badly contaminated
by animal or vegetable debris as a simulation of subaquatic archaeology (modified after Smith 2003). (d) A
Meso-American corroded metal axe-head (modified after Bouchard & Smith 2005b). (e) An Egyptian inscribed
commemorative scarab in polycrystalline enstatite established by Raman mapping with a RENISHAW® Invia®
spectrometer (modified after Smith 2004a). (f) A Chinese sculptured pendant in jadeite-jade (modified after Smith
2005a). (g) A Medieval cloisonnr-gold style fibula encrusted with garnets (photo D. C. Smith'S). (h) A Teotihuac~in
sculptured mask in marble with the DILOR® LabRaman® horizontal microscope (modified after Nasdala et al. 2004).
(i) A Florentine table in stone marquetry being analysed vertically with a KAISER® Holoprobe® remote head through
the thick protective plate glass (invisible here) (modified after Smith 2005a).
D. C. S M I T H

elastic inelastic inelastic


scattering scattering scattering

Rayleigh Raman Stokes Raman Anti-Stokes


diffusion diffusion diffusion

Ee + E i virtual state

+E, E~+E,

vibrational Ee excited state


energy
levels Es ~round state

extra
input (i) relations
energy E, E, Ei = h. v i
frequency v, = E , / h v, = E i / h vi = E i ] h = c / Li
wavelength k~ = c /v, ~.~= c / v , k, = c / v , = h . c / Ei
wavenumber (absolute) W, = 1 / k, W i = 1 / k~ W, = 1 / k i = v, / c
wavenumber (relative) W, set at zero W, set at zero

change to sample none (EcEg) gained (E~-Eg) lost


change to light none (Ee-Eg) lost (Ee-Eg) gained

output (o~
energy Eo = Ei Eo = Ei - ( E e-E~) E o = E, + ( E e - E 0
frequency vo = E o / h vo= E o/ h vo = E o / h
wavelength k o = c / Vo ~.o = c / v o ko = c / v o
wavenumber (absolute) Wo= I /~o W o = ! /ko Wo= 1 /k o
comparison: input to output none lower higher
wavenumber (relative) Wr = W, - W o Wr = W o - W 1 Wr= W 0- W
= Raman shift zero negative positive

c = speed o f light; h = Planck's constant

Fig. 2. S c h e m e o f the different ways in which inter-atomic vibrational energy levels give rise to three types o f light
scattering (diffusion): Rayleigh, R a m a n Stokes, R a m a n Anti-Stokes.

t h e a b s o l u t e w a v e n u m b e r is l o w e r t h a n t h a t o f l e v e l (e.g. s y m m e t r i c s t r e t c h i n g , a n t i - s y m m e t r i c
t h e e x c i t i n g l i n e ( F i g . 2). A n i m p o r t a n t p o i n t is stretching, deformation, bending, rocking,
that Raman shifts are constant for any wave- w a g g i n g , t w i s t i n g ) , a n d all o f this f o r e a c h k i n d
l e n g t h o f t h e e x c i t i n g l a s e r as t h e s h i f t s a r e of combination of chemical elements (depending
f i x e d r e l a t i v e to t h a t w a v e l e n g t h a n d a r e l i n e a r upon the Raman 'selection rules', which depend
in c m - ~ ; v e r y f e w e x c e p t i o n s to this r u l e o c c u r upon the crystal or molecular symmetry and
(e.g. t h e D b a n d o f g r a p h i t e ) . also u p o n the n u m b e r o f c h e m i c a l e l e m e n t s
As there are many different kinds of present), there are several distinct Raman bands
v i b r a t i o n a l s y m m e t r y , e a c h w i t h its o w n e n e r g y created (which occasionally overlap) such that
NON-DESTRUCTIVE RAMAN SPECTROSCOPY 13

a spectrum is obtained (where the ordinate shows temperature (T) and/or high or low pressure
photon intensity, and the abscissa shows the (P); this is not discussed further here. The
wavenumber) (Fig. l a and c). According to these second is to use 'Raman spectral fingerprinting'
rules, some materials give only one band (e.g. (Dhamelincourt & Bisson 1977; Smith 1987) to
diamond), simple carbonates and sulphates give identify mineral or molecular species, as differ-
fewer than 10 bands, silicates such as garnet give ent species cannot give the same spectrum and
about 20, and more complex silicates such as the same species will always give the same spec-
micas and amphiboles may give more. Organic trum (at the same P - T, if there are no differences
molecules may give rise to hundreds of bands. in chemical composition, crystal structural order,
Spectra are variably plotted with the zero at etc.). This of course requires spectral databases;
the left or the right, but the zero is never several now exist, but all are limited in scope
plotted as this is where Rayleigh scattering (see White 1975; Griffith 1987; Guineau 1987;
occurs; this involves the restitution of the excit- Pinet et al. 1992; Bell et al. 1997; Burgio &
ing light with the same wavelength (Fig. 2) Clark 2001; Bouchard & Smith 2003, 2005a)
(physically not the same, but effectively the and numerous others are in preparation as
same as simple reflection). every Raman research group builds its own.
Rayleigh scattering is very approximately 1012
times more efficient than Raman scattering and
this important fact has several consequences: Why has Raman microscopy become so
(1) a Raman spectrum cannot show the intensity
at 0 c m - i as it would plot somewhere in inter- polyvalent and powerful?
planetary space; (2) it would burn the detector, This is principally because of its great versatility
or create a plasma from it, and has to be filtered owing to its unique combination of capabilities,
out; (3) a 'Rayleigh tail' occurs in the 10- as follows.
100 cm -1 spectral range where the Rayleigh (1) It characterizes simultaneously the
scattering intensity decreases to zero; (4) only physical structure and the chemical composi-
about one photon in several billion incoming tion of an unknown species by comparison
photons is subject to the Raman effect, so the of its Raman spectrum with reference spectra
development of RM necessitated strong laser (compare IR and X-ray diffraction (XRD)).
sources and powerful detectors of very weak This is extremely useful for distinguishing
signals as well as coupling to a microscope polymorphs such as quartz-moganite-
(Dhamelincourt & Bisson 1977); (5) commonly tridymite-cristobalite-coesite (SiO2), aragonite-
1 - 1 0 0 mW power is used to analyse a 1 Ixm calcite (CaCO3), sanidine-orthoclase-microcline
sized portion of a sample or an art object; if the (KA1SiO3), rutile-anatase-brookite (TiO2),
same power per ixm2 were applied over a 1 m 2 etc., which cannot be done with any purely
surface it would need 1012 times more power, chemical technique.
i.e. 1 - 1 0 0 GW, which brings us to the scale of (2) It can do this with inorganic or organic
several nuclear power stations (and this ignores material in different states or forms, such as crys-
the third dimension and another 106). Thus we talline, molecular, glassy or amorphous; whether
are dealing with an extremely powerful energy solid, powdery, suspended, plastic, vitreous,
applied to an extremely small location to detect liquid or gaseous; and whether pure or mixed.
an extremely weak effect. Apparently only IR can also do this. Mixed
It is important to appreciate that the intensity phases, such as in a pigment or in sub-micron-
of a Raman band of a crystal depends, often sized mineral intergrowths in a rock, gem or
strongly, on the orientation of its crystal sym- ceramic, are commonly encountered in
metry with respect to the polarization of the archaeometry.
laser (compare X-ray diffraction) such that in (3) The analysed volume may be on a micro-
certain situations a Raman band may disappear metre scale, from about 0.5 p~m to about 50 l~m
completely. If it is not possible to rotate either in surface diameter, commonly 1 - 2 txm, but the
the art work or the RM, one can introduce a analysed object may have any size and different
half-wave plate and rotate it to see the missing parts thereof may be systematically analysed.
band (Smith 1996). IR and XRD cannot do this except with a
There are basically two ways of using RS. synchrotron (which must be the least mobile
One approach uses RS to satisfy the chemist's, analytical apparatus).
physicist's or mineral physicist's need to try (4) No sample preparation whatsoever is
to predict and calculate Raman phenomena and required (no extracting, drilling, scraping,
to extract thermodynamical data, often by sawing, cutting, grinding, polishing, liquefac-
measuring Raman spectra at high or low tion, gasification, etc., nor a vacuum chamber,
14 D.C. SMITH

KBr pelleting, or other kind of processing) as the few minerals give no Raman band at all
method is non-destructive; with an appropriate because they have a high symmetry and a low
reflection configuration IR can also be number of different atoms in the unit cell (e.g.
non-destructive. This non-destructive property halite (NaCI)). Most pure metals give no
is true as long as one maintains a laser power Raman signal, partly for the preceding reason,
sufficiently low to avoid damage; if, unfortu- and partly because of their high reflectivity; on
nately, this is not achieved then a micron-sized the other hand, as soon as a metal is corroded
volume of the analysed object may be 'burned' to form oxides, hydroxides, carbonates,
or otherwise disintegrated, but fortunately this sulphates, chlorides, etc., RM works very well.
will be invisible to the naked eye and harmless Opaque or semi-opaque minerals absorb too
to most materials such as gemstones, although much light and give either no Raman signal or
it could become dangerous for inflammable a very weak one; manganese oxyhydroxides are
materials such as the paper of a priceless a good example as they have been difficult to
ancient book. recognize in pigments; however, with more
(5) RM can provide micro-mapping or micro- recent instrumentation one can now obtain
imagery of textures of intergrown phases, of Raman spectra from many of these phases
chemically zoned crystals or of physically (Ospitali & Smith 2005). Some materials are
deformed crystals. Other techniques can map rather photosensitive and need low laser power
structures, but IR is on a larger scale. to avoid instantaneous dehydration (e.g. iron
(6) With the use of mobile optical fibres one hydroxides and lead hydroxides).
can analyse any part of an artefact (including The detector picks up not only the Raman
re-entrant angles such as under the arm of a signal but also various kinds of 'parasite'
statue or gemstones mounted inside a crown). signals, such as laser lines from the laser source
(7) MRM may be carried out almost anywhere, that have not been sufficiently well filtered,
such as in situ inside a museum display cabinet, cosmic rays, daylight, incandescent room light,
a conservation or storage building, or on an Hg and Ne emissions in common neon 'fluor-
archaeological site. escent tube' lamps, photoluminescence (PL)
(8) One can identify a phase under another from chemical impurities in the sample or in
transparent one, such as microinclusions inside the optical trajectory (e.g. the infamous
a mineral, as well as pigments under glass, 843 c m - I band from the Olympus × 50 objec-
gems under plastic, or statues under water, so tive), or fluorescence. These sources can be
that submarine archaeology by MRM has attenuated by laser filters, by reducing daylight
become possible (Smith 2003). or room light, or by changing the exciting
(9) One can obtain semi-quantitative chemical laser wavelength such that photoluminescence
analysis of mineral solid-solutions by RM for lines occur elsewhere in the spectrum.
example, by using the RAMANITA method Background fluorescence, which gives a very
devised by Smith & Pinet (1989), calibrated by high baseline that partially or totally obscures
Pinet & Smith (1993, 1994) and updated by the Raman spectrum, is no doubt the worst
Smith (2002b, 2004d, 2005b). The method is problem, but its true cause is not always
based on the time-consuming calibration of obvious. It is known that it can come from elec-
wavenumber shifts along each binary join (if tronic transitions in imperfectly crystallized
natural or synthetic samples are available) and minerals, from some nanocrystalline materials
then within various choices of multivariant such as clays, and from mixed organic materials
chemical space. (living or dead). If the parasite does not interfere
All these possibilities and developments led in the same spectral range as relevant Raman
Smith (2002a) to declare that 'The new age of bands then the problem is avoided. Waiting a
"don't move it, don't even touch it" archaeometry few minutes before acquiring spectra usually
has now arrived to allow remote non-destructive reduces the baseline, perhaps as a result of
characterisation in all the domains of ARCHAE- some annealing by heating. Analysing under
ORAMAN and in situ almost anywhere'. water is beneficial (Smith et al. 1999a; Smith
2003). Changing the exciting laser wavelength
often (but not always) creates drastic improve-
What disadvantages exist with Raman ments. Pulsing the laser is an excellent antidote
but it is not easy to acquire the necessary con-
microscopy? figuration. Interchanging a troublesome optical
As with all analytical techniques there are some component (e.g. filter, mirror, objective) in the
disadvantages with RM, but they are small in RM system with one of a different kind will
number compared with the advantages. Very cure the problem in some cases.
NON-DESTRUCTIVE RAMAN SPECTROSCOPY 15

Raman spectra frequently need some amount Table 1. The 10 domains of ARCHAEORAMAN,
of spectral treatment if we are to be able to updated from Smith (1999, 2002a)
exploit the data by spectral fingerprinting (on
(1) GEMMORAMAN from 'gems':
the other hand, treatments are usually avoided
gemstones (rough, cut or mounted), cameos,
for thermodynamical studies as one must not corals, intaglios, jewellery, collection stones, etc.
modify the raw data upon which certain calcu- (2) CERAMIRAMAN from 'ceramics':
lations are based). First, the 'baseline correction' brick, china, earthenware, faience, glass,
tries to make the background line horizontal, porcelain, pottery, slags, tiles, other vitrified
regardless of the cause of it not being flat (fluor- minerals, etc.
escence, luminescence); this procedure can (3) PETRORAMAN from 'petros' for rocks:
dramatically increase signal-to-noise visibility. axeheads, building columns, ceremonial stones,
Subtracting an oblique straight line is acceptable inlaid rock, millstones, mosaics, necklaces,
sculptures, etc.
if the baseline has a sub-linear steep slope, but
(4) METALLORAMAN from 'corroded metals':
often it is necessary to subtract a polynomial corroded bracelets, coins, cutlery, necklaces,
'best line' curve calculated from selected land- statues, swords, tools, etc.
marks on a distinctly curved baseline. Automatic (5) RESINORAMAN from 'resin' as an example of
correction can be disastrous as the computer a non-cellular organic material composed of only
program may confuse wide Raman bands with a few different molecules or of amorphous
an undulating baseline. More than a × 2 poly- hydrocarbons without a growth texture:
nomial can produce major distortions and, in amber, glue, gum, oil, putty, wax, bitumen,
any case, it is not necessary to achieve a perfectly lignite, coal, etc.
(6) TISSUERAMAN from 'tissue' as an example of
flat baseline. Second, one may eliminate known
cellular organic molecules or biominerals with a
parasite peaks or known detector defects by growth texture:
'rubbing out' with the computer mouse instead bone, claw, cotton, feather, fur, hair, hoof, horn,
of a piece of rubber. An automatic 'peak elimin- ivory, leather, linen, nail, papyrus, parchment,
ation' procedure may be useful for eliminating silk, skin, teeth, wool, wood, etc.
narrow cosmic rays that are distinctly narrower (7) FRESCORAMAN from 'fresco' as an example
than Raman bands, but it needs to be used with of pigments/inks/dyes on or in an inorganic
care. Third, 'smoothing' by averaging all intensi- substrate:
ties over a selected small wavenumber zone is brick, ceramic, plaster, stone, stucco, etc.
(8) ICONORAMAN from 'icon' as an example of
very useful to make real Raman bands more
pigments/inks/dyes on or in an organic
visible by eliminating the basic zigzags of the substrate:
irreducible background flutter, but must not be bone, canvas, paper, skin, textile, wood, etc.
done over zones too wide or real Raman bands (9) VITRORAMAN from the 'vitreous' state:
will become too diluted in intensity or separate pigments on or in enamel, glass or glaze, etc.
nearby bands (doublets) may become fused (10) ENVIRORAMAN from 'environmental'
together. With these three treatments one can fre- deterioration of any of these materials by climate,
quently transform apparently hopeless spectra burial or immersion:
into perfectly exploitable ones, and this is original materials, corrosive agents involved,
intermediate and final products
because the basic information exists in the raw
spectrum and it just needs to be rendered
visible. A variety of more sophisticated com-
puterized techniques exist, such as spectral
combination, peak-fitting, Fourier transforms useful criterion, and this was used by Smith &
and 3D-plotting, but they will not be dealt with Edwards (1998) as there may be different
further here. analytical protocols for different materials;
Table 1 lists the 10 domains of research activity
as updated by Smith (2002a). The analytical
Classifications of Raman microscopic configuration employed is also relevant (macro
or micro; vertical or horizontal microscope;
studies of the cultural heritage optical fibres or not; mobile or immobile;
To demonstrate applications of RM to the cul- in situ or in a laboratory; under air, glass,
tural heritage it is convenient to classify the mineral, or water). Figure 1 plots the seven
examples according to some criteria. Here the domains relevant to geomaterials against com-
cultural period (Prehistoric, Roman, Medieval, binations of analytical configurations and lists
Renaissance, etc.) is not used as this paper is the studies (by the author's research group) that
more mineralogical-technological than archaeo- are mentioned here as being representative of
logical. The type of material analysed can be a research in A R C H A E O R A M A N in general.
16 D.C. SMITH

RM analysis of pigments, whether inorganic Smith & Bouchard (2002) and Martens et al.
or organic materials on inorganic (FRESCORA- (2003); (4) VITRORAMAN on the minerals
MAN) or organic (ICONORAMAN) substrates colouring stained glass by Edwards & Tait
has dominated ARCHAEORAMAN from the (1998), Smith et al. (1999c) and Bouchard &
early works of Delhaye et al. (1985) and Smith (2002).
Guineau (1987) to the production of mini- ENVIRORAMAN studies are less common
catalogues of Raman spectra of pigments (Bell (e.g. Seaward & Edwards 1998). The RM
et al. 1997; Burgio & Clark 2001), and from spectral catalogues of Bouchard & Smith
applications to prehistoric rock art (e.g. (2003, 2005a) included minerals of relevance
Bouchard 1998, 2001; Edwards et al. 1998; to prehistoric paintings, corroded metals and
Smith et aL 1999a,b; Smith & Bouchard stained glass.
2000a) via Roman art (e.g. Smith & Barbet Probably at least 80% of all ARCHAEORA-
1999) through various periods of the last millen- MAN publications to date concern pigments.
nium (e.g. Rull-Perez et al. 1999; Withnall 1999; Apparently over 90% of all RM analysts are phy-
Rull-Perez 2001) to modem art (e.g. Vandena- sicists or chemists, which is logical given the
beele et al. 2000). physico-chemical basis of the technique. Thus,
The biomaterials domains RESINORAMAN like botanists and zoologists, geologists of one
and TISSUERAMAN have been mainly limited kind or another (e.g. crystal chemists, mineralo-
to specialists in biology and/or organic chem- gists or petrographers) engaged in archaeometry
istry (e.g. the early works of Edwards et ai. via RM make up a very small community world-
1996a,b,c; Brody et al. 1998). wide. However, each specialist brings his own
Turning to geomaterials, the earliest known particular competence and, similar to the need
work was on GEMMORAMAN (D~lr-Dubois for an experienced botanist to identify a kind of
et al. 1978). The advantages for gemmology tree, geologists are clearly necessary when study-
are considerable, as RM can be employed for ing natural rock artefacts from the cultural
several different purposes: to verify the nature heritage (and solid-solutions, microinclusions,
of the gemstone itself, to examine for treatments transformations, etc. in their constituent min-
(e.g. heating, resin impregnation, pigmentation), erals, and their possible provenance in one or
to explore solid or fluid microinclusions, or to other geological unit). It was argued by Smith
detect synthetic and imitation stones. Certain & Edwards (1998) that ARCHAEORAMAN
aspects of gemmology have been studied in studies really require three co-authors, a spectro-
detail by RM by Lasnier (1989) and Maestrati scopist for the analysis, a natural scientist for the
(1989), and the first catalogue of the Raman species of the natural raw material, and a social
spectra of gemstones was published by Pinet scientist for the artefact (form and cultural
et al. (1992); more recent studies have been context). Individual scientists can often manage
made notably by Coupry & Brissaud (1996), to adequately cover two of these disciplines, but
Schmetzer et al. (1997), Smith & Robin (1997), to cover all three properly (or all five if one separ-
Smith & Bouchard (2000b), Kiefert et al. ates geology, botany and zoology) would be utopia,
(2001) and Smith (2001a, 2005a). surely requiring a born-again Leonardo da Vinci.
Apart from extremely few early works The following sections, organized by analyti-
(Coupry et al. 1993; Macquet 1994; Wang cal configuration, focus on the geomaterials
et al. 1995), 1997 saw the effective beginning applications listed in Table 1.
of RM studies in the remaining four geomaterial
domains, in particular: (1) PETRORAMAN of
jade and eclogite by Smith & Gendron Representative examples of RM
(1997a,b) or of sculptured polished ceremonial
rocks by Smith & Bouchard (2000b) and Smith applications
(2005a); (2) CERAMIRAMAN of vitrified forts I m m o b i l e a n a l y s i s in a l a b o r a t o r y : u n d e r
by Smith & Vernioles (1997), of the minerals
constituting pottery by Fry et al. (1998) or of air with a vertical microscope
the pigments in glazes by Colomban & Methods. This is the standard method of per-
Treppoz (2001), Colomban et al. (2001) and forming archaeometry with RM, either by
Liem et al. (2000, 2002); (3) METALLORA- placing on the microscope stage micro-samples
MAN on corroded metal coins and various extracted from a cultural item (i.e. not strictly
archaeological metals (Fig. l b and d) by non-destructive in this case) or by placing
McCann et al. (1999), Bouchard & Smith the whole item under the microscope if it is
(2000a,b, 2001, 2005a,b), Bouchard (2001), Di small enough to squeeze between the objective
Lonardo et al. (2002), Frost et al. (2002a,b), and the stage, or by taking away the stage.
NON-DESTRUCTIVE RAMAN SPECTROSCOPY 17

i
Wavenumber (cm -I) 500 1000 1500 Wavenumber ( cm- I ) 400 600 800 1000

~ (c)

.... oo ,ooo 'z°°


(d)

Fig. 3. Raman spectra of selected subjects. (a) Raman spectra of pigments from the Roman tomb at Kertsch (Ukraine):
red minium (BJMI55yy, bottom left); blue cuprorivaite (BHCV03zz, top left); black carbon (BHCA21hh, right)
(modified from Smith & Barbet 1999). Int, intensity. Eight-digit codenames are the computer spectra filenames.
(b) Raman spectra of minerals from the new type of jadeite-jade from Guatemala: from top to bottom: jadeite alone
(AHCP03 mm); jadeite + quartz (key peak at 468 cm- 1, AJQZ05 mm); jadeite + rutile (key peak at 445 cm- ~,
AGCP22 mm); jadeite + titanite (key peak at 543 cm- 1, AHUN 16 ram). Some of the key peaks of jadeite are present
in all spectra: 203, 373,698, 986, 1039 cm -1 (modified from Gendron et al. 2002). (e) Raman spectra of
Cu-hydroxysulphates, from top to bottom: archaeological brochantite (DGCU 17je); standard brochantite (BSCUO6je);
archaeological antlerite (CRCU08je); standard antlerite (BOCU08je). Some bands are at the same wavenumber in all
spectra but there are significant shifts between the two species, notably the SO]- vibration just below 1000 cm-l
(modified from Bouchard & Smith 2005b). (d) Raman spectra of the interior of two modem glasses: colourless 'verre
cord616' (top, BUVE071f) showing intense bands revealing a high Na content (573 cm-i) and a tectosilicate Si-O
arrangement (1100 cm- 1); red 'verre antique' (bottom, BQCO04jv) dominated by the bands at 195 cm-1 (CdSe) & 288
c m - l (CdS) characteristic of CdSo.g5Seo.55(modified from Bouchard & Smith 2005b).

A D I L O R ® X Y ® spectrometer belonging to this is a very c o m m o n phase in all cultures


the M u s e u m National d'Histoire Naturelle (often called 'carbon black', but such varietal
(MNHN) was employed. names are not always used with precision) and
it was probably the first pigment ever used by
Pigments: Roman wall-paintings. Black, red mankind. The blue pigmentation derived from
and blue are the major colours in decorations cuprorivaite (CaCuSi4Olo) (Fig. 3a), which is
on a wall-painted Roman tomb at Kertsch, the key constituent in the pigment called
Ukraine. Micro-samples more or less invisible 'Egyptian Blue' and which was widely used in
to the naked eye were extracted by the archaeo- the Roman Empire. The red turned out to be
logist A. Barbet and submitted to RM m i n i u m (Pb304) (Fig. 3a); although k n o w n else-
examination. It was easy to focus the 1 - 2 tzm where in the R o m a n Empire it was not previously
diameter laser beam onto any selected mineral k n o w n as far NE as Kertsch.
grain or part of a composite micro-assemblage
to determine its mineral constitution (Smith & Pigments: Prehistoric cave paintings. Although
Barbet 1999). In this way it was found that the RM work on pigments had begun in the mid-
black is semi-amorphous carbon (C) (Fig. 3a); 1980s, it was not until the late 1990s that R M
18 D.C. SMITH

analysis of Prehistoric pigments from surface from a Roman site at Lut~ce (Paris) by the
rock art (Edwards et al. 1998; Smith et al. archaeologist S. Robin. When they were
1999b) or cave wall-paintings (Smith et al. studied on a microscope stage it was rapidly
1999a; Smith & Bouchard 2000a; Bouchard established by RM that they were all composed
2001) was attempted. Prehistoric pigments are, of quartz (SiO2) (Smith & Robin 1997). The
in general, far more difficult to determine than texture under the microscope indicated polycrys-
pigments from historical times. This is not only talline quartz, i.e. chalcedony, but this mineral
because they tend to give an enormous fluor- has a great number of varieties. Two intaglios
escence but also because the three most were apple-green in colour and it was first
common phases used, other than carbon black, thought that they were of chrysoprase, a variety
each have an additional problem. Thus yellow coloured green by Ni. Subsequently, some
goethite (a-FeO(OH)) rapidly dehydrates to other green chalcedonies in other rocks were
form red hematite (a-Fe203) even at very low shown to be green because of Cr and have been
laser power; red hematite strongly absorbs a called Cr-onyx. Because RM does not detect
green laser beam, overheats and decomposes trace elements, as about 1 atomic % of an
into a black dot that might contain magnetite element is necessary to create a detectable spec-
(Fe304); black MnxOvOHz phases absorb so tral difference, the naming of the mineral variety
much light that they give particularly bad of these intaglios could not be established with
Raman spectra. In the case of the limestone confidence, but the mineral species was unequi-
caves Pergouset, Les Merveilles and Les Fieux, vocal. One of them had a small mineral
in the Quercy district, Lot, France, it was inclusion, which turned out to be zircon
possible to identify on various drawings (lines, (ZrSiO4). The third intaglio was metallic blue
dots, negative hands, etc.) predominant hematite under reflected light but bordeaux red under
with minor goethite in the red colours, and transmitted light; RM showed that this was
carbon in most black parts. Some other black also of quartz; its variety name could be jasper
parts were not of carbon and did not give a or sard.
Raman signal until the micro-fragments were
covered with water to keep them cool (Smith
et aL 1999a). The Raman signal obtained Rocks: M e s o - A m e r i c a n axe. A Meso-American
resembled that of bixbyite (Mn203), a rare polished axe-head from Cozumel Island,
species in nature. This raised the question of Mexico, now in the collection of the Musre de
the possible creation of bixbyite by heating l'Homme, Paris (Gendron 1998), had previously
some other MnxOyOHz phase, either by prehis- been classified as a 'greenstone', which literally
toric man or by the laser beam during the means a green rock that has not been identified.
analysis. Using more recent Raman apparatus, This one contained at least two reddish minerals
better spectra from some MnxOyOH: phases as well as two greenish minerals. With RM
have been obtained both from samples in the four kinds of Raman spectra were obtained
MNHN mineral collection (Ospitali & Smith and identified as clinopyroxene ((Na,Ca)(A1,
2005) and from other limestone caves in Fe3+,Mg,Fe2+)Si206) (green), 3clinoam~hi-
Quercy (Roucadour and Combe N~gre 1) bole ((D,K,Na)(Na,Ca)z(A1,Fe ,Mg,Fe )5
(Ospitali et al. 2005). Thus it is now easier to (Si,AI)sOzz(OH)2) (darker green), garnet
distinguish carbon from MnxOyOHz, which ((Mg,Mn,Fe~+,Ca)3(A1,Cr,Fe3+)2Si3012) (red)
helps enormously in deciding which drawings and titanite (CaTiSiOs) (brown) (Fig. la)
to sacrifice for carbon isotope dating. A spec- (Smith & Gendron 1997a). The positions of
trum of an interesting orange microphase the T - O - T bands of the clinopyroxene and the
was obtained at Pergouset, which is neither SiO4 bands of the garnet implied considerable
goethite nor hematite because of a strong band proportions of respectively jadeite (NaA1Si2Or)
at precisely 400 cm -j that lies between the and pyrope (Mg3A12Si30~2) in solid-solution,
values for well-crystallized goethite or well- based on the semi-quantitative analytical
crystallized hematite; it was called 'disordered method RAMANITA (mentioned above)
goethite' as it shared several bands with (Smith 2005b). These two species indicated an
goethite (Smith et al. 1999a) and was probably eclogite, a rock type in which clinoamphibole
created by prehistoric man heating 'yellow and titanite often occur (Smith 1988). The
ochre' (a mixture coloured by goethite). kinds of clinoamphibole cannot be established
as there are over 50 amphibole end-members
G e m s t o n e s : R o m a n intaglios. Gemstone identi- and relatively few published data on their
fication is one of the applications where RM Raman spectra. Eclogite does not occur geologi-
excels. Three small intaglios were excavated cally on Cozumel Island, thus proving its
NON-DESTRUCTIVE RAMAN SPECTROSCOPY 19

transport from afar, possibly from Guatemala c. AD 1000 Celtic world from Portugal to
(McBirney et al. 1987). Sweden, and especially in Ireland and Scotland
(Ralston 1983; Buchsenschutz et al. 1998;
Rocks: jades. A second axe head, from Guate- Kresten et al. 1998). They have in common the
mala but of uncertain provenance, was shown to fact that stone building blocks at the lower
be a true jadeite-jade by comparison with the levels are often found to have been fused
Raman spectrum of a Burmese jadeite-jade together by melting. Whether fused for defence,
(Smith & Gendron 1997a). Indeed, RM is by attack or for religious reasons, a second
undoubtedly the best technique for rapidly and major archaeological problem is to elucidate
non-destructively distinguishing the three types how such high temperatures were achieved, and
of jade: jadeite-jade (clinopyroxene); nephrite over long surfaces (e.g. 100 m) and sometimes
jade (clinoamphibole close to the tremolite- several centimetres depth. A few fragments of
actinolite series (Ca2(Mg,Fe)5(Si)8022(OH)2)) and vitrified wall were collected by the archaeologist
'tourist jade' (anything else) (Smith 2005c). J. Vernioles from the vitrified base of the fre-
Thanks to RM, a fiver pebble subsequently quently rebuilt fort at St. Suzanne, Mayenne,
collected by the archaeologist F. Gendron was France. Amongst glass, some crystals were
shown to be a new sub-type of jade (quartz- shown by RM to be of e~-cristobalite (SiO2),
jadeitite) composed also of rutile (TiO2) and which is supposed to require a temperature of
titanite (CaTiSiOs) (Fig. 3b) formed at higher 1470 °C if created by cooling from [3-cristobalite
pressure than usual Meso-American jade (Smith & Vernioles 1997). There is considerable
(albite-jadeitite) (Smith & Gendron 1997b; doubt over the real temperature achieved, as
Gendron et al. 2002) from a new locality, on the literature on this topic is poor and some-
the south side of the Motagua River Valley, times contradictory, and the presence of other
whereas all previous findings of geological jade elements such as A1 or Na could reduce this
had come from the north side (Harlow 1994). temperature; furthermore, polymorphic and
The light greyish-green 'type' jadeite in the order-disorder phenomena are also relevant, as
MNHN mineral collection, which is itself a metastable forms of c~- and [3-tridymite and
Neolithic jade axe whose provenance was most or- and [3-cristobalite can exist. Nevertheless,
probably in the Western Italian Alps, as well the temperature must have been high (at some
as a strong green 'chromo-jadeite' from Burma other localities quartzite has been melted
both gave typical spectra of jadeite (NaA1Si206) (P. Kresten, pers. comm.) and pure quartz melts
with > 9 0 mol% Jd characterized by the S i - O - at 1713 °C). This enigma, strangely unheard of
Si Raman band at 701 -t- 2 c m - l (Gendron et al. by many archaeologists, is likely to remain a
2002; Smith 2005c). mystery for some time. Chemists have confirmed
The singlet (OH) Raman vibration of nephrite that wood smouldering during rain could produce
at c. 3673 cm-1 is very useful proof of the pre- gaseous unsaturated hydrocarbons (e.g. acety-
sence of nephrite jade, when found in addition lene), which could migrate and burst into flame
to the lower wavenumber of the S i - O - S i stretch- at extremely high temperature, but the energy
ing vibration close to 675 c m - l , which is much available would not be sufficient to penetrate
lower than that in jadeite. The nephrite jade deep into the rock wall. Accumulated lightning
nature of a series of artefacts, mainly polished strikes over a few millennia provide an alterna-
flat bracelets or rings, but also some geological tive possible explanation, otherwise it might be
source rocks, all from China, was analysed by necessary to invoke UFOs (unidentified flying
Smith et al. (2003b). Many were found to be of objects)! Interestingly, identical Raman spectra
nephrite, but one of the six source rocks was a were obtained (Smith & Vernioles 1997) from
serpentine (Mg3SizOs(OH)4),and three artefacts c~-cristobalite in glass in 'Libyan Desert Glass',
were not nephrite but either calcite or quartz. A which is believed to have been formed by some
few darker artefacts revealed only a weak band kind of extra terrestrial impact event.
at about 675 cm-~ suggestive of nephrite.
Two probable tourist jades from SE Asia were Corroded metals: copper coins. Coins consti-
also examined: a supposed sculptured 'lilac jade' tute one of the most obvious kinds of metal arte-
was only quartz with a colour between that of fact of the cultural heritage and their size is ideal
amethyst and 'rose quartz', and a green and for being placed under a fixed microscope objec-
white bracelet of supposed jade turned out to tive. Coins from different periods and composed
be of calcite (Smith 2005a). of various metals (Fe, Cu, Zn, Pb, Ag, A1, Ni, Sn)
were thus examined by Bouchard (2001) and
Ceramics: vitrified wall. Enigmatic vitrified Bouchard & Smith (2001, 2005b). As mentioned
forts are known throughout the c. 1000 BC to above, the pure metal or even many alloys do not
20 D.C. SMITH

give a Raman signal, but their corrosion products Stained glass: experimental, modem and archae-
do. Care must be exercised in interpretation, as ological. Glass can be coloured in various
the metal in an identified corrosion product ways. The colour may derive from a single
may not be a major constituent of the original chemical element dissolved in trace amounts
coin because of 'preferential corrosion'; thus inside the glass, in which case there is no
Cu salts are often found on Ag coins that longer any crystalline mineral phase left to
contain a small amount of Cu (Fig. l b). Hence provide a Raman spectrum. Alternatively, there
the main purpose is to recognize the kind of may be micro- or nano-crystalline inclusions,
corrosion process that has occurred, so as to which can provide a Raman spectrum.
help restorers and curators decide on the appro- However, the most common situation in stained
priate method to treat and conserve the coins glass in church windows (apart from unheated
(or tools, weapons or statues, etc.) (Fig. ld). superficial paint) is coloured reaction products
Concerning copper, the products observed formed after pigment minerals (with or without
by RM on coins and other artefacts of various fluxes such as minium and silica to produce a
ages included Cu-oxides (cuprite (Cu20), P b - S i - O glass) had been spread on the surface
tenorite (CuO)), Cu-hydroxycarbonates (azurite of the glass and then heated; this produces
(Cu3(CO3)2(OH)2), malachite (Cu2CO3(OH)2)), several distinct phenomena: dissolution of some
Cu-hydroxychlorides (atacamite (Cu2CI(OH)3), original material into the glass; migration of
clinoatacamite (Cu2CI(OH)3)) and Cu- certain elements from the glass onto the surface
hydroxysulphates (antlerite (Cu3SO4(OH)4), (especially alkalis and alkaline earths); intercrys-
brochantite (Cu4SO4(OH)6))(Fig. 3c). Particular talline reaction between the applied pigments
attention was paid to the RM distinction of the with or without involvement of the glass; relict
Cu-hydroxychlorides by Bouchard (2001) and original pigment; or glass that did not react at
Bouchard & Smith (2005b), as clinoatacamite all. A project involving the study of commer-
has only recently been recognized by the cially available mineral pigments (whose
International Mineralogical Association (IMA) precise chemical composition is not provided
(Jambor et al. 1996) and in earlier works this by the manufacturers), experimentation to create
mineral species may have inadvertently been stained glass and to study the reaction products,
called paratacamite, which is a C u - Z n solid- and analysis of real archaeological stained glass
solution ((Cu,Zn)2CI(OH)3)). from the 13th to 20th centuries was described by
Smith et al. (1999c) and Bouchard (2001).
Corroded metals: lead plates and an iron The experimentation showed that there is not
ingot. A fragment of a strongly corroded so much chemical reaction between the original
Roman sarcophagus in lead is archived in the glass and the mixture placed on top as multiple
MNHN mineral collection and is labelled 'cotun- reactions within the mixture. Blue stain caused
nite', which thus indicates corrosion by chloride. by superficial cobalt aluminate 'smalt' or
A R M study found no cotunnite (PbC12) nor any 'cobalt blue' (CoO.nAl203) was easily recog-
other chloride, but only a mixture of several Pb- nized by characteristic strong Raman bands
hydroxycarbonates: plumbonacrite (Pblo(CO3)6 along with relict initial corundum (A1203). In a
O(OH)6 ), hydrocerussite (Pb3(CO3)z(OH)2) and green superficial experimental stain on glass the
cerussite (PbCO3) (Bouchard 2001; Bouchard complex Raman spectrum revealed a consider-
& Smith 2005b). Another similar plate revealed able number of intermixed phases: principally
only the two oxides litharge (PbO) and massicot blue smalt with orange crocoite (PbCrO4) to
(PbO), hence only the valency Pb 2+ (as no minium create the average green colour by 'colour sub-
(Pb304) or plattnerite (PbO2) was detected) and traction' (i.e. the opposite of the 'colour addition'
no chloride, carbonate or hydroxide. rules that apply to RGB computer screens) along
A Roman ingot brought up from a shipwreck with minor relict green eskolaite (Cr203) and red
at Sainte-Marie-de-la-Mer off the French coast minium (Pb304), which had created the crocoite
was examined (Bouchard 2001; Bouchard & by the oxidizing reaction 6Cr203 + 4 P b 3 0 4 +
Smith 2005b). The minerals found on the 702 = 12PbCrO4. A modern commercial deep
highly corroded surface included the Fe-oxide red glass gave an interesting strong Raman
maghemite (~/-Fe203) and the Fe-oxyhydroxides spectrum from the interior of the glass
akaganrite, goethite and lepidocrocite (all (Fig. 3d); it was possible to identify bands of
(FeO(OH))). There were also RM spectral CdS and CdSe typical of a CdS-CdSe solid-
indications of the presence of the ion FeCI42-, solution (Bouchard 2001), and even deduce the
and it is known that in akaganrite some (OH)- S/(S + Se) proportion to be about 45 atomic %
may be replaced by C I - , especially in marine on the basis of a Raman shift calibration made
environments (Arnould-Pernot et al. 1994). by Schreder & Kiefer (2001).
NON-DESTRUCTIVE RAMAN SPECTROSCOPY 21

The most common mineral pigment found in micron-sized inclusions in the clinopyroxene
real archaeological stained glass from earlier grain cores (Gendron et al. 2002). Micro-
periods is hematite (e.g. 13th century from mapping of a 50 txm x 90 ~ m surface with a
Mans; 16th-17th century from the Mus6e motorized step of 0.4 Ixm acquired over 20 000
Carnavalet, Paris; 18th-19tb centuries from complete spectra overnight. These data were
Strasbourg), but 19th-century glass from Mans then treated and presented in different ways; for
and Strasbourg revealed respectively smalt example, the integrated area of the main band
and crocoite. Minerals created by environmental of quartz (Fig. 4a) or of the T - O - T band of
alteration of stained glass included calcite the clinopyroxene was used to reveal the distri-
(CaCO3) and gypsum (CaSO4.2H20), and in bution of the presence and absence of the
contact with Pb structural supports a mixture quartz microinclusions, and the Raman wave-
of lead carbonates was found (Bouchard 2001). number shift of the T - O - T band was used to
reveal the tool% Jd distribution in detail
(Fig. 4b). The latter map summarizes the col-
immobile analysis in a laboratory: under lision of the North American Plate with the Car-
air with micro-mapping ibbean Plate, subduction and exhumation, all in a
50 ~ m x 90 Ixm surface.
Micro-inclusions in Guatemalan jade. The
rutile-quartz-jadeitite from Guatemala mentioned
above was examined by Raman micro-mapping Crystal orientation in an Egyptian scarab. An
with a RENISHAW ® INVIA ® spectrometer inscribed Ancient Egyptian commemorative
to gain more information on the nature of scarab was supposed to be made of enstatite
the quartz-jadeite contacts (Smith 2004b,c, ((Mg,Fe)SiO3 with Mg > Fe) (Fig. le). Despite
2005d). It was already established from Raman a strong fluorescence, possibly due to patina
point analysis that the Jd content of the clinopyr- formed over several millennia, it was possible
oxene is highest in the grain cores (c. 95 mol%) to confirm from the Raman spectra obtained by
and diminishes sharply at the grain boundaries placing the scarab on a Raman microscope
(sometimes 1-2mo1% lower, sometimes 1 0 - stage that it does contain enstatite, and so far
20 mol% lower), and that the quartz occurs as no other mineral has been found except minor

(a) I~ (b)

E~

-j
-~z:7

40
"<.~.."~ -~'o X

Fig. 4. Raman micromaps of the quartz-jadeitite RET27 from Guatemala. (a) 3D plot of the 2D spatial distribution of
the intensity (signal-to-baseline) of quartz microinclusions over a 95p~m x 50 p~m part of the thin section involving
three jadeite grains: they occur only in the core of the larger grain (centre right). (b) 3D plot of the same XY surface as in
(a) but with the wavenumber position of the Si-O-Si Raman band around 700 cm- ~plotted increasing upwards (more
Jd upwards). This single 3D map summarizes a complex geodynamical history of tectonic plate collision and
subduction that created the high-pressure jadeite + quartz assemblage (the 'hills'), and the subsequent exhumation
during which element migration allowed Ca + Mg to enter during retrograde depressurization metamorphism and
replace Na + A1, thus reducing the Jd content towards the grain boundaries (the 'valleys').
22 D.C. SMITH

iron oxides. As the patina prevented a good gloves were worn to avoid any surface damage,
visual observation, it remained possible that the so that the artefacts were effectively not
scarab was made of one monocrystal (with touched by hand. The configuration proved
minor iron oxide inclusions) or of millions of excellent for the purpose and produced data on
sub-millimetric crystals as in the case of many objects, a few of which are mentioned
jadeite-jade. A short Raman map was made and below.
the relative intensity of two bands around
1000cm -1 was examined, as this parameter Rocks: Teotihuacrn, Ta~'no, Totonac and Aztec.
would vary with crystal orientation under the A Teotihuacan mask (Fig. l h) labelled 'marble'
polarized laser beam. The bands were found to was composed of layers of greenish-white and
vary in relative intensity, which confirms that greenish-grey colour with parts polished to
their orientation varies and hence that the create angular patterns (glyphs); this artefact
scarab is polycrystalline (Smith 2004a). rapidly revealed calcite (CaCO3) in both colour
zones. A large heavy well-polished Tamo
object in a horseshoe shape and labelled 'rock'
Mobile analysis in situ inside a museum: also yielded only calcite. (This object has been
referred to as a 'ceinture/joug' (belt or yoke in
with a horizontal microscope English), although this shape has also been con-
Methods. A DILOR ® LabRam ® spectrometer sidered as a form upon which leather was worked
equipped with a prototype horizontal microscope to make large objects, such as a saddle. However,
was carried by four people into the Musre de the quality of the finish implies a ceremonial
l'Homme in Paris in an to attempt to identify usage.) These data suggested that the rock in
various Meso-American sculptured rocks. each case was composed essentially of calcite
This LabRam also had a vertical microscope, (Smith 1999, 2005a), probably marble, the
which allowed the identification of the natural compact dense metamorphosed form of chalk
pigment indigo in blue paint on an Aztec or limestone.
whistle in 'terra cotta' (Smith 2000), as this A strangely shaped three-pointed double-
item was small enough to be placed on the micro- headed sculpture from the Ta'ino culture labelled
scope stage. Most of the other artefacts were 'rock' was mostly white or grey with some very
much larger. They were also too heavy, some dark parts. This object revealed spectra of calcite
up to c. 60 kg, to place on a special moving accompanied by a Raman band at 1006 cm-1,
platform designed to place objects in front of compatible with gypsum, but one band is not
the horizontal objective. The objects were thus enough for a definitive identification. Spectra in
placed on top of various supports, usually the dark parts yielded the four Raman bands at
strong wooden boxes, and various other pieces 145, 395, 513 and 635 cm - t characteristic of
of wood, metal or plastic were used to support anatase (Smith 1999, 2005a). Anatase is one of
the artefact in the desired position at which the the polymorphs of (TiO2) (compare rutile and
focused laser beam arrived exactly on that part brookite) but it is usually brilliant white in
of the artefact to be analysed. A knob on the hori- colour (it is often used as a white pigment)
zontal objective permitted focusing movement although it can be light grey. It would appear
in the z direction, but the xy positions could not that the anatase occurs as inclusions in the dark
be moved. An extra computer screen visualized parts, which were not identified in the short
a magnified image of the artefact and also the time available for this analytical operation. The
precise position of the laser beam. The only combination of anatase + calcite or of anatase +
problem encountered was when it was necessary gypsum is not common in nature and hence no
to move the artefact only a few microns so as to name was attributed to this enigmatic rock.
be able to analyse a particular micron-sized Another 'ceinture/joug', but from the Taino
crystal. The 'handyman' solution was to slightly culture, was reddish in colour and labelled
wobble the heavy artefact; when it settled down 'rock'. It revealed the presence of quartz and
again after a few moments, the laser beam was of albite (NaAISi308) (Smith 1999, 2005a).
never in exactly the same spot; after several Several types of igneous, metamorphic or sedi-
attempts the laser beam fell upon either by mentary rocks may contain the association
good luck the desired crystal or one that was of quartz + albite, so no name was given, but at
the same species. These analyses are considered least these mineral species were easily identified.
as being in situ in the sense that they took place A third 'ceinture/joug', Totonac this time,
inside the conservation room of the objects, but dark green and labelled 'diorite', revealed
which therefore did not have to leave their the presence of clinopyroxene close to
room but only be moved a few metres; also, diopside (CaMgSi206) and plagioclase close to
NON-DESTRUCTIVE RAMAN SPECTROSCOPY 23

labradorite ((Na, Ca)(A1, Si)408) (Smith 1999, Mineralogy at the MNHN in 2000. A remote
2005a). This association is typical of the dark head was suspended from a tube on a tripod
igneous rock gabbro, in which these two and in most cases orientated such that the laser
mineral species are essential, but they can beam was focused downwards onto an artefact
also occur in the metamorphic rock granulite. placed on a table (see Fig. 5b). Occasionally it
The two mineral species essential to a diorite was more convenient to direct the laser horizon-
(amphibole + andesine) were not observed. It tally (see Fig. 5a) but any orientation was poss-
was thus deduced that this artefact was probably ible as an optical fibre carried the incident laser
made of gabbro. and directed the Raman signal back along an
Diopside was also discovered in a dark reddish adjacent fibre to the spectrometer box (contain-
'feathered serpent' from the Aztec culture ing the laser source, spectrometer, detectors,
labelled 'red porphyry', but diopside is a etc.) placed on a trolley on the floor to facilitate
typical ferromagnesian mineral from a basic moving around the Gallery. The technique was
rock and is not a typical mineral of red porphyry, impeccable and gave good results on many
an acid igneous rock. The Raman analysis stones.
provided support for the idea that it also is a
gabbro, as the reddish colour can be explained Sculptured rocks. Several Chinese jade arte-
by a superficial pigment (see below). facts in the gallery were examined to confirm
their jade nature as well as the type of jade. A
Mineral pigments: Aztec and Timshian. The polychrome white + chromium-green pendant
above-mentioned 'feathered serpent' has a with the colour and texture typical of Burmese
surface that is dark red and smooth. Several jade sculptured in China, a much darker green-
spectra revealed hematite. A small Aztec to-black pendant whose jadeite nature was less
reddish sitting statue labelled 'andesite' again obvious (Fig. l f), and a homogeneous pale
yielded analyses of hematite (Smith 1999, grey-green sculptured buckle were all proven
2000). Hematite is a mineral not normally to be made of jadeite (Smith 2001a, 2005a). A
found abundantly in either 'red porphyry' or Chinese grasshopper cage, a large Chinese cup
andesite. However, the ease of finding hematite studded with other encrusted gemstones
implied that hematite had been painted on the (Fig. 5a), and a Mogul dagger head mentioned
object as a pigment that masks the real colour below encrusted with diamonds, emeralds and
of the rock (it is recognized by ethnologists 'rubies' were all proven to be made of nephrite
that hematite was sometimes painted on (Smith 2001a, 2005a).
Meso-American ceremonial works).
A more obvious pigment is the red colour of Gemstones: Mogul. The Mogul dagger head
the ears and lips of a Timshian mask sculptured from NW India (Fig. 5b) is encrusted with
out of a heavy bluish rock. This quickly proved emeralds surrounded by a string of diamonds,
to be cinnabar (HgS) (Smith 1999, 2000). and rubies are neatly dispersed throughout the
artefact. All the emeralds and diamonds were
rapidly shown to be correctly identified.
Monocrystals: Aztec. Several small clear trans-
However, only about half of the rubies were
parent carved objects had been labelled 'quartz'
red corundum (A1203); the others, of the same
or 'calcite'. These could have been verified by
colour, were found to be red spinel
traditional mineralogical methods but it was con-
((Mg,Fe)AI204) (Smith 2005a). This may not
venient to pass them rapidly under the laser
indicate any kind of fraud or even of error as
beam. Most identifications were rapidly con-
the term 'ruby' in certain languages is synony-
firmed, but in a few cases a 'calcite' turned out
mous with both corundum and spinel.
to be quartz and a 'quartz' turned out to be
calcite. The famous life-size Aztec skull said to
Gemstones: Navaratna. An armband and a
be in 'rock crystal' proved indeed to be in
bracelet encrusted with the specific nine gem-
quartz (Smith 1999; Smith & Carabatos-
stones (including diamond in the centre) of the
N6delec 2001).
Navaratna legend (India) were also examined
(Rondeau & Smith 2002). The correct mineral
Mobile analysis in situ inside a museum: varieties and species were found in eight gems
in the bracelet (species in square brackets):
under air with optical fibres coral (red) [calcite] (CaCO3); emerald (green)
Methods. A KAISER ® Holoprobe ® mobile [beryl] (Be3AlzSi6018); (colourless) [diamond]
Raman microscope was carried by one man (C); (red) [grossular] (Ca3A12Si3OI2); pearl
into the treasure vault of the Gallery of (white) [aragonite] (CaCO3); ruby (red)
24 D.C. SMITH

Fig. 5. Photographs of different MRM configurations. (a) Treasure Vault, MNHN, Paris, 2000. A KAISER®
Holoprobe ® remote head connected by optical fibres to the spectrometer box on a trolley below the table. A Chinese
nephrite jade cup; the laser beam, coming horizontally from the objective suspended from the tripod, can be seen
through the jade (photo modified after Smith 2005a). (b) Treasure Vault, MNHN, Paris, 2000. The KAISER®
Holoprobe ® remote head as in (a). A Mogul inlaid jade dagger handle encrusted with rubies, spinels, emeralds and
small diamonds analysed vertically (photo modified after Smith 2005a). (c) Louvre Paris, 2000. The KAISER®
Holoprobe ® remote head as in (a), but with the spectrometer in another room. An Oceanian 3 m high wooden statute
painted blue. Noteworthy features are the laser impact spot and that the optical fibre cable is 100 m long (~hoto
modified after Smith 2005a). (d) Roucadour cave, Quercy, France, 2004. A DELTA NU ® Inspector Raman with the
entire MRM system inside the small black box, oriented here to examine prehistoric pigments on an inclined wall
(photo D. C. Smith' ).

[corundum] (A1203); sapphire (blue) [corundum] that at some stage in the history of the armband
(A1203); (yellow) [topazl (A12SiO4(OH,F)2)). the original stone was replaced by a zircon.
H o w e v e r , the expected 'cat's eye' [chryso-
beryl] (BeA1204) is in fact a 'cat's eye' quartz Gemstones." Medieval cloisonn~ gold. Earl~
(SiO2). In the Navaratna armband, w h i c h has in 2001 a similar remote head, a D I L O R ~
three rows each of three large gemstones, the 'Superhead '® plus a spectrometer were carried
central supposed d i a m o n d is in fact a zircon, into the Mus6e des Antiquit6s Nationales in
the expected ruby is a spinel, the expected St G e r m a i n - e n - L a y e near Paris. The same kind
chrysoberyl is again 'cat's eye' quartz and the of configuration was e m p l o y e d to analyse numer-
last stone is yellow sapphire [corundum]. ous stones encrusted in cloisonn6-gold style
The last three stones could easily be due to Medieval jewellery. Most stones were red and
genuine misidentifications at the historical all but one were shown to be garnet; all green
time of mounting, but the central zircon has a stones were glass. The garnets in Medieval cloi-
noticeably lower-quality cut and is rather small sonn6-gold j e w e l l e r y from Vicq, France
for the space available; it is thus very likely (Fig. l g), were e x a m i n e d in a routine fashion by
NON-DESTRUCTIVE RAMAN SPECTROSCOPY 25

rapidly placing each crystal beneath the laser the early 20th century after lazurite had become
beam, one after the other without the need to a synthetic pigment ('ultramarine').
verify the laser focusing (Smith & P6rin 2003).
They were all almandine-pyrope solid-sol- Mobile analysis in situ inside a museum:
utions, which have been called 'rhodolite'
under glass with optical fibres
((Mg,FeZ+)3AlzSi3Oi2), although this is not an
official IMA term. Such compositions were Methods. RM has the great advantage over
already known, but by non-mobile analytical many other analytical techniques that it can
techniques, e.g. by XRF (Greiff 1998), energy- analyse through transparent media such as
dispersive SEM (Quast & Schltisser 2000) and glass, mineral or plastic. It is thanks to this
by Proton Induced X-ray Emission spectroscopy capacity that micro-inclusions within minerals,
(PIXE) (Calligaro et al. 2002). Most analyses at and especially within gemstones, can be deter-
Vicq were closer to almandine but in two bird's mined precisely, as mentioned in the introduc-
eye fibulae made of silver instead of gold the tion. To test the MRM method through thick
stone was closer to pyrope. Their chemical dis- plate glass, the KAISER Holoprobe was used
tinction was possible by employing the RAMA- in 2000. The usual tripod with the remote head
NITA method of semi-quantitative analysis (see suspended below it was simply placed on the pro-
above) (Smith 2005b). tective plate glass, as were the computer, key-
The same method was employed on other board and mouse. The laser beam was focused
Medieval cloisonne-gold jewellery from Brut, through the glass onto the mineral below,
North Ossetia, Russian Federation, and similar which reduced enormously the intensity of the
almandine-pyrope solid-solutions were found Raman spectrum of the glass itself. When rela-
(Smith et al. 2003b; Smith 2005a). However, tively significant Raman bands occurred from
some garnets were found to be very rich in the glass (because of a weak Raman signal
andradite (Ca3Fe3+Si3Ol2); as far as is known from the mineral below and hence longer count-
andradite has never been recorded before in ing times) they were in different spectral zones
this kind of archaeological material. from the Raman bands of the mineral of interest,
and were wider and hence distinct, so that the
glass was not a problem at all.
Mineral pigments: Oceanian statue. The
above-mentioned KAISER ® Holoprobe ® mobile Gemstones encrusted in stone marquetry:
Raman microscope was also carried into the Florentine tables. Three 17th-century tables
Louvre in 2000 to examine some pigmented with various stones encrusted into black or
artworks. Of particular interest was a 3 m high white marble are exhibited in the Treasure
wooden statue from Oceania painted light blue. Vault of the Gallery of Mineralogy at the
It was easy to position the remote head on the MNHN. They are covered by heavy 1.6 mm
tripod just in front of the statue and direct thick plate glass, which was not removed. The
the laser at any angle onto the statue (Fig. 5c). stones had been inlaid in delicate designs of
In this analytical operation a 100m optical flowers, fruit, birds and insects. The laser beam
fibre was used and the mobile Raman micro- was focused on the mineral surface, and as it is
scope's spectrometer was placed in another flat, it was sufficient to merely slide the tripod
room of the museum. Mobile telephones were over the table and the computer screen gave the
used to communicate between the person Raman spectrum of the mineral under the laser
adjusting the focusing and the person controlling (Fig. l i). In this way it was possible to confirm,
the computer, so this is an excellent example for example, the quartz nature of purple crystals
of 'remote' analysis (Smith 2001a, 2005a). composing grapes, quartz or calcite in many
Very little time was left for this analysis before designs, quartz in the thorax of a green insect
having to evacuate the building at closing time, suspected to be a mineral other than quartz, and
and the neon lights of the room in addition to dolomite (CaMg(CO3)2) in yellowish-white
considerable daylight increased the background 'lily-of-the-valley' flower petals that could have
so much that only one poor spectrum could be been in calcite, quartzite or even ivory (Smith
collected. However, after extended spectral & Rondeau 2001; Smith 2002a,c). Blue flowers
treatment it was just possible to see a Raman in lazurite were recognized by their lumines-
band at the characteristic wavenumber for lazur- cence spectrum. The most exciting discovery
ite ((Na,Ca)4_8(A16Si6024)(S,SO4,C1) 1- 2)- It is concerned the red pips of a pomegranate design
highly unlikely that the expensive rock 'lapis that were presumed to be of garnet; in fact,
lazuli' was ground up to be used as a pigment; some were indeed of garnet but others were of
it is more likely that this statue was painted in ruby. Thus a very precious stone had been used
26 D.C. SMITH

and one may wonder if the manufacturer had rea- waters more realistically, a second set of exper-
lized that he was mixing two different mineral iments was carried out with very impure water
species in a single kind of design (compare the full of fish dejections or rotten vegetation
Mogul dagger head mentioned above). (Smith 2003) (Fig. lc). The former increased
This short study demonstrated very well that the baseline but did not reduce the Raman
analysing under thick glass is perfectly feasible signal, whereas the latter reduced the Raman
and indeed rather easy, as exploitable spectra signal but did not increase the baseline. Thus
were obtained in a reasonable time. the relevant Raman bands were still visible and
after spectral treatment there was effectively no
loss of information. Hence even if lake or
Raman analysis under water ocean water does inhibit subaquatic archaeome-
Methods. As RM can analyse under glass, it try by MRM at certain natural sites of con-
can also analyse under water. The world's lakes centrated impurities and at places polluted
and oceans are littered with sunken ships still by human activities, in general terms there are
with their cargos, often at shallow depths, and no physical, chemical, botanical or zoological
numerous cities from Alexandria to Zeugma obstacles.
have been submerged. Of course, if sufficient
finance is available one could build a special Ultra-mobile analysis in situ inside a museum
submarine and take an entire mobile Raman
microscope to great depths and make analyses with a hand-held Raman microscope
though a window, i.e. through both glass and Methods. A very recent development is an even
water, and this has been done as deep as more extreme miniaturization of an MRM appar-
3600 m (Brewer et al. 2002). However, for atus, which allows it to be even lighter in weight
much shallower depths a simpler solution was and easier to manipulate in any direction. The
proposed (Smith 2001b): to take a tripod (or entire DELTA NU ® 'Inspector Raman ~ can be
rather a more robust stand) to the sea floor and held in one hand, except for the mini-computer,
have a diver focus the laser beam onto part of which can be operated with the other hand; it
an artefact of interest. This is possible as there can run on batteries and hence be used effectively
is no electricity at the remote end of the optical anywhere in air (N.B. there is electricity inside
fibres. Thus the spectrometer could be in a boat this particular 'remote head', as it also contains
just above. In this way, one could verify sup- the laser source, the detector and the spec-
posed beryl as the eyes of an Egyptian statue in trometer). An optional special plastic nozzle
granite, supposed lazurite as the toenails, and fitted over the objective gives exactly the fight
even the kind(s) of feldspar in the granite itself. focusing distance so that for artefacts that may
However, before attempting to mount an be touched, such as tough gemstones, it is suffi-
expedition, it was important to evaluate if dirty cient to place the nozzle on the gem and literally
water would cause too much fluorescence and 'shoot' the laser from the 'gun'. For less tough
thus hamper if not prohibit the exercise. materials the nozzle can be quickly taken off,
and for analysing mixtures such as pigments a
Simulation with gemstones. Three gemstones special video attachment with triple illumination
chosen for their Raman response (strong, zircon gives an enlarged view of the grains so that the
(ZrSiO4); medium, microcline (KA1Si3Os); precise zone to be analysed can be chosen. Of
weak, sodalite (NasA16Si6024C12)) were placed course, with all these advantages there must be
in a plastic bowl and successively analysed some disadvantages; these are principally a
under air, pure distilled water, and various lower spatial resolution, c. 50 p~m minimum
impure waters. These were concocted to create compared with c. 1 ~m for a high-resolution
colour, solute and/or suspensions by initially mobile Raman microscope, and a lower spectral
making saturated sugar or salt solutions and resolution such that the bands are wider and their
then using pure red wine (Smith 2001b). These centres less precise. An Inspector Raman was
results were very positive, as pure water actually tried in 2004 on the same Florentine tables as
increased the Raman intensities (perhaps because mentioned above (Smith & Ospitali 2005), and
of cooling), the solutes did not make the spectra it was also carried down the Roucadour cave,
any worse, and although the wine considerably Quercy, France, in 2004 to examine some other
reduced the Raman signal because of absorption Prehistoric paintings (Smith et al. unpub, data).
by the colour and the suspensions, simple spec- The first data were disappointing because of
tral treatment made it possible to recognize all several desired features not being available in
of the Raman bands except for those of deep the supplied software (these problems are being
blue sodalite. To simulate natural impure remedied at the time of writing), but the
NON-DESTRUCTIVE RAMAN SPECTROSCOPY 27

apparatus excelled in its mobility, especially The author is pleased to acknowledge the help, during
during the short speleological expedition, and it various stages of his projects mentioned above, kindly pro-
fully merits the term ultra-mobile (Fig. 5d). vided by museum or university staff, especially A. Barbet,
M. Bouchard, C. Carabatos-Nedrlec, P.-J. Chiappero,
J.-M. Fourcault, F. Gendron, E. Gonthier, M. Kazanski,
Discussion and conclusions D. LEvine, M. Lorblanchet, C. Naffah, F. Ospitali,
P. Prrin, M. Pinet, S. Robin, B. Rondeau, H.-J. Schubnel,
There can be no doubt that archaeometry in F. Valet and J. D. Vernioles, and also the representatives
general has gained enormously by the develop- of four manufacturers, M. Belleil (RENISHAW),
ment of a wide range of analytical techniques, K. Carron (DELTA NU), B. Lenain (KAISER), and
especially non-destructive ones. It has been S. Morel and J. Oswalt (DILOR/JOBIN-YVON/
demonstrated here that RM and MRM are power- HORIBA).
ful. It has also been mentioned that more
A R C H A E O R A M A N research has been made
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que. Archiologie du jade. Doctoral thesis, Ecole the study of the copper and brass corrosion and
Hautes Etudes Sciences Sociales, Paris. 'bronze disease'. Neues Jahrbuch far Mineralogie,
GENDRON, F., SMITH, D. C. & GENDRON-BADOU, A. Abhandlungen, 178(2), 197-215.
2002. Discovery of jadeite-jade in Guatemala MCBIRNEY, A., AOKI, K.-I. & BASS, M. N. 1967. Eclo-
confirmed by non-destructive Raman microscopy. gites and jadeite from the Motagua Fault Zone,
Journal of Archaeological Science, 29, 837-851. Guatemala. American Mineralogist, 52, 908-918.
GREIFF, S. 1998. Naturwissenschaftliche Untersuchen- MCCANN, L. I., TRENTELMAN, K., POSSLEY, T. &
gen zur Frage de Rohsteinquellen ftir friihmittelalter- GOLDING, B. 1999. Corrosion of ancient Chinese
lichen Almandingranatschmuck rheinfr~inkischer bronze money trees studied by Raman microscopy.
Provenienz. Jahrbuch des R6misch-Germanischen Journal of Raman Spectroscopy, 30, 121-132.
Zentralmuseums, Mainz, 45, 599-646. NASDALA, L., SMITH, D. C., KAINDL, R. & ZIEMANN,
GRIFFITH, W. P. 1987. Advances in the Raman and M. A. 2004. Raman spectroscopy: Analytical per-
infrared spectroscopy of minerals. In: CLARK, spectives in mineralogical research. In: BERAN,
R. J. H. & HESTER, R. E. (eds) Spectroscopy of A. & LIBOWlTZKY, E. (eds) EMU Notes in Miner-
Inorganic-based Materials. Wiley, New York, alogy. Spectroscopic Methods in Mineralogy, 6,
119-187. 281-343.
GUINEAU, B. 1987. L'6tude des pigments par les OSr'ITALI, F. & SMITH, D. C. 2005. A Raman micro-
moyens de la microsp6ctrometrie Raman. In: scopic library of natural Mn oxides and oxyhydro-
DELAMARE, F., HACKENS, T. & HELLY, B. (eds) xides. In: 3rd International Conference on the
Datation-Caractdrisation des Peintures Parid- Application of Raman Spectroscopy in Art and
tales et Murales (PACT-t7). European University Archaeology, Louvre, Paris, 31 August-3
Centre for Cultural Heritage, Ravello, 259-294.
September 2005, Abstract volume, 82.
OSPITALI, F., SMITH, D. C. & LORBLANCHET,M. 2005.
HARLOW, G. E. 1994. Jadeitites, albitites and related
Raman microscopic analysis of prehistoric pig-
rocks from the Motagua Fault Zone, Guatemala.
ments in wall-painted caves: Roucadour, France.
Journal of Metamorphic Geology, 12, 49-68.
In: 3rd International Conference on the Appli-
JAMBOR, J., DUTRIZAC, J. & ROBERTS, A. 1996.
cation of Raman Spectroscopy in Art and Archaeol-
Clinoatacamite, a new polymorph of Cuz(OH)3CI, ogy, Louvre, Paris, 31 August-3 September 2005,
and its relation to paratacamite and 'anarakite'. Abstract volume, 20.
Canadian Mineralogist, 34, 61-65. PINET, M. & SMITH, D. C. 1993. La micr0spectrom~-
KIEFERT, L., H,~NNI, H. A. & OSTERTAG, T. 2001. trie Raman des grenats X3Y2Z3012: I. La s6rie
Raman spectroscopic applications to gemmology. calcique naturelle ouvarovite- grossulaire-
/17: LEWIS, I. & EDWARDS, H. G. M. (eds) A andradite. Schweizerische Mineralogische and
Handbook on Raman Spectroscopy. Marcel Petrographische Mitteilungen, 73(1), 21-40.
Dekker, New York, 469-489. PINEY, M. & SMITH, D. C. 1994. La microspectrom6-
KRESTEN, P., LARSSON, L. & HJARTHNER-HOLDAR,E. trie Raman des grenats X3Y2Z3012: II. La s6rie alu-
1998. Thermometo' of ancient iron slags from mineuse naturelle pyrope-almandin-spessartite.
Sweden, and of vitrified material from various Schweizerische Mineralogische and Petrogra-
hill-forts in western Europe. Geoarchaeology phische Mitteilungen, 74(2), 161 - 179.
Laboratory, Uppsala, Research Report, R9601. PINEY, M., SMITH, D. C. & LASNmR, B. 1992. Utilit6
LASNIER, B. 1989. GEORAMAN-89: CONTRI- de la microsonde Raman pour l'identification
BUTIONS. Special Publication, Association Natio- non-destructive des gemmes, avec une s~lection
nale de la Recherche Technique, Paris, 17. representative de leurs spectres Raman. In: La
LIEM, N. Q., SAGON, G., QUANG, V. X., TAN, H. V. & Microsonde Raman en Gemmologie. Revue de
COLOMBAN, P. 2000. Raman study of the Gemmologie, numdro spdcial hors sdrie, 11-61.
microstructure, composition and processing of QUAST, D. & SCHL13SSER, U. 2000. Mineralogische
ancient Vietnamese (proto)porcelains and celadons Untersuchungen zur Herkunft der Granate mero-
(13-16th centuries), Journal of Raman Spec- wingerzeitlicher Cloisonn6arbeiten. Germania,
troscopy, 31, 933. 78, 75-96.
LIEM, N. Q., THANH, N. T. & COLOMBAN, P., 2002. RALSTON, I. B. M. 1983. Vitrified walls. Bulletin of
Reliability of Raman microspectroscopy in analyz- Experimental Archaeology, 4, 10-11.
ing ancient ceramics: the case of ancient Vietn- RONDEAU, B. & SMITH, D. C. 2002. Non-destructive in
amese porcelain and celadon glazes. Journal of situ identification of gemstones on two 'Navaratna'
Raman Spectroscopy, 33, 287-294. jewels by MRM (mobile Raman microscopy). In:
MACQUET, C. 1994. Contribution h l'dtude des sur- 'ART 2002', 7th International Conference on
faces vitreuses anciennes; application b Non-destructive Testing and Microanalysis for
30 D.C. SMITH

the Diagnostics and Conservation of the Cultural SMITH, D. C. 2001a. Recent MRM (mobile Raman
and Environmental Heritage, University of microscope) analytical operations in situ in four
Antwerp, June 2002, Abstracts volume, 223. French museums. Colloquium: 'Raman Spec-
RULL-PEREZ, F. 2001. Applications of IR and Raman troscopy in Archaeology and Art History', British
spectroscopy to the study of Medieval pigments. Museum, bmdon, 20 November 2001.
In: LEWIS, I. & EDWARDS, H. G. M. (eds) A SMITH, D. C. 2001 b. Simulation of submarine archaeo-
Handbook on Raman Spectroscopy. Marcel merry by non-destructive physico-chemical analy-
Dekker, New York, 835-862. sis of gemstones by MRM (mobile Raman
RULL-PEREZ, F., EDWARDS, H. G. M., RIVAS, A. & microscopy) in situ under impure water. Congrks
DRUMMOND, L. 1999. Fourier transform Raman "Archdomdtrie 2001", GMPCA, La Rochelle
spectroscopic characterization of pigments in the Universit3.', 108.
Mediaeval frescoes at Convento de la Peregrina, SMITH, D. C. 2002a. ARCHAEORAMAN and mobile
Sahagun, L6on, Spain, Part 1--Preliminary study. Raman microscopy (MRM): from pigments in
Journal of Raman Spectroscopy, 30, 301-305. aerial wall-paintings to gemstones in submarine
SCHMETZER, K., KIEFERT, L., BERNHARDT, H.-J. & archaeometry. Congress GEORAMAN-2002. Acta
BEILI, Z. 1997. Characterisation of Chinese hydro- Universitatis Carolinae, Geologica, Praha, 46(1),
thermal synthetic emerald. Gems & Gemmology, 84-86.
33, 277-291. SMITH, D. C. 2002b. Semi-quantitative chemical
SCHREDER, B. & KIEFER, W. 2001. Raman spec- analysis of garnet and jade in mounted jewels by
troscopy on I I - V I semiconductor nanostructures. non-destructive Raman microscopy: recent pro-
In: LEWIS, I. & EDWARDS, H. G. M. (eds) Hand- gress with the analytical method. Congress
book of Raman Spectroscopy. Marcel Dekker, GEORAMAN-2002. Acta Universitatis Carolinae,
New York, 491-547. Geologica, Praha, 46(1), 87-89.
SEAWARD, M. R. D. & EDWARDS, H. G. M. 1998. SMITH, D. C. 2002c. MRM (mobile Raman
Biological origin of major chemical disturbances microscopy) in situ in four national museums.
on ecclesiastical architecture studied by Fourier 'ART 2002', 7th International Conference on Non-
transform Raman spectroscopy. Journal of Raman destructive Testing and Microanalysis for the
Spectroscopy, 28(9), 691-696.
Diagnostics and Conselvation of the Cultural and
SHARMA, S. K., ANGEL, S. M., GHOSH, M., HUBBLE,
Environmental Heritage, Universita' of Antwerp,
H. W. & LUCEY, P. G. 2002. Remote pulsed laser
Belgium, June 2002. Abstracts volume, 46.
spectroscopy system for mineral analysis on plane-
SMITH, D. C. 2003. In situ mobile subaquatic archaeo-
tary surfaces to 66 meters. Applied Spectroscopy,
metry evaluated by non-destructive Raman
56, 699-705.
microscopy of gemstones lying under impure
SHARMA, S. K., LUCEY, P. G., GHOSH, M., HUBBLE,
waters. Special Volume, Proceedings, GEORA-
H. W. & HORTON, K. 2003. Stand-off Raman
MAN-2002 Congress, Prague, 2002. Spectrochi-
spectroscopic detection of minerals on planetary
surfaces. Special Volume, Proceedings, GEORA- mica Acta, Part A, 59, 2353-2369.
MAN-2002 Congress, Prague, 2002. Spectrochi- SMITH, D. C. 2004a. An ancient Egyptian commem-
mica Acta, Part A, 59, 2391-2407. orative scarab carved in rock: non-destructive
SMITH, D. C. 1987. The Raman spectroscopy of natural mineral identification by Raman microscopy, ln:
and synthetic minerals: a review. International FREDERICKS, P. M., FROST, R. L. & RINTOUL, L.
Conference 'GEORAMAN-86'. Terra Cognita 7, (eds) XIXth International Conference on Raman
20-21. Spectroscopy, ICORS, Gold Coast, Australia,
SMITH, D. C. 1988. A review of the peculiar mineral- 8-13 August 2004, Proceedings, (CD-ROM).
ogy of the 'Norwegian coesite-eclogite province', SMITH, D. C. 2004b. Raman micromapping of physical
with crystal-chemical, petrological, geochemical and/or chemical transformations of minerals of
and geodynamical notes and an extensive bibli- interest in geology or archaeology. GEORAMAN-
ography. In: SMITH, D. C. (ed.) Eclogites and 2004, University of Hawaii, Honolulu, Hawaii,
Eclogite-Facies Rock~. Developments in Petrology, 6-11 June 2004. School of Ocean and Earth
12, 1-206. Science Technology Publications, 04-02, 71-72.
SMITH, D. C. 1996. The importance of using a half- SMITH, D. C. 2004c. Raman micro-mapping of chemi-
wave plate for the Raman spectroscopy of minerals cal and/or physical mineral phase transformations
which cannot be rotated under the laser beam, involving jadeite, coesite, diamond or zircon in
especially large objects of gemmological or natural ultra-high pressure metamorphic environ-
archaeological interest. GEORAMAN-96, Terra ments (UHPM). ht: FREDERICKS, P. M., FROST,
Abstracts, Supplement 2. Terra Nova, 8, 23-24. R. L. & RINTOUL, L. (eds) XIXth International
SMITH, D. C. 1999. Letting loose a laser: MRM Conference on Raman Spectroscopy, ICORS,
(mobile Raman microscopy) for archa~ometry and Gold Coast, Australia, 8-13 August 2004, Pro-
ethnomineralogy in the next millennium. Minera- ceedings (CD-ROM).
logical Socie~ Bulletin, December, 3-8. SMITH, D. C. 2004d. Non-destructive semi-quantitat-
SMITH, D. C. 2000. Pigments rouges et bleus sur cinq ive chemical analysis of a garnet gemstone by
oeuvres d'Am6rique: analyse non-destructive par Raman microscopy compared with analysis by
MRM (microscopie Raman mobile). Techne, 11, PIXE. hTternational Congress GEORAMAN-2004,
69-83. Honolulu, UniversiO' of Hawaii, 6-11 June 2004.
NON-DESTRUCTIVE RAMAN SPECTROSCOPY 31

School of Ocean and Earth Science Technology, quartz-jadeitite. Fifth International Eclogite Con-
Special Publications, 04-02, 73-74. ference. Terra Nova, 9, Abstract Supplement 1, 35.
SMITH, D. C. 2005a. Jewellery and precious stones. In: SMITH, D. C. & OSPITALI, F. 2005. First use of a hand-
EDWARDS, H. G. M. & CHALMERS, J. (eds) Raman held self-contained ultra-mobile Raman micro-
Spectroscopy in Archaeology and Art History. scope for non-destructive in situ analysis of gem-
Royal Society of Chemistry, London, 335-378, stones inlaid in XVIIth century Florentine stone
SMITH, D. C. 2005b. The RAMANITA ~- method for marquetry tables. 3rd International Conference
non-destructive and in situ semi-quantitative on the Application of Raman Spectroscopy in Art
chemical analysis of mineral solid-solutions by and Archaeology, Louvre, Paris, 31 August-3
multidimensional calibration of Raman wave- September 2005, Abstract volume, 66.
number shifts. Proceedings, 6th International SMITH, D. C. & PER1N, P. 2003. Non-destructive
GEORAMAN Congress, Hawaii, June 2004. Spec- in situ MRM (mobile Raman microscope) semi-
trochimica Acta, Part A 61, 2299-2314. quantitative chemical analysis of garnets in Mero-
SMITH, D. C. 2005c. Mesoamerican jade. In: EDWARDS, vingian cloisonn~ style jewellery from Vicq,
H. G. M. & CHALMERS, J. (eds) Raman Spec- France. International Congress 'Application of
troscopy in Archaeology and Art History. Royal Raman Spectroscopy in Art and Archaeology',
Society of Chemistry, London, 412-426, Ghent, September 2002, 62.
SMITH, D. C. 2005d. Raman mapping of the clinopyr- SMITH, D. C. & PINET, M. 1989. A method for single
oxene/silica contacts in the quartz-jadeitite rock, variable plotting of multi-dimensional chemical
possibly an 'Olmec Blue' jade, from Guatemala. data for comparing Raman wavenumbers with
3rd International Conference on the Application chemical variations in solid-solutions. GEORA-
of Raman Spectroscopy in Art and Archaeology, MAN-89: Contributions. Special Publication,
Louvre, Paris, 31 August-3 September 2005, Association Nationale de la Recherche Technique,
Abstract volume, 63. Paris, 24.
SMITH, D. C. & BARBET, A. 1999. A preliminary SMITH, D. C. & ROBIN, S. 1997. Early-Roman Empire
Raman microscopic exploration of pigments in intaglios from 'rescue excavations' ign Paris: an appli-
wall-paintings in the Roman tomb discovered at cation of the Raman microprobe to the non-destructive
Kertch, Ukraine, in 1891. Journal of Raman characterisation of archaeological objets. Journal of
Spectroscopy, 30, 319- 324. Raman Spectroscopy, 28(2-3), 189-193.
SMITH, D. C. & BOUCHARD, M. 2000a. Analyse de SMITH, D. C. & RONDEAU, B. 2001. Non-destructive
pigments des peintures pari&ales de Pergouset mineralogical analysis of precious stones in situ
par microscopie Raman, In: LORBLANCHET, under thick glass by MRM (mobile Raman
M. (ed.) La Grotte de Pergouset. DAF, Paris, 174. microscopy). Congress 'Archdomdtrie 2001',
SMITH, D. C. & BOUCHARD, M. 2000b. PETRORA- GMPCA, La Rochelle Universi~. , La Rochelle, 101.
MAN. Archdom~trie, Dossiers de l'Archdologie, SMITH, D. C. & VERNIOLES,J. D. 1997. The tempera-
253, 54. ture of fusion of a Celtic vitrified fort: a feasibility
SMITH, D. C. & BOUCHARD, M. 2002. Bronze disease: study of the application of the Raman microprobe
non-destructive distinction of three polymorphs of to the non-destructive characterisation of unpre-
Cu2CI(OH)3 by Raman microscopy (RM). 'ART pared archaeological objects. Journal of Raman
2002', 7th International Conference on Non- Spectroscopy, 28(2- 3), 194-197.
destructive Testing and Microanalysis for the SMITH, D. C., BOUCHARD, M. A. & LORBLANCHET,
Diagnostics and Conservation of the Cultural and M. 1999a. An initial Raman microscopic investi-
Environmental Heritage, University of Antwerp, gation of prehistoric rock art in caves of the
June 2002, Abstracts Volume, 227. Quercy district, S. W. France. Journal of Raman
SMITH, D. C. & CARABATOS-NEDI~LEC, C. 2001. Spectroscopy, 30, 347-354.
Raman spectroscopy applied to crystals: phenom- SMITH, D. C. EDWARDS, H. G. M. and Russ, J. 1999b.
ena and principles, concepts and conventions. In: Congress GEORAMAN'99, Abstracts. Valladolid
LEWIS, I. & EDWARDS, H. G. M. (eds) A Handbook University Press, Valladolid, 61-62.
on Raman Spectroscopy. Marcel Dekker, SMITH, D. C., CARABATOS-NEDI~LEC, C.
New York, 349-422. BOUCHARD, M. 1999c. VITRORAMAN: establish-
SMITH, D. C. & EDWARDS, H. G. M. 1998. A wave- ing a database on the Raman spectra of pigments on
number-searchable tabular indexed catalogue for and in stained glass. GEORAMAN'99, Abstracts.
'ARCHAEORAMAN~':~': Raman spectra of Valladolid University Press, Valladolid, 36-37.
geomaterials and biomaterials of interest in archae- SMITH, D. C., EDWARDS, H. G. M., BOUCHARD, M.,
ology (sensu lato). In: HEYNS, A. M. (ed.) ICORS BRODY, R., RULL-PEREZ, F., WITHNALL, R. &
Capetown'98. Wiley, Chichester, 510-511. COUPRY, C. 2000. MRM (mobile Raman
SMITH, D. C. & GENDRON, F. 1997a. Archaeometric microscopy): a powerful non-destructive poly-
application of the Raman microprobe to the non- valent in situ arch~eometric tool for microspectro-
destructive identification of two Pre-Columbian metrical analysis of cultural heritage in the next
ceremonial polished 'greenstone' axe heads from millennium (ARCHAEORAMAN): geomaterials,
Mesoamerica. Journal of Raman Spectroscopy biomaterials and pigments. In: GUARINO, A. (ed.)
28, 731-738. 2nd International Congress on 'Science and
SMITH, D. C. & GENDRON, F. 1997b. New locality and Technology for the Safeguard of Cultural Heritage
a new kind of jadeite jade from Guatemala: rutile- in the Mediterranean Basin, Nanterre, Paris, 5 - 9
32 D.C. SMITH

July 1999, Proceedings, Vohone 2. Elsevier, studies. Journal of Raman Spectroscopy, 31(6),
Amsterdam, 1373-1375. 509-517.
SMITH, D. C., GONTHIER, E. & REINHARDT,A. 2003a. WANG, A., JOLLIFF, B. L. & HASKIN, L. A. 1996.
Raman Microscopy of Chinese nephrite jades, both Raman system for robotic exploration on planets.
ancient cultural artefacts and geological sources in GEORAMAN-96, Terra Abstracts, Supplement N
China. International Congress 'Application of 2. Terra Nova, 8, 25.
Raman Spectroscopy in Art and Archaeology', WANG, C., LU, B., ZUO, J., SUZUKI, M. & CHASE,
Ghent, September 2002, 85. W. T. 1995. Structural and elemental analysis of
SMITH, D. C., PI~RIN, P., KAZANSKI,M. & GABUEV, T. the nanocrystal SnO2 in the surface of ancient
2003b. Andradite-rich pentary garnet compositions Chinese black mirrors. Nanostructured Materials,
deduced from non-destructive in situ MRM (Mobile 4, 489-496.
Raman Microscope) semi-quantitative chemical WHITE, W. B. 1975. Structural interpretation of
analysis of Vth century cloisonn~ garnets from an lunar and terrestrial minerals by Raman spec-
Alan warrior burial mound at Brut, Northern troscopy. In: KERR, C. (ed.) hlfrared and Raman
Ossetia, Russian Federation. International Con- Spectroscopy of Lunar and Terrestrial Materials.
gress "Application of Raman Spectroscopy in Art Academic Press, New York, 325-357.
and Archaeology', Ghent, September 2002, 39. W1THNALL, R. 1999. h7 situ identification of pigments,
VANDENABEELE, P., MOENS, L., EDWARDS, H. G. M. manuscripts and prints using Raman microscopy.
& DAMS, R. 2000. Raman spectroscopic database GEORAMAN'99. Valladolid University Press,
of azo-pigments and application to modern art Vailadolid, 15- ! 6.
The Neolithic pottery of Abri Pendimoun (Castellar, France):
a petro-archaeometric study
E. B A S S O 1, D. B I N D E R 2, B. M E S S I G A 1'3 & M. P. R I C C A R D I 1'3
1Dipartimento di Scienze della Terra, Universit~ degli Studi di Pavia,
via Ferrata n. 1, 27100 Pavia, Italy
2CEPAM-CNRS, rue Albert Einstein n. 250, Valbonne-Sophia Antipolis 06560 France,
3CISRiC-Beni Culturali, Universith degli Studi di Pavia, via Ferrata n. 1,
27100 Pavia, Italy (e-mail: riccardi@crystal.unipv.it)

Abstract: Middle and Late Neolithic ceramics from Abri Pendimoun (Castellar, France)
and their geological raw materials have been investigated to characterize the ceramic
bodies and to determine the possible provenance of raw materials. Petrographic, minera-
logical and energy-dispersive spectrometry analyses were undertaken to define the
compositional parameters of sherds and to clarify the relationship between Square
Mouthed Pottery-phase I (VBQ I) and Chassey Culture, The ceramic bodies were gener-
ally made from glauconite-rich layers and terra rossa, unprocessed or mixed in variable
proportions. Different kinds of temper, such as carbonates and/or aplite fragments,
were added to the mixtures. Although most of the analysed ceramics were produced
locally, a few mixtures show the addition of exogenous rocks. Although these ceramics
could be interpreted as imported, we demonstrate that local clayey materials were used
at Abri Pendimoun. The hypothesis that pottery was imported can therefore be ruled
out. A small amount of crushed calcite (5%) was added to some glauconitic pellet mix-
tures. Pots made with this mixture are normally referred to the VBQ I. This combination
of mixture and shape indicates that there was an important link between the VBQ I and
Chassey Cultures.

The Square Mouthed Pottery-phase I Culture The site of Abri Pendimoun is in a key position
(VBQ I) played an important role in the develop- along the communication route between Liguria
ment of Chassey Culture, as seen at the Villa (Italy) and eastern Provence (France). The clear
Giribaldi site in Nice (Binder 1990; Binder evidence of contacts with the VBQ I, seen in
et al. 1994) and in the diffusion of Chassey the geometric 'graffita' decorations on potsherds
Culture in northern Italy (Crepaldi 2001). The from the more ancient horizons (Binder 2000),
VBQ I appears in northern Italy from the sixth makes Pendimoun an important site in the
millennium BP: Chassey Culture arose in Prov- study of interactions between the VBQ I and
ence during the first half of the same millennium. Chassey Cultures in the transalpine area, which
The expansion of Chassey Culture in Italy occurred during the Middle and Late Neolithic
(Fig. 1) is very complex and it is today acknowl- age. This pottery is therefore particularly import-
edged that this cultural change was accompanied ant, not only because it enriches the collection
by ethnic transfer from southern France to the of artefacts from the Middle and Late Neolithic,
east, contributing to the spread of the Western but also because the technological and cultural
Neolithic in Italy (Bagolini & Pedrotti 1998). evidence may be extended to coeval archaeologi-
The occurrence of Bedoulian chert from Prov- cal contexts.
ence in Chassey Culture layers at the Arene These topics necessarily touch on a broader
Candide cave (Western Liguria) (Starnini & issue in the archaeology of ceramic production,
Voytek 1997; Binder 1998) demonstrates raw i.e. the concept of 'local pottery' or 'trade
material circulation as a factor in spreading the pottery', which in turn has important implica-
pot shapes, styles and technique of Chassey tions for the reconstruction of ancient economies.
Culture in Italy (Binder 1998). The VBQ I influ- Prehistoric ceramic products are generally
ences in France are less clear. Figure 1 shows the assumed to be local, although the temper may
VBQ I sites recorded in Provence. well have been obtained elsewhere (Martineau

From: MAGGETTI,M. & MESSIGA, B. (eds) 2006. Geomaterials in Cultural Heritage.


Geological Society, London, Special Publications, 257, 33-48.
0305-8719/06/$15.00 ~ The Geological Society of London 2006.
34 E. BASSO E T AL.

J s u ~ s s E ~ ~ ' ~ decorative variations as a result of, for instance,


a widespread exchange of ideas and traditions.
Archaeological sites, especially prehistoric
ones, rarely coincide with the source area of
raw materials. At Abri Pendimoun, archaeologi-
z_.C o -.. ,"~v..,. cal evidence, such as the discovery of potter's
T~no Pia6e.za " " k -- '~ ./ tools and raw materials (Binder 2002), suggests
that pottery was produced locally. In this study
the term 'local pottery' is applied to pottery
produced from natural materials available over
a sometimes vast geographical area containing
the archaeological site. The local boundaries
may be natural or man-made barriers that
:++i : 6 II limited access to other possible source areas.
The investigated ceramic material, abundant
in all stratigraphic levels, provides a detailed
+,.m "+,+/ ',..., " record of the evolution of shapes, decoration
styles, surface treatments and of ceramic mix-
Fig. 1. Simplified index map of Chassey sites in Italy tures at the site between Ancient and Late Neo-
and of VBQ I sites in Provence (modified from Crepaldi lithic time.
2002). This work presents a petro-archaeometric
study of Middle and Late Neolithic ceramics
(1245 artefacts) from the Abri Pendimoun exca-
2000; Di Pierro 2003). The choice of temper may vation. Geomaterials possibly used in the
indeed have been 'cultural', sometimes deter- ceramic production will be also studied. The
mining the selection of source areas that were aim of the research is to identify raw materials
far from the site (Constantin & Courtois 1985). (geomaterials) and production technology used
The definition of 'local pottery' has been to make the clay body mixture, and to give an
discussed in an ethno-archaeological study by insight into relationships between VBQ I and
Arnold (1985), who redefined the term in 2001 Chassey Culture in Provence.
(Arnold 2001). Arnold considered that the clay
and temper used to manufacture pottery should
be sought within a 1 - 2 k m radius of the Archaeological framework
production site, whereas a vessel produced with First excavated in 1955-1956 by Louis Barral
material from more than 10 km from the archae- (curator of the Museum of Prehistoric Anthropol-
ological site was brought to the site for reasons ogy in Monaco) and his staff, the Abri Pendi-
not strictly related to its manufacture. moun site (Castellar, Alpes Maritimes, France)
The concepts of local or imported are was then known for the numerous finds from
still unclear, as the provenance of raw materials the Ancient Neolithic and for an important
seems to vary in relation to different parameters, sepulchre ascribed to the Cardial period of the
including the geological and/or geographical Ancient Neolithic in Provence (Barral 1958).
context, the cultural traditions of certain groups, These elements made it an important point of
trade among groups, and social-economic reference between Fontbr~goua to the west
factors influencing the selection of source areas (Courtin 1976) and the Arene Candide cave to
(Martineau 2000). the east (Bernab6 Brea 1946, 1956) for analysing
Actually, considering how demanding prehis- the spread of Neolithic culture in the north-
toric populations were in the selection of raw western Mediterranean.
materials for lithic production, Arnold's affirma- The Abri Pendimoun ('abri', rock shelter) docu-
tion is not necessarily true (Bir6 1998). Indeed, ments a stratigraphic sequence from the upper
there is clear evidence of differential manage- Epipalaeolithic (about 10th millennium BP) to
ment of lithic resources, and it is likely that obsi- the final Neolithic (about third millennium BP)
dian (Crisci et al. 1994) and Bedoulian chert (Binder et al. 1993). The Pendimoun excavations
were transported over long distances (Binder & reveal one of the most peculiar and detailed
Perlrs 1990) to be traded for 'greenstone' (i.e. stratigraphic sequences (including the seventh
eclogites) (Odetti 1991; D'Amico 2005; and sixth millennia BP) studied so far in the
D'Amico & Starnini 2005). western Mediterranean area. The sequence
Even assuming the local origin of many shows great research potential, and its peculiar
ceramics, there may be large technological and characteristics may help to solve some issues
NEOLITHIC POTTERY OF ABRI PENDIMOUN 35

regarding the Mediterranean Neolithic, such as layers. The grey marls are in contact with
intercultural relations in the area between the yellow marls resulting from the alteration of
domains of Provence and Italy. The interpret- the limestones. This contact enhances water cir-
ations, already discussed by Binder et al. culation, as evidenced by the numerous springs
(1993), make Abri Pendimoun one of the most at the foot of the Ormea cliff. The principal geo-
important sites providing insight into the spread logical formations in this area (Fig. 2) are Upper
of Neolithic culture in western Europe. Cretaceous marly-calcareous undifferentiated
rocks (C3_7), with massive limestones, and Neo-
comian units, characterized by marly limestones,
Geological setting calcareous marls and layered marls interbedded
The rock shelter is a natural cavity formed at with glauconite-rich layers (N|_4). The Portlan-
the contact of limestones (Kimmeridgian- dian limestones (J9) a r e massive, and their
Portlandian) with grey marls (Neocomian), which colour varies from grey (northwestern area) to
are in turn interbedded with glauconite-rich white (southern area). The Upper Jurassic is

N,~: Marly limestones, calcareous marls, marls


D E: debris chaotic deposits
l interbedded with gtauconitic layers (Early Cretaceous)

[~G: Annot sandstone and Otigocene flysch 1"[]]]] Jg-J~:Limestones and marls (Jurassic)

[~ E~_~:Melobesiae limestones (Upper Eocene) ]T~: marls and gypsum (Late Triassic)

~ z ] Es: Nummulitic limestone (Middle Eocene) ] M e d i t e r r a n e a n Sea

[~ C3_~:marls and limestone (Cretaceous) " ' : France-Italy boundary

Fig. 2. Location of the archaeological site (A) and sampling points (.) of raw materials, on a simplifiedgeological map
(after Geze 1968). The Ormea cliff is located near the Abri Pendimoun site. The numbers correspond to the samples
listed in Table 2.
36 E. BASSO ETAL.

represented, in the south, by a pseudo-oolitic Table 1. Ceramic finds analysed in thin section
massive limestone.
Thin Inventory no. Subgroup Wall
section thickness
Sampling (mm)

Ceramic finds AP37 AP 23075 1G 8.7


AP4 AP 105 LI9 IG 6.8
The study of ceramic finds entailed a preliminary AP5 AP 11003 1G 5.6
phase, in which all potsherds (1245 finds) AP6 AP 112 LI9 1G 9.8
ascribed to the Middle and Late Neolithic were 12-14 R3
analysed under the optical stereomicroscope. A AP8 AP 11723 1G 4.4
selection of 46 ceramic fragments was used for AP9 AP 12 M19 1G 6.0
archaeometric investigation (Table 1). These AP10 AP 122 LI9 12-14 1G 7.8
AP11 AP 12416 IG 4.2
were chosen from among those artefacts belong- AP13 AP 190 M21 n60-82 1G 5.0
ing to the most representative groups of mix- AP14 AP 20606 1G 5.0
tures; also 'anomalous' finds, i.e. with unusual AP15 AP 20645 + 20763 IG 4.0
textural and/or compositional characteristics AP17 AP 22708 1G 5.4
with respect to those of the main ceramic AP20 AP 26 M20 IG 7.0
groups, were taken into account. AP21 AP 3 MI9 7 IG 7.2
AP22 AP 77 LI9 IG 7.3
AP25 AP M21 CPE 1G 6.5
R a w materials diag str 11
To identify the source area of raw materials, AP29 AP 11223-4 1G 4.2
samples of geological materials (15 specimens) AP32 AP 68 L19 8-10 RI IG 6.0
suitable for the production of ceramics were AP34 AP 12045 IGS 7.8
collected within an approximately 5 km radius AP36 AP 13586 IGS 5.0
of the archaeological site (Fig. 2). The sampling AP38 AP 74 L19 8-10 R3 1GS 6.4
was determined by: (1) geological knowledge AP39 AP HS 2002 I GS 9.0
of the area; (2) petrographic data obtained
AP30 AP 12454+ 12436 IGCc 5.2
from ceramic artefacts; (3) excavated raw AP31
AP 12346 1GCc 5.5
materials. The geological formations involved
were (1) Neocomian marly carbonate clays and API9 AP 23720 1GC 7.3
the intercalated glauconite-rich layers (Nj_4); AP7 AP 11272 IGC 4.2
(2) Portlandian (J9) and Upper Cretaceous (C3_7) API2 AP 13541 1GC 6.3
marly clays; (3) terra rossa (Fig. 2; Table 2). AP23 AP 83 K19...RI 1GC 10.6
AP24 AP 97 LI9 12-14 RI IGC 9.0
AP26 AP 13639 1GC 5.3
Analytical strategy AP28 AP 23072 1GC 7.6
AP 16 AP 21 M20 7 1GC 4.8
The sampling strategy strictly follows the multi- API8 AP 23074 1GC 6.5
disciplinary investigative procedure defined by AP27 AP 22699 1GC 6.4
Basso (2004). This procedure involves three
stages ( M A C R O 1 - M I C R O - M A C R O 2 ) and AP2 AP 10911 IGSCc 6.8
entails the study of finds at different scales of AP3 AP 8955 1GSCc 7.0
observation, as well as a complete integration of AP33 AP 103 L 19 2S 7.3
archaeometric and archaeological data. This 12-14 R2
approach aims to apply both the first (MACRO1) AP35 AP 12539 2S 9.3
and last (MACRO2) stages to all the excavated AP40 AP 9781 2S 4.3
ceramic materials using an optical stereomicro- AP41 AP 10313 2S 5.5
scope (a non-invasive and low-cost procedure). AP42 AP 8972 + 8973 2S 5.9
The archaeometric stage sensu stricto, completed AP44 + 8977 + 9038
AP 8996 2S 5.5
at a detailed observation scale (MICRO), was AP45 AP 9361 2S 5.5
applied to samples containing variations in tex-
tural and compositional characteristics identified API AP HS 2C 6.0
during the MACRO1 stage. The extremely
detailed observational characters, obtained at AP43 AP 20225* 3F 8.0
AP46 AP 5243 3F 9.0
the MICRO scale, were then applied to all
samples during the following MACRO2 stage. *VBQ ! fragment.
NEOLITHIC POTTERY OF ABRI PENDIMOUN 37

Table 2. Geomaterials sampled near the lack of spheroidal glauconitic pellets. The most
archaeological site statistically diffuse texture is the 'hiatal' one, as
defined by Maggetti (1994), which was identified
Sample Geomaterial Geological Location
no. formation no.* with certainty under the stereomicroscope by the
evident discontinuity between the grain size of
AP.S2 Glauconitic layer Nl_ 4 2 non-plastic inclusions (temper and framework)
AP.S3 Carbonatic clay J9 3 and that of the matrix. All 1245 ceramic finds
AP.S4 Marly clay C3_7 4 have been grouped into three petrographic
AP.S5 Gauconitic layer N1_4 5 groups (Table 3; Fig. 3a). Only a few finds
AP.S9 Gauconitic layer Nl_ 4 9 lack non-plastic inclusions and have thus
AP.S10 Gauconitic layer NI_ 4 10
been placed in a specific petrographic group.
AP.S 11 Gauconitic layer N1-4 11
AP.S14 Terra rossa E 14 Subgroups were defined according to the pre-
AP.S15 Marly clay C3_7 15 sence of glauconitic pellets and their association
AP.Sl6 Gauconitic layer NI_ 4 16 with other non-clayey materials (Table 3;
AP.S17 Gauconitic layer NI_ 4 17 Fig. 3b), whose mineralogy was determined by
AP.S 18 Gauconitic layer N 1-4 18 evaluating the hardness of single fragments,
AP.SI9 Marly clay C3_ 7 19 their shape and colour. The carbonate fragments
AP.S20 Terra rossa E 20 are softer and may be scratched with a metal
AP.S24 Giauconitic layer N1_4 24 point, whereas silicate fragments are harder and
*Numberscorrespond to sampling points in Figure 2. cannot be scratched. Fragments of non-uniform
colour were classified as lithic clasts.
Most of samples belong to Chassey Culture;
In this way, the dataset acquires statistical val- the 41 remaining samples are related to the
idity, as all typologies of ceramic mixtures from VBQ I (Basso 2004). These latter in turn have
the excavation area are included and it can be only one sample belonging to group 1.
integrated with archaeological data.
In the MACRO 1 stage, the most representative
artefacts of each group and subgroup of ceramic The MICRO stage
mixtures were selected, along with some speci- The multi-analytical strategy (MICRO) applied
mens showing 'anomalous' characteristics. The to the study of ceramic artefacts and raw
MICRO stage was applied to 46 highly fragmen- materials combines textural (using polished,
ted ceramic finds representing common wares C-coated thin sections), microchemical and
(plates, bowls, tall pots, jars, basins, cups, etc.), bulk analyses. The textural analysis of thin sec-
whose shape cannot always be reconstructed. tions is the most straightforward approach to
investigate ancient ceramics (Courtois 1976;
Maggetti 1994; Dickinson & Shutler 2000). Pet-
The MACRO1 stage rographic studies under the optical microscope
The diagnostic character for the pottery of Abri provide data on the mineral composition and pro-
Pendimoun, identified during the first stage of portion (modal amount) of temper, non-plastic
investigation (MACRO1), is the presence or inclusions and clay matrix. Furthermore, the

Table 3. Groups and subgroups recognized under optical stereomicroscope (MACROI column) and under
polarized-light microscope, in thin section (MICRO column)
Group Fabric Glauconitic Subgroup Temper
pellets
MACRO 1 MICRO
1G 1G Untempered
1GS IGS Aplitic rocks
1GCc Calcite
1 Hiatal Yes 1GC 1GC (a) Glauconitic limestone
(b) Oolitic limestone
(c) Micritic limestone
1GSC IGSCc Aplitic rocks + calcite
2 Hiatat No
{ 2Cc
2s 2S Aplitic rocks
2Cc Calcite
3 Seriate No 3F 3F Untempered
38 E. BASSO ETAL.
(a) (b) 2S (3%)~2Cc (1%)
(1%)

i'fi'iil
Group 1 (95%)
1GS (13%)

1245 SAMPLES I
1G (69%)

Fig. 3, (a) Finds distribution among the three groups (MACRO phase). (b) Finds distribution among subgroups
(MACRO phase). G, glauconitic pellets: S, silicate fragments:C, carbonate fragments:Cc, sparry calcite; F, fine mixture.

scanning electron microscope (SEM) is used for OES) technique. Samples were prepared and
the microstructural and microchemical investi- analysed in batches. Each batch contained a
gation of the intergranular clay matrix. The method reagent blank, certified reference
analytical procedure combines microanalytical material, and 17% replicates. Samples were
data on the clay matrix with mineralogical mixed with a flux of lithium metaborate and
(qualitative composition) and petrographic data lithium tetraborate and fused in an induction
on the ceramic bulk sample. Micro-analytical furnace. The molten melt was immediately
data were determined at the University of Siena poured into a solution of 5% nitric acid contain-
(Earth Science Department) using a Philips XL ing an internal standard, and mixed continuously
30 SEM equipped with a Philips EDAX-DX4 until completely dissolved (c. 30min). The
energy dispersive spectrometer. The expected samples were then run for major oxides on a
error for major and minor element measurements combination simultaneous-sequential Thermo
is 5% and 15%, respectively. Jarrell-Ash ENVIRO II ICP. The sample solution
The qualitative mineralogical composition was also spiked with internal standards and was
was obtained by X-ray powder diffraction further diluted and introduced into a Perkin
(XRPD) and polarized-light microscope examin- Elmer SCIEX ELAN 6000 inductively coupled
ation of thin sections. X-ray powder samples plasma mass spectrometer using a proprietary
were prepared by crushing in an agate mortar sample introduction technique. Calibration was
followed by addition of 10% diluted HC1. This performed using USGS and CANMET certified
last procedure was adopted to avoid the interfer- reference materials (Table 4).
ence due to the presence of abundant calcite,
which could mask the diagnostic reflections of
firing phases such as gehlenite, pyroxene and Results
anorthite. This procedure was not applied to The results of the petro-archaeometric and
raw materials. Bulk chemical data was deter- chemical analyses of ceramic finds and raw
mined at Activation Laboratories Ltd (Ontario, materials are discussed for each mixture group
Canada) using the fusion inductively coupled and for each typology of raw materials; only the
plasma-optical emission spectrometry (ICP- clay matrix petrography is described separately.

Table 4. Typical ICP analysis (wt%) of some USGS and Canmet Standards (%) (detection limits are given
in parentheses)

Standard SiO2 A 1 2 0 3 Fe203 MnO MgO CaO Na20 K.O TiO2 P205
(0.01) (0.01) (0.01) (0.001) (0.01) (0.01) (0.01) (0.01) (0.001) (0.01)
SY3 59.51 11.62 6,47 0.32 2.54 8.25 4.17 4.23 0.14 0.52
MRG1 39.43 8.59 17.93 0.17 13.74 14.77 0.73 0.18 3.78 0.07
DNC1 46.91 18.46 9.76 0.15 10.05 11.27 1.99 0.24 0.47 0.07
BIR1 47.78 15.43 11.52 0.17 9.70 13.75 1.86 0.02 0.95 0.02
W2 52.58 15.35 10.72 0.16 6.37 10.98 2.31 0.64 1.05 0.12
G2 68.72 14.95 2.65 0.03 0.71 1.87 4.08 4.48 0.48 0.13
STM1 59.64 18.07 5.24 0.22 0.07 1.09 8.87 4.24 0.13 0.1
NEOLITHIC POTTERY OF ABRI PENDIMOUN 39

The textural and compositional parameters small fossils with carbonate shells were
(i.e. grain size, shape, mineralogy of non- observed.
plastic inclusions and non-plastic inclusions/
clay matrix ratio) allowed the detailed definition
of the different types of ceramic mixtures. The Ceramic finds
presence or lack of glauconitic fragments and Group 1. This group always shows the pre-
of other kinds of non-plastic inclusion defines sence of glauconitic pellets, sometimes associ-
the petrographic groups of ceramic mixture ated with rock fragments (silicate or carbonate)
(Fig. 3a). Within these groups, the association of and/or sparry calcite. These are rounded,
different types of temper defines seven subgroups 25 lxm to a few millimetres in size (Fig. 4a)
(Fig. 3b; Table 3) and 10 types of mixture and, in contrast to the bright green colour of
(Table 3). Artefacts with a seriate texture form a unfired materials (Fig. 5a), they are yellowish-
separate group (Table 3). Table 5 reports the brown, brown, red, or black.
mineralogical association of the non-plastic The glauconitic pellets are cracked during firing,
inclusions of the ceramic finds according to and the cracks often are filled with secondary
group and subgroup mixtures. calcite aggregates of a few tens of microns in size.
Two types of clay matrix, dark brown or light Silicate rock temper is commonly of milli-
brown-reddish, may be identified in thin section metre scale (5001xm to 2mm), with an
under the polarized microscope. Often, in the irregular, angular and subordinately subrounded
dark brown matrix, the framework is absent or morphology (Fig. 4b), and occurs in amounts
undetectable. The framework essentially consists ranging from 10 to 15 vol% in subgroup 1GS.
of small quartz fragments sometimes associated In the fragments, the mineralogical associations
with plagioclase, K-feldspar, rare muscovite are quartz + plagioclase, quartz + plagioclase +
lamellae and small rock fragments (microcrystal- K-feldspar and quartz + muscovite + plagioclase
line siliceous and sedimentary rocks). In contrast, (feldspars are well preserved). Textural relations
the light brown-reddish matrix has a rather among minerals suggest that fragments derive
abundant framework of <200 txm grain size from igneous rocks such as aplites. This kind of
consisting of quartz, K-feldspar, plagioclase, temper is associated with glauconitic pellets in
muscovite and/or biotite as major phases, associ- subgroup 1GS (Fig. 4b) and with glauconitic
ated with rare fragments of microcline and pellets and sparry calcite in subgroup 1GSCc.
zircon. Occasionally, fragments of calcite, In this latter subgroup calcite and aplite frag-
microcrystalline silicate rocks and, occasionally, ments do not exceed 10 vol%. The presence

T a b l e 5. Petrographic composition of sherds (rough average for every subgroup)

Group 1 2 3
L

Subgroup G GS GCc GC.a GC.b G C . c GSCc S Cc F


T/M >0.4 >0.4 >0.4 >0.4 >0.4 >0.4 >0.4 >0.4 0.1 <T/M<0.4 >0.4
Glauconitic pellets : ! ..... | ] [ [
Quartz :. : , m Bt
Micas ....... ......... J - - ~
K-feldspar I
Plagioclase ' ' ,. ,
. . . . .........
Sparry calcite ~i ~"

Calcite .. ,.I
Aplite :~ii~:. ....
Sandstone i
Glauconitic limestone I

Oolitic limestone ,,,,

Micritic limestone
Jasper
Fe-oxides : . .". . •

The estimated value of 0.4 is the minimum T/M ratio calculated for each subgroup. G, glauconitic pellets; GS, glauconitic pellets +
silicate grains; GCc, glauconitic pellets + carbonate grains; GC, glauconitic pellets + carbonate grains; GSCc, glauconitic pellets +
silicate grains + calcite; S, silicate grains; Cc, calcite; F, fine; T/M, non-plastic inclusions/clay matrix ratio.
40 E. BASSO ET AL.

of carbonate rock fragments characterizes This group is characterized by the constant


subgroup 1GC (Table 5). Fragments have an presence of a clay mineral peak at d = 10.1 A,
irregular, subangular shape and vary in size which in this case may correspond to glauconite.
from a few hundred microns to 1 mm. The abun- Quartz is the most abundant mineral detected by
dance of carbonate rock fragments ranges from XRPD (Table 6). The intensity of quartz reflec-
5 to 20 vol%. tions in group I GS is the highest (Table 6).
Microscopic analysis allowed the identifi- The major amount of quartz and the constant
cation of three lithologies: (I) glauconitic lime- presence of feldspar reflections (plagioclase and
stones; (2) oolitic and/or fossiliferous K-feldspar) are attributed to the rock fragments
limestones; (3) micritic limestones. These types of the non-plastic fraction. Neoformed minerals
of temper are always associated with glauconitic such as pyroxene and/or hematite were identified
pellets and define three types of mixture within in rare cases; in they occur particular in groups
subgroup 1GC (Table 5): glauconitic pellets I GS, 1GCc and 1GC (Table 6). Nevertheless,
and glauconitic limestone (1GC.a, Fig. 4c), glau- the presence of firing phases cannot be excluded
conitic pellets and oolitic and/or fossiliferous for two reasons: either the dimensions of crystals
limestone (1GC.b), and glauconitic pellets and are too small to yield a significant XRD response,
micritic limestone (1GC.c). or neoformed phases may have been weathered
The sparry calcite as temper is rather sporadic during burial, as emphasized elsewhere for geh-
and often associated with other types of tempers lenite (Courtois 1973; Heimann & Maggetti
(subgroups 1GC c and 1GSCc). In subgroup I GCc 1981 ; Maggetti 1994).
(Fig. 4d), a minimum percentage of sparry calcite In this group the clay matrix corresponds to the
(5%) is associated with the glauconitic pellets. dark brown typology. In the matrix, S i O 2 and

. t j,~" ..It .

Fig. 4. Micrographs of ceramic mixtures. (a) Hiatal texture, subgroup 1G (plane-polarized light); (b) hiatal texture,
subgroup 1GS (crossed Nicols); (c) hiatal texture, subgroup IGC.a (plane-polarized light); (d) hiatal texture, subgroup
1GCc (crossed Nicols);
NEOLITHIC POTTERY OF ABRI PENDIMOUN 41

A1203 contents very widely in group 1, from 57 to never exceeds 20 vol% and the fragments never
63.1 wt% and from 8.2 to 21.8 wt% on average, show any evidence of decarbonation.
respectively (Table 7). MgO and FeO show a posi- Group 2 is characterized by the almost total
tive correlation when the clay matrices of group 1 absence of mica/illite-glauconite reflections.
and the glauconite-rich layers are considered. Only Quartz is the most abundant phase, followed by
a group of finds and of glauconite-rich layers K-feldspar and plagioclase (Table 6). Neoformed
varies from this general trend in MgO content. pyroxene, probably diopside, is scarce or rare.
Group 1 contains up to 95% of finds (Fig. 3a). This mineral was detected only by XRPD. The
In this group, the VBQ I pottery corresponds to clay matrix corresponds to the reddish typology.
the subgroups 1GCc (56%), 1G (34%) and 1GS Group 2 contains up to 4% of finds (Fig. 3a). In
(10%) (Basso 2004). this group, the VBQ I pottery corresponds to
subgroup 2S (20%) (Basso 2004).
Group 2. Ceramics ascribed to this group
contain aplite fragments in subgroup 2S (Fig. 4e;
Table 5) and sparry calcite in subgroup 2Cc Group 3. Group 3 only contains subgroup 3F, it
(Fig. 4f; Table 5). In subgroup 2S, the abundance lacks temper fragments and is characterized by a
of igneous rock fragments (25-30 vol%) is fine-grained mixture (Fig. 4g). The mineralogical
greater than in subgroups 1GS and 1GSCc. composition is similar to that of Group 2, except
Rarely, only sparry calcite is used as a temper for a minor content of quartz and feldspars
(subgroup 2Cc, Fig. 4f). In this latter group, con- (Table 6).
sisting of a single specimen, rhombohedral In this group the clay matrix corresponds to
calcite is 100 ~m to 1 mm in size. Calcite the light brown or reddish typology.

Fig. 4. Continued(e) hiatal texture, subgroup 2S (crossed Nicols); (f) hiatal texture, subgroup 2Cc (crossed Nicols);
(g) seriate texture, subgroup 3F (plane-polarizedlight). G.p., glauconiticpellets; A.r., aplite; G.I., glauconitic
limestone; Cc, sparry calcite.
42 E. BASSO ETAL.

- •

,.- - ? ~.~" ~ , ,
" ,'~ ,~ 'adD~ill "

~ ~ , . ~.-~- .,"

• '" q ." " -,j ~. ~" ;6. ,, ' • " ~ .

.- - lu,r

- . : ~., &~ . ," ~ & ~, ,~.. / -,


• ,. ~ . i t
• ..
, , ~ . • - . ~ . . *

I~. . -"

i . . b

, . Jl~ o, ~ f ;.

a ." ' . . ~ "~i[, "

Fig. 5. Micrographs of raw materials. (a) Carbonate clay (plane-polarized light); (b): glauconitic layer (plane-polarized
light); (c) terra rossa (plane-polarized light); (d) clay pellets (subgroup IGC; crossed Nicols). C.p., clay pellet.

Group 3 contains up to 1% of finds (Fig. 3a). In Glauconite-rich layers. These layers consist of
this group, the VBQ I pottery comprises 10% of abundant glauconitic pellets held together by
finds (Basso 2004). a very fine matrix (Fig. 5a). The pellets are
rounded, with diameters ranging from fine
(50-250 p.m) to coarse (250-700 txm), depend-
Raw materials ing on the position within the sampled layer: the
coarser pellets are at the bottom of the layer.
Carbonate and marly clays. These are very Although the pellets are bright green under the
fine, fat clays (Fig. 5b). The variable carbonate optical microscope, they sometimes show
component is easily detected by XRD yellow to green colour. The matrix, which is
(Table 6). The framework consists of small dark green under the optical microscope, binds
angular quartz fragments, some muscovite the pellets and is very fine-grained. Commonly
lamellae and rare sedimentary rock fragments. it contains a framework consisting of small,
Small glauconitic pellets (< 150 p.m) are angular quartz fragments, calcite fragments and
scanty. Small gastropod fossils in the marlier sporadic muscovite lamellae. The glauconite-
portions may also occur. Clay minerals are rich layers are inhomogeneous in both clay
chiefly i l l i t e + k a o l i n i t e _ chlorite (Table 6). matrix/pellets ratio and mineralogical compo-
The marly layers contain a moderate amount of sition of the matrix; they show also a wide
kaolinite and high contents of calcite (Table 6); chemical variability (Table 7).
they show low SiO2 and A1203 contents and
very high values of CaO (Table 7). The carbonate Terra rossa. This is a clayey fine-grained
layers are the richest in calcite, with moderate material, bright red in colour, with quartz, mus-
K-feldspar and low quartz contents (Table 6). covite lamellae and rare calcite fragments
In Table 7, they show A1203 and CaO contents (Fig. 5c). XRPD analysis reveals an association
of 13 wt% and 15 wt%, respectively, associated of clay minerals consisting of chlorite + illite +
with low values of MgO and Fe203. kaolinite (Table 6). Hematite is also present•
NEOLITHIC POTTERY OF ABRI PENDIMOUN 43

Table 6. Semi-quantitative contents of minerals in sherds and raw materials, based on X R P D data

Sample Chl M/I-G1 Kaol Qz P1 K-f Cc* Dol Px Hem CaO

Subgroup 1G
AP6 ++ + + +
AP1 ++ ++ - +

AP8 ++ ++
AP9 + +
AP15 ++ +
AP21 ++ +
AP22 ++ +
AP25 ++ ++
AP29 + +
Subgroup 1GS
AP34 XX + + - + +
AP38 ++ X + + +

Subgroup 1 GCc
AP3 - ++
AP31 ++ +
Subgroup 1GC
AP19 ++ ++
AP23 + ++
AP24 + ++ _ D

AP27 + ++ m m _

AP28 + X + - +

Subgroup 2S
AP33 X ++ ++
AP42 + XX ++ + +
AP45 - XX ++ ++ + +

Subgroup 3F
AP43 ++ - +
R a w materials
Carbonatic clay + - ++ - X XXX
Marly clay - + X X - XX
Terra rossa - - - X + + +
Chl, Chlorite;M/I-G1,mica/illite-glauconite;Kaol,kaolinite;Qz, quartz; PI, plagioclase;K-f, K-feldspar;Dol,dolomite;Px, pyroxene;
Hem, hematite;CaO, calciumoxide. Abundance:XXX, very high (>40%); XX, high (30-40%); X, moderate(15-30%); ++, low
(5-15%); +, scarce (3-5%); -, rare (<3%).
*Cc not detectedin sherdsbecauseof the HCI treatmentof samples.

The chemical composition of terra rossa has temper. In fact, in the outcrop the glauconite-
high A1203 and Fe203 contents and low values rich layers are characterized by the hiatal
of MgO and CaO (Table 7). texture, with a gap between the dimension of
pellets and the fine matrix (Fig. 5a). In the
outcrop the inhomogeneity of the geological
Discussion and conclusions
material explains the wide variation of CaO
The ceramics studied here belong to three and A1203 contents in some glauconite-rich
mixture groups corresponding to different layers. The composition of the clay matrix of
'recipes'. The ternary diagram in Figure 6a these subgroups is compatible with a mixing of
shows a good match between the compositional glauconite-rich layers and terra rossa (Fig. 6 b -
field of clay matrix in subgroup 1G and e). The petrographic evidence (Figs 4 and 5)
glauconite-rich layers sampled in the vicinity of and the compositional similarities between the
the rock shelter. This suggests that an unpro- clay matrix of the artefacts and the raw
cessed mixture was used. The hiatal texture of materials (Fig. 6), available close to the site
finds in this subgroup has led to an important (marls and glauconite-rich layers) or nearby
technological consideration, because the hiatal (terra rossa) suggest that the pottery was
texture does not always indicate the addition of produced locally.
T a b l e 7. Average chemical contents determined by SEM-EDS fi)r each group of mixtures, and standard deviations for clay matrix of finds and raw materials';
bulk chemical data for raw materials are also reported
Average Number of SiO2 TiO2 A1203 Cr203 Fe203t MnO MgO CaO Na20 K20 P20.~
compositions analyses* (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%)

l G matrix 30 57.0 ± 4.6) 0.2 (_+0.1) 8.2 ( + 2.8) 0.2 ±0.1) 23.8 (4-4.4) 0.1 (+0.1) 4.0(+0.5) 3.8 (+2.0) 0.7 (+0.3) 5.0 ( + 2.2) 0.5 +0.5)
IGS matrix 10 63.1 4- 3.2) 1.0 (_+ 1.41 20.1 ( + 1.3) 0.0 +0.1) 10.2 + 1.1) 0.1 (±0.1) 1.5 (_+0.4) 2.3 (_+0.8) 1.0 (+0.7) 2.7 ( _+0.5) 0.0
1GCc matrix 22 58.4 +2.5) 0.4 ( ± 0.2) 13.1 (+3.9) 0.2 _+0,11 15.0 + 5.9) 0.1 (__+0.1) 3.8(_____1.0) 4.9 (+2.2) 0.81+0.31 4.7 ( + 0.6) 0.3 ±0,31
IGCc clay pellets 4 61.5 +2.0) 0.5 ( + 0.2) 21.8 (4- I.I) 0.1 +0.1) 7.0 +0.7) 0. I ( + 0 . 2 ) 2.4(__+0.2) 2.1 (±0.1) 1.21_0.3) 4.5 ( ± 0.3) 0.0 i 0.1 )
1GC matrix 50 58.2 ± 4.9) 0.3 (+_0. I) 10.4 (+2.4) 0,2 +_0.1) 20.7 ±5.5) 0.21+___0.11 4.1 ( + I . I ) 4.01±0.1) 0.6 (+0.11 4.5 (_+ 1.2) 0.5 +0.4)
1GC clay pellets 1 67.2 1.7 15.2 0. I 9.2 0.1 3.5 1.7 0.3 2.5 0.3
1GSCc matrix 10 58,1 _+ 1.2) 0,5 ( + 11.2) 14.5 ( + 1.9) 0.3 +0.1) 16.1 -t- 1.6) 0.31±0.1) 4.1 (±0.6) 2.9 (+0.5) 0.7 14-11.1) 5.0 (±0.31 0.7 +O.3)
2S matrix 30 62.1 +_3.71 0.6 ( + 0.2) 21.7 (+2.11 0.2 _+0.11 7.5 -t-0.9) 0.2 ( ± 0. I ) 1.8 ( 4- 0.6) 2.61±11.9) 0.81_0.5) 3,2 (___0.7) 0.4 ±0.4)
3F matrix 12 58.7 ± 3.0) 1.2 (+2.11 24.7 ( + 2.3) 0. I 9.4 ± 2.2) 0.1 (±0.1) 2.4(+0.4) I.I (_+0.3) 0.8 (±0.4) 3.3 (___ 1.0) 0. I ±0.1)
Glauconitic 25 57.5 _+6.4) 0.4 ( + 0.5) 9.1 ( + 1.7) 0.0 20.4 _+4.7) 0.2(__+0.3) 3.9(+__1.41 4,71_+3.91 0.41±0.41 6.6 14-2.1) 0.8 ±_0.8)
layers matrix
I G glauconitic 33 55,2 + 5.2) 0.2 ( _ 0 . 1 ) 6.6 (4- 1.9) 0.2 4-0.1) 29.2 _+4,0) 0.2 +0. I) 4.6 (_+0.5) 1.3 (_+11.3) 0.6 (+0.2) 7.4 (_+2.5) 0.2 +0.2)
pellets
1GS glauconitic 10 59.9 ± 1.7) 0. I (+0.1) 7.8 ( + 11.8) 0.1 ±0.1) 27.5 ( ± 1.6) 0. I 3.7 ( + 0 . 2 ) 1.0 (+_0.3) 0.8 ( ± 0 . 4 ) 4.4 ( + 0 . 6 ) 0.0
pellets
1GCc glauconitic 27 58.3 + 1.6) 0.1 (+_0.11 8,6 +_ 1.0) 0.I ±0.l) 24.0 ( + 1.5) 0. I -I-0.11 4.7 ( ± 0 . 3 ) 1.1 +11.3) 0.91±0.5) 6.1 _+11.6) 0.1 +11.21
pellets
1GC glauconitic 511 56.5 _+3.11 0.2 (_+0.1) 8.5 + 1.2) 0.2 ( ___0. I ) 25.4 ( ± 3.0) (1.2 ±0.11 4.6 ( ± 0 . 5 ) 1.5 ±1.1) 0.51±0.1) 6.6 ___I.I) 0,4 +11.3)
pellets
1GSCc glauconitic 10 54.9 ( ± 3,5) 0.2 ( ± 0 , 1 ) 8.3 + l.l) 0.2 ( + 0 . I) 26.3 ( ± 3.0) 0.2 ±0. I) 4.9 _+11.41 1.3 ±0.3) 0.61±0.1) 7.6 ± 1.8) 0.5 ±O.4)
pellets
Glauconitic 40 56.2 ( _ 2.7) 0.2 ( + 0.4) 8.6 ± 1.4) 0.2 24.3 (+3.11 0.3 +0.4) 4.4 ±0.8) 0.6 +_0.9) 0.4 (±0.3) 9.3 _+ 1.0) (1.6 (+0.8)
layers pellets
Glauconitic 15 54.7 ( + 2.8) (1.2 (_+0.1) 4.0 ± 1.51 0.2 (+0.1) 29.3 (+5.3) (1.3 ±0.2) 2.1 ±0.7) 7.7 _+5.8) 0.3 (±0,51 6.4 + 1.01 11.11
pellets of finds
Carbonatic clay:I: 3 64.3 ( ± 1,2) O.7 12.8 _+11.8) 3.9 (+0.7) 0.0 1.1 ±0.3) 14.8 4- 1.9) 0.1 2.2 +0.1) 0.2 ( ± 0. I )
Terra rossa~- 3 59.0 ( 4- 1.9) 1.0 19.9 +0.5) 8.7 ( +_0.2) 0.2 3.1 __+0.1) 4.7 ±2.5) 0.4 3,0 _+0.1) 11.2
Marly clay:l: 5 48.1 (+_5.4) O.4 (4-11.11 8.2 ( + 2.0) 2.8 ( + 0.6) 0.0 1.0 +0.2) 37.8 ±7.21 0.1 1.5 _+0.3) 0. I

*Number of analyses per group.


+Calculated.
SXRF data.
NEOLITHIC POTTERY OF ABRI PENDIMOUN 45
(a) Fe203 (100%) (b) Fe~O~(100%)

1G 1

CaO(100%) AI203(100%) CaO (100%) AI203(100%)


Fe203(100%) Fe203(100%)
(c) / ~ (d)
1G

CaO(100%) AI20~(100%) CaO (100%) AI203(100%)


Fe203(100%) Fe203(100%)

(e)IG / ~
2

CaO(100%) AI2Os(100%) CaO (100%) AI203(100%)


1 2 %...,,s 3(' ,/ 4" "'" ", 5 l' "

80 90 10¢ _ 110 12©

Fig. 6. FeO-CaO-A1203 diagram, showing not only the correlation between the clay matrix in finds and the local raw
material compositions, but also the mixture between several clay materials. Differences in chemical composition of
glauconite-rich layers are due to a natural chemical inhomogeneity. Clay matrix chemical compositions: 1, subgroup
1G; 2, subgroup 1GC; 3, subgroup 1GCc; 4, subgroup 1GS; 5, subgroup 1GSCc; 6, group l; 7, group 2; 8, group 3. Raw
materials: 9, terra rossa; 10, carbonate clays; 11, marly clays; 12, glauconite-rich layers; 13, clay pellets.

These mixtures were sometimes tempered with The association of glauconitic pellets and car-
carbonate rocks (subgroup 1GC), sparry calcite bonate rocks in the pottery may be ascribed to a
(subgroup IGCc) and/or aplite (subgroups natural mixture when the carbonate temper is less
1GSCc and 1GS). Table 8 summarizes all the than 20% (Table 8), because in the literature this
recipes used in the ceramic production at Abri value is considered a minimum technological
Pendimoun during the Middle and Late Neolithic. value suitable to produce a good ceramic
46 E. B A S S O ET AL.

Table 8. Synoptic table of the recipes used in the ceramic production of Abri Pendimoun with the
percentage of temper
Subgroup Raw materiaL~ Number cd Number o f
Glauconitic layers Terra rossa Limestones Calcite Aplites linds VBQ / f i n d s
1G 869 14
5~20% 37
• ,. . . . . . . . .... |~. . . . . ! .%2tWo
, <5%
1G C c ' -+' + " 114 23
.~.

1GS ' . . . . • ,>20% 147 1


1GSCc . . . . . . . . . . . . . . . ~+..... . ~<!0% . . . . <IIP/b 14
2S 25-30*/, 36 2
2Cc , - , ,
9
3F . ,r~ 19 1

The last two columns report the numbers o f all f i n d s c o n s i d e r e d in t h i s w o r k a n d the n u m b e r s of VBQ 1 finds belonging to the
various subgroups.

(Hoard et al. 1995). In subgroup IGC, the low adding crushed aplite to the local clay materials,
content of carbonate rock fragments (around although aplite was not available in the vicinity
5%) can be interpreted as natural mixture; in of the site. The presence of these fragments is dif-
contrast, in a mixture with around 20 vol% ficult to explain, as their association with glauco-
of carbonate fragments, these fragments were nitic pellets has not been found in raw materials.
intentionally added. In Provence, igneous and metamorphic rocks
The use of limestone and monocrystalline crop out in the ancient Maures, Est&el and
calcite as temper in ceramics has long been Tanneron massifs and in the Southern Alps
established (Arnold 1985; Porat 1989): pure (Ricq-de Bouard 1996). The Alpine Argentera
crystalline calcite was used for cooking ware, massif essentially consists of granites, gneiss
whereas limestones were employed only in and silicate rocks such as aplite. However, the
vessels not used for cooking (Arnold 1985). main sources of crystalline rocks in Provence
Studies on limestone and/or calcite ceramic are Tertiary and Quaternary sediments, which
mixture (Heller-Kallai et al. 1987; Shoval et al. often contain pebbles and cobbles of igneous
1993) indicate that monocrystalline calcite, and metamorphic rocks. In eastern Provence,
stable at higher temperatures, is more suited to the sediments in the Nice region contain Argen-
the production of cooking ware, whereas frag- tera rock fragments of Pliocene conglomerates
ments of limestone were apparently employed in transported by the Var, Tin6e and Vesubie
the production of vessels not used for cooking. rivers (Ricq-de Bouard 1996). The temper
Indeed, monocrystalline calcite produces pottery undoubtedly consists of crushed aplites rather
with lower mechanical resistance, which degrades than natural sand, because of the angular shape
rapidly when the firing temperature exceeds 700 of rock and mineral fragments (Fig. 4b and e).
°C in an oxidizing atmosphere. A semi-reducing Also the good preservation of alterable minerals
atmosphere, however, increases the stability of (feldspars), which disappear in detrital for-
calcite and of mixtures to 800 ~C (Peters & Iberg mations far from source rocks, corroborates this
1978; Letsch & Noll 1983; Fabbri et al. 1997). hypothesis.
At Abri Pendimoun it is impossible to define In the mixture 1GS and 1GSCc, the low quan-
the functionality of carbonate tempers because tity of the temper does not represent a functional
the artefacts are too fragmented to reconstruct tempering (Tire et al. 2001). Moreover, we could
vessel shapes and their usage. The presence of infer that the addition must have been intentional
crushed sparry calcite, always less than 5% (sub- because of the non-local origin of the
group 1GCc, Table 8), which at Abri Pendimoun material. At Abri Pendimoun, the addition of
seems to be strictly linked to the 'graffita' pottery crushed aplite is < 2 0 vol% for glauconitic
of the Square Mouthed Pottery phase I Culture, pellet-bearing mixtures, whereas it is >20
may be mainly dictated by cultural rather than vol% for the terra rossa mixtures (Table 8).The
technological factors. This combination of scanty knowledge of the function of the pots pre-
mixture and shape indicates that there was an vents speculation about a technological or cul-
important link between the VBQ I and Chassey tural reason for the tempering. Probably the
Cultures. pots' shape and their use constrain both minera-
A small percentage of ceramic finds (sub- logical composition and temper/matrix ratio of
groups 1GS, 1GSCc and 2S) were produced by the mixtures.
NEOLITHIC POTTERY OF ABRI PENDIMOUN 47

The use of glauconitic material in 95% of the BERNAB() BREA, L. 1946. Gli scavi nella Caverna
pottery (Fig. 3a) indicates that raw materials delle Arene Candide, 1. The Istituto di Studi
and the production technology remained constant Liguri, Bordighera.
through the Middle and Late Neolithic. BERNABO BREA, L. 1956. Gli scavi nella Caverna
Current literature data (Nung/isser & Maggetti delle Arene Candide, 2. Istituto di Studi Liguri,
Bordighera.
1978; Nung/isser et al. 1985, 1992; Maggetti
BINDER, D. 1990. N~olithique moyen et sup~rieur
1994; Martineau et al. 2000; Di Pierro 2003) dans l'aire liguro-provenqale: le cas de Giribaldi
highlight that the temper was carefully selected (Nice, Alpes-Maritimes, France). In: GUILAINE,J.
from outcrops even quite distant from the archae- & GUTHERZ, X. (eds) Premibres communautds
ological site. In particular, in Prehistoric times it paysannes. Autour de Jean Areal, Montpellier,
was common practice to add granitic rocks to 147-161.
ceramic mixtures. These lithologies are easily BINDER, D. 1998. Silex blond et complexit6 des
crushed when heated and rapidly quenched in assemblages lithiques dans le N6olithique liguro-
water (Nung/isser et al. 1992), as thermal shock provenqale. Rencontres mdridionales de Prdhis-
causes 'self-crushing'. toire rdcente, Juan-les-Pins. Association pour la
Promotion et la Diffusion des Connaissances
Another aspect regarding the functionality of
Archaeologiques, Juan-les-Pins. Aries, 111-128.
mixtures is linked to the use of temper mixtures BINDER, D. 2000. Mesolithic and Neolithic interaction
with white rocks, either silicates or carbonates. in southern France and northern Italy: new data and
The technological aspects linked to the use current hypotheses. In: PRICE, T. D. (ed.) Europe's
of carbonate rocks are well documented in litera- First Farmers. Cambridge University Press,
ture, whereas issues linked to the addition of sili- Cambridge, 117-143.
cate rocks have been less tackled. Experimental BINDER, D. 2002. Castellar--Abri Pendimoun (Alpes
data presented by Kilikoglou et al. (1995, Maritimes). Deuxibme rapport interm6diaire,
1998) demonstrate that concentrations of quartz Campagne de 2001. Centre d'~tudes Pr~histoire,
temper > 20 vol% result in a decreasing fracture Antiquitd Moyen Age (CEPAM-CNRS).
BINDER, D. & PERLI~S,C. 1990. Strat6gies de gestion
strength. Did the addition of granites or aplites
des outillages lithiques au N6olithique. Paldo, 2,
actually fulfil a technological requirement (for 257-283.
instance, for quartz) or was it simply dictated BINDER, D., BROCHIER,J.-E., DUDAY,H., HELMER,D.,
by tradition? This remains an open issue. MARINVAL,P., THII~BAULT,S. & WATTEZ,J. 1993.
L'Abri Pendimoun ~ Castellar: nouvelles donn~es
We would like to thank the Earth Science Department sur le complexe culturel de la c6ramique imprim6e
(University of Siena) for the SEM analyses. We also m6diterran6enne dans son contexte stratigraphique.
wish to thank J.-C. l~challier, who has provided his geo- Gallia Prdhistoire, 35, 177- 251.
logical survey data. A special acknowledgement is due BINDER, D., GASSIN, B. & St~NI~PART, I. 1994.
to F. Crepaldi, who deals with archaeological aspects of l~16ments pour la caract~risation des productions
VBQ I-Chassey interactions. The authors would like to c~ramiques n6olithiques dans le Sud de la France.
express their gratitude to the anonymous referees, who L'exemple de Giribaldi. Terre Cuite et Socidtd.
improved the first draft of this paper. La Ciramique, Document Technique, Economique,
Culturel. Association pour la Promotion et la
Diffusion des Connaissances Archaeologiques,
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Provenance and technology of Apulian Neolithic pottery
R O C C O L A V I A N O I & I T A L O M. M U N T O N I 2'3
1Dipartimento Geomineralogico, University of Bari, Via E. Orabona 4, 70125 Bari, Italy
(e-mail: rocco.laviano @geomin, uniba, it)
2Museo delle Origini, Universith degli Studi di Roma 'La Sapienza' University, Piazzale Aldo
Moro 5, 00185, Rome, Italy
3Department of Archaeometry, Science Faculty, University of Bari, Via E. Orabona 4,
70125 Bari, Italy

Abstract: Apulia is the best-represented region in Italy as far as archaeometric analyses of


Neolithic pottery are concerned. Cross-checked use of petrological (optical microscopy),
mineralogical (X-ray powder diffraction) and chemical analyses (X-ray fluorescence)
have been performed, in the Dipartimento Geomineralogico of Bari University, on 375
Early to Late Neolithic (from the seventh to the fourth millennium Bc) pottery samples
from the Tavoliere and Murge areas. A correlated analysis of 134 samples of the main
clayey deposits of the two areas was also conducted. Generally local clays were used
and, in some cases, the exploitation of a range of different local fabrics has been verified.
In Middle Neolithic sites, the use of non-local clay, probably imported, has been also deter-
mined. Few finished pots were actually exchanged at an inter-site scale during the Neolithic.
Preparation of raw materials has shown different choices followed by ancient potters. Clays
are usually more or less refined and the use of mineral temper such as sand, quartz, calcite
and grog has been found. The maximum temperature reached during firing is usually
between 600-700 and 850 °C. For some Middle Neolithic fine painted pottery higher temp-
eratures have been suggested (between 850 and 1050 °C), revealing a better firing control
and the use of kilns.

Archaeometric analysis of Italian Neolithic and sociocultural frame of reference in which


pottery, developed only in the last 20 years, has physical and chemical data are placed.
assumed a particular importance in relation to In light of awareness of both the potentialities
innovations in pottery production and the emer- and limits of analytical techniques, the status of
gence of productive economies and structured technological and archaeometric studies of
settlements from the end of the seventh millen- Apulian Neolithic pottery will be briefly
nium Bc. reviewed (Muntoni 2002b).
On a regional scale Apulia is the best represented, The number of analysed samples per site is
in terms of both sampled sites (about 45 settle- normally small: the number of fragments varies
ments) and analysed fragments (more than 600). between one and 49 sherds per site, sampled
The chronological range and the archaeological from surveyed or excavated materials. Of the
facies of the Neolithic period, from Early to Late, various archaeometric analytical methods, the
have been entirely covered. Many Italian (from most widespread technique is petrological exam-
Milan, Florence, Genoa and Bari University) and ination on thin-sections optical microscopy
foreign teams (from the UK and Canada) have ana- (OM), often employed alone or in conjunction
lysed Apulian Neolithic pottery (Muntoni 2002a). with other mineralogical methods, such as X-ray
Within the framework of Matson's concept powder diffraction (PXRD) and/or thermal
of Ceramic Ecology (Matson 1965; Kolb 1989), analyses (thermogravimetric analysis (TGA);
the emphasis here will be on research strategies, differential thermal analysis (DTA)). Chemical
the relation between goals and methods, and instrumental neutron activation analysis (INAA),
on the sampling techniques of such studies. The inductively coupled plasma-atomic emission
ideal development should be the shift from spectrometry (ICP-AES) or morpho-chemical
pottery as a simply finished product, whose (scanning electron microscopy plus energy-
origin is to be understood, towards an ecological dispersive spectrometry (SEM-EDS)) analyses

From: MAGGETTI,M. & MESSIGA,B. (eds) 2006. Geomaterialsin CulturalHeritage.


Geological Society, London, Special Publications, 257, 49~52.
0305-8719/06/$15.00 © The Geological Society of London 2006.
50 R. LAVIANO & I. M. MUNTONI

are even now rarely used in Apulian Neolithic arrangements involved in the production, use
pottery studies, and distribution of ceramics.

Our approach to archaeometric analyses Analytical methods


Since 1990 a new approach to the archaeometric Mineralogical studies were carried out by PXRD
analysis of Apulian Neolithic pottery has been using a Philips diffractometer (PW 1710) with
applied in the Dipartimento Geomineralogico Ni-filtered Cu K,~ radiation and employing NaF
of Bail University, in collaboration with different as internal standard. Petrological observation
archaeological teams from the 'La Sapienza' was made on thin sections, with a polarized
University, Rome, and the Soprintendenza per i light microscope (OM). Modal analysis was
Beni Archeologici della Puglia and, more carried out using a Swift & S. Point Counter on
recently, from the Dipartimento di Beni Culturali 2500-4500 points for each sample (according
e Scienze del Linguaggio of Bari University. to their wall thickness), with a line distance of
A crucial problem in the study of prehistoric 0.05 mm and a lateral step of 0.2 mm. Major
ceramics is the fabric variability. The use of appro- and trace element determination was performed
priate sampling strategies, number of samples and by XRF, using a Philips PW 1480/10 spec-
archaeometric techniques is essential if meaning- trometer (Cr anticathode for major and minor
ful technological studies are to be done. To elements, Rh anticathode for Rb, Sr, Y, Zr, Nb
verify adequately the variability and heterogeneity and W anticathode for Ce, La, Ba, Ni, Cr, V), fol-
within and between pastes, archaeologists had to lowing the analytical techniques outlined by
construct rigorous and explicit sampling schemes Franzini et al. (1972, 1975) and Leoni & Saitta
that could encompass the full range of variability. (1976). About 5 g of representative powder for
Cross-checked use of mineralogical and each sample was subjected to XRF. Two refer-
chemical analyses was then employed: complete ence standards (AGV-1 of the USGS, USA and
combinations of petrological (OM), mineralogi- NIM-G of NIM, South Africa) were used to
cal (PXRD) and chemical (X-ray fluorescence check the accuracy of the analytical data. Loss
(XRF)) analyses have been performed on 375 on ignition was determined by heating the
archaeological samples, all analysed in the samples at 1000 °C for 12 h; then PXRD patterns
Dipartimento Geomineralogico of Bail Univer- of the same previously heated samples, for the
sity (Table 1). Twenty-three settlements, identification of mineralogical changes, were
located in the Tavoliere plain and in the Murge recorded at room temperature.
plateau along the Adriatic coast, were sampled
(Fig. lb). A correlated analysis of 134 pelitic
and clayey samples was also conducted The geological context
(Laviano & Muntoni 2004).
Only the analysis of clay sources can give The Tavoliere plain
more information on which clay source was The Tavoliere plain (Fig. 1a), the most extensive
used, and why, and what kind of problems were one in Southern Italy, is a Mesozoic-Palaeogene
encountered by the ancient potters in the modifi- limestone depression filled with marine deposits
cation of the materials. 'Any investigation of of Plio-Pleistocene silty clay (Bradanic cycle),
ceramic technology at an archaeological site or often overlain by post-Calabrian marine sands
region is most fruitfully conducted within the (terraced marine deposits), Upper Pleistocene
perspective of ceramic ecology: it is essential (terraced alluvial deposits) and Holocene alluvial
to search out deposits and sample them so as to and lacustrine deposits of continental origin.
compare the pottery of interest with the proper- Marine Plio-Pleistocene clays of the Bradanic
ties of local clays' (Bishop et al. 1982, p. 319). cycle, also named the Argille Subappennine,
As all the archaeometrical data are separately crop out along the western margin of the Tavo-
published or are still in press, in this paper we liere plain. The depth of the outcrops may vary
aim for the first time at a geographical and from a few metres to 350 m. The clays consist
chronological synthesis of our results. The recon- of silty clay or clayey silt, with little sand, and
struction of the working sequence used in pottery have (Balenzano et al. 1977; Dondi et al. 1992)
manufacturing (from raw material provenance, a very similar mineralogical composition (clay
to preparation of bodies and firing techniques) minerals, carbonates, quartz and feldspars). The
should help to obtain insights into the potter's clay minerals are a mixture of 2 M illite, Mg-
role as an active and controlling agent in the pro- bearing smectite, Fe-bearing chlorite, kaolinite
cedure of a specific pottery manufacture, and into and randomly interstratified illite-smectite with
the pottery economics or the socio-economic 30-70% montmorillonite-like layers. Natural
APULIAN POTTERY 51

Table 1. Sampled Neolithic settlements of Tavoliere and Murge areas


Code Samples Excavation Survey Early Middle Late
Neolithic Neolithic Neolithic

Tavoliere
Monte Aquilone MA 15 X X
Masseria Valente MV 13 X X
Coppa Nevigata CN 8 X X
Masseria Candelaro MC 61 X X X
Masseria Santa Tecchia ST 11 X X
Podere 96 P96 7 X X
Masseria Cascavilla MCS 6 X X
Capo di Lupo CL 5 X X
Masseria Centonze MCZ 3 X X
Masseria Mischitelli MM 3 X X
Casello Amendola CA 2 X X
Total 134
Murge
Balsignano BALS 30 X X
Pulo di Molfetta PU 59 X X
Ciccotto CC 33 X X
Madonna delle Grazie MG 6 X X
Torre delle Monache TM 6 X X
Santa Barbara SB 43 X
Setteponti SP 15 X
Cala Colombo CCL 10 X
Grotta della Tartaruga GT 10 X
Grotta Scanzano GS 9 X
Masseria Chiancudda CH 1 X
Cala Scizzo CS 19 X
Total 241

non-plastic material consists of carbonates The Murge plateau


(calcite, as bioclastic or detrital granules, and
The large geologically homogeneous Murge
dolomite), quartz and feldspars (orthoclase, plateau (Fig. 1a) is formed by the limestone for-
microcline and Na-plagioclase). mations of Calcare di Bari and Calcare di Alta-
Very different Holocene alluvial clays can be mura, with terra rossa deposits present in the
found on the coastal plain, deposited by the sequence. Terra rossa are silty-clayey
numerous ancient rivers and streams. The clay continental sedimentary deposits, very poor in
composition is very variable depending on the carbonate (Dell'Anna 1967; Dell'Anna & Gara-
erosion of different clayey and arenaceous-
velli 1968; Dell'Anna et al. 1973) composed of
marly deposits (Cassano et al. 1995b; Eramo dominant clay minerals (illite and kaolinite)
et al. 2004). Alluvial clays have volcanic min-
and Fe-oxides or hydroxides, with subordinate
erals and rock fragments as a distinctive
quantities of quartz, feldspars, micas and pyrox-
feature. Heavy minerals are represented by domi-
enes. SiO2, A1203 and Fe203 are the main oxides,
nant diopside-augite pyroxene, magnetite, both in the clay fraction and in the whole speci-
biotite and garnet, together with debris of volca- men. Marine Plio-Pleistocene silty clays of the
nic glass.
Bradanic cycle (Argille Subappennine) crop out
Marine and alluvial clays are characterized by
extensively along the western margin of the
the relative abundance of SiO2, A1203, CaO, Murge plateau (Dell'Anna & Laviano 1991)
Fe203, K20 and MgO. Because of their mainly and locally in the Rutigliano area (Dell'Anna
calcareous composition (up to 17 wt% CaO),
1969; Moresi 1990).
both groups can be classified as marly clays. In
general, clay fractions ( < 2 Ixm) have a lower
CaO content than the whole specimens, Raw material provenance
whereas the A1203 and Fe203 concentration is Our studies indicate that generally local clays
higher. were used for Neolithic pottery production, in
52 R. LAVIANO & I. M. MUNTONI
(a)

o. . . . . . . . . . 50 km i~,,.N

Adriatic sea
-. .

-%
:----" ( :i4~-~.~ - , - ~,

"\ .

[~ Alluvial and lacustrine deposits (Holocene)


[] Terraced alluvial deposits (Upper Pleistocene) ~;:-: :
[] Terraced marine deposits (Upper-Middle Pleistocene)
[] Bradano Units (Pliocene-Lower Pleistocene)
[] Calcarenites (Miocene)
Apenninic Chain Units (from Cretaceous to Pliocene) Ionian sea
I~ Calcarenites (Eocene)
[~ Limestone (Mesozoic)

(b)

50
km

v o l i e r e

\--"-'--~r-,~.
,
h! D

3CCL

Fig. 1. (a) Geological and geomorphological map of Apulia (from Caldara et al. 1990, fig. 5). (b) Location of sampled
Neolithic settlements (*) of Tavoliere and Murge areas.
APULIAN POTTERY 53

both the Tavoliere and Murge areas, with some


differences between the two areas.

Early Neolithic (6200-5500 BC) of


300
the Tavotiere plain
Plio-Pleistocene silty clay and Holocene alluvial
deposits of continental origin were exploited
in the Tavoliere plain (Cassano et al. 2004).
Archaeometric data from eight neighbouring
Early Neolithic villages, located in a small area
(150 km 2) of the plain near the Adriatic coast, IOO08 ~ 300
show that ceramic production seems fairly homo-
geneous (raw material supply, grain-size varia- Sr 400 2 0 0 ~ 0 0 ~ / / " lO0 Zr
bility and firing techniques) in these villages,
although some degree of variation in grain-size
composition of natural non-plastic material is (b)
also present between different wares (Cassano
et al. 1995b; Muntoni & Laviano 2005).
As far as the ecological and technological 1000
aspects are concerned, the same alluvial
deposits, as shown by the well-preserved minera-
logical component, from three river valleys were
exploited. This hypothesis is also sustained
by the presence in the pottery of clasts of pyrox- 4 o o F ~ . . . ~ ..... .I
enes and volcanic glass typical of alluvial
clays. Behavioural and technical similarities in
Early Neolithic pottery technology are thus
confirmed.
The concentration of chemical elements is
,oo
1000~ , ~ J ~ . ~ ~ 300

very useful to identify a strong affinity between


Early Neolithic samples that can be all defined
as 'Ca-rich'. A very few finished pots were con- Fig. 2. (a) Crv. Sr v. Zr plot (ppm) for all Early
Neolithic pottery samples (+, n ----73) from the
sidered as outliers (Fig. 2a), probably exchanged
Tavoliere area (note the cluster and the few samples
at an inter-site scale during Early Neolithic. The (labelled) that could be considered as outliers). (b), Ba
ternary diagram (Fig. 3a) also shows a good v. Sr v. Zr plot (ppm) for all Early Neolithic pottery
chemical correspondence between pottery samples from the Tavoliere area and the samples
samples and alluvial clay deposits from the (marked) from sites located in two alluvial basins (D,
Tavoliere plain. The difference of CaO content samples from CN and MV villages; V, samples from
between some pottery samples and alluvial CL, MM and MCS villages).
clays (Fig. 3b) is due to the compositional varia-
bility of alluvial deposits and to the addition of
calcareous sand in some samples of coarse ware, were completely autonomous as far as raw
mainly from Monte Aquilone village. Three prin- material supply and pottery manufacture are
cipal criteria have been used to identify temper: concerned.
(1) the hiatal distribution of the inclusions;
(2) a proportion of inclusions >30%; (3) the
relative abundance of micritic bioclasts (mainly Early Neolithic (6200-5500 BC) of
bivalves), limestone clasts and fine-grained
calcite. the Murge plateau
XRF concentrations have also shown very The exploitation of different local deposits in the
fine local distinctions (Fig. 2b) between sites same Early Neolithic site has been verified with
located in different alluvial basins (Muntoni & an extended range of analysed samples, as in
Laviano 2005). Therefore, villages collected the large karst doline of Molfetta (locally
their clays in areas around the settlement itself known as 'pulo') or in the village of Balsignano,
in the nearest alluvial basin. Thus groups that both located near the Adriatic coast of the Murge
had the same taste and behavioural choices plateau (Muntoni 2003).
54 R. LAVIANO & I. M. MUNTONI
(a) Si02 ._
;,,,

, ,, kj

/' \ . - ', . \,

-~/ C a - r i c h " ~'~ ,./.,~ C a - p o o r ,,,.

./ \ ~.~ '\ !, An . ~',.

-.// "-\ " ,. ~"'Gh , ]", .......... [ ~ ~-


/.' ,

~" \ ', , ,,,


/. , •

CaO+MgO! ' ' AI203


0 25 5O 75 100

(b) 60.00
+
+ 4-
5000
t,++t -,*+ ~ +
40.0O
+ .~
30.00 + ,4-
+

2000

10.00

0.00
0.00 500 10.00 15.00 20.00 25 00 30.00
CaO

Fig. 3. (a) (CaO + MgO)-A1203-SiO2 wt% diagram (Di, diopside; Gh, gehlenite; An, anorthite); (b) S i O 2 v . CaO
plot (wt%). Early Neolithic pottery samples (+, n = 73) from the Tavoliere area and the fields (A, whole sample;
B, clay fraction) of alluvial deposits (n = 7).

Three paste groups with different dominant fossil fragments (mainly molluscs and rare
mineralogical constituents (predominant quartz benthonic Foraminifera), which characterize the
and calcite, with little K-feldspar and plagio- Cal-rich fabric, is due to an intentional addition
clase) were found in the Early Neolithic strata of a calcareous temper. In this case two principal
of Pulo di Molfetta (Laviano & Muntoni 2003). criteria have been used to identify temper: (1) a
Raw material variability is evident mainly on a proportion of inclusions >_30%; (2) the exclusive
synchronous level: three pastes (Cal fabric, presence of carbonate fossil fragments (from
Qtz + Cal fabric and Qtz fabric) were used in 2 0 0 - 4 0 0 p,m to 1.5-2 mm).
the same village and in the same archaeological XRF analyses are consistent with mineralogical
horizon. The dominant clastic constituents are data (obtained by PXRD and OM). SiO2, CaO and
all compatible with the geological deposits that AI203 are the dominant oxides, with some vari-
crop out in the site hinterland. The differences ations in CaO percentage. The ternary diagram
in mineralogy and grain-size distribution show a clear differentiation of the Cal-rich
(detected by PXRD and OM) between samples, the Qtz + Cal-rich samples being charac-
Qtz + Cal and Qtz fabrics could be explained if terized by relatively more balanced amounts of the
we hypothesize that Neolithic potters collected three main oxides, whereas the Qtz-rich samples
different clays in more areas around the settle- are characterized by higher quantities of Qtz
ment itself. The large amount of carbonate (Fig. 4a). This last group shows a good overlap
APULIAN POTI'ERY 55
(a)

Di \ //

x,\\\ ,/ \ /

×\ • /

~ " V G . ......... ~ ............ ::~


"7 \ , \ ~ \ ' X"
/ \ / \ , \ ! \

./
-./ \\\X
\ '"' "X /'"" '\, //
/' XX
,.~ "-/ \ / \ , \ , xe-
~'~ .... / \ , \ , \ , \ / o

CaO+MgO( ' ' ' 1 ' ' ' ' r , ,, I ' '' /AI203
0 25 50 75 100

(b) 50

A ~ ........ t
- t

30 roe
Nb 25

20 T ! T- [a a ', - +-
4 r'l I Z3.-=,.-.-~-,~_
15 ! I J -- ~ " I
' ' " ai - t
i ; IArgitle diRutigliano
5 q ~.............
. . . . . . . . . . . . !
o L i '~ ,
0 5 10 15 20 25 30 35 40 45 50
Y

Fig. 4. (a) (CaO + MgO)-A1203-SiO2 wt% diagram (Di, diopside; Gh, gehlenite; An, anorthite); (b) Nb v. Y plot
(ppm). Early Neolithic Cal-rich (×), Qtz + Cal-rich (El) and Qtz-rich (A) pottery samples (n = 47) from Pulo di
Molfetta and the fields (whole sample) of Argille di Rutigliano (n = 5) and terra rossa (n = 25).

with the chemical composition of the terra rossa quantity of quartz inclusions was probably
and the Qtz + Ca1 group with the Argille di Ruti- reserved for pots generally used for serving or
gliano of the Murge plateau. Also, some trace display. Large jars are more concentrated (60%)
elements, such as niobium (Nb) and yttrium (Y), in Cal-rich fabrics, with carbonate rock and
are important for distinguishing the three groups fossils: the higher proportion of carbonate
of pottery (Fig. 4b). inclusions, mainly in coarse wares, could suggest
In a few cases, different paste types can be actu- their use as cooking and/or storage vessels. In
ally related to typological groups of vessel form or low-fired cooking vessels, which are heated and
archaeological classes, as in the Early Neolithic cooled during use, because the thermal expansion
village of Balsignano (Modugno). At this site of calcite is similar to that of average fired clays
(Muntoni 2003) all Neolithic fragments were (Bronitsky & Hamer 1986; Fabbri et al. 1997),
macroscopically analysed and attributed to the stresses owing to differential expansion of the
paste groups. Only four basic vessel forms were clay matrix and temper are usually minimal.
distinguished in the analysed materials: dishes-
plates, bowls, large jars and collared jars. The Middle Neolithic (5500-4400 or 4200 Bc)
occurrence of bowls and large jars in pastes is
different (Muntoni 2003, table 60). Bowls are of Tavoliere and Murge
more concentrated (77%) in Q t z + Cal-rich Middle Neolithic pottery shows a substantial
fabrics, with few carbonate clasts: the high shift in the whole production sequence; in
56 R. LAVIANO & I. M. MUNTONI

particular, the systematic exploitation of Marine element concentrations confirm the homogeneity
Plio-Pleistocene silty clays, even in sites where between samples. This finding is in agreement
they could be considered non-local materials, with the geochemical homogeneity of the Plio-
has been determined in both the Tavoliere Pleistocene Apulian clays. Nevertheless, some
(Cassano et al. 1995b; Muntoni 1999) and the trace elements, such as Ba, Sr and Zr (Fig. 6),
Murge areas (Muntoni 2003; Muntoni et al. are important for distinguishing sub-groups of
2006). All red and/or brown painted pots (figu- pottery related to their geographical setting.
lina), which are typical of the Middle Neolithic Mineralogical and chemical data clearly show
of Southern Italy, show a very fine paste in the two areas the exploitation of the Plio-
texture, with a fairly fat clay matrix: of the Pleistocene silty clay, which in some cases
sheet silicates only mica crystals are recogniz- crops out more than 30 km from the sites. The
able. Non-plastic inclusions are homogeneous use of specific clay-beds shows a more
fine-grained (< 150-200 ~m) quartz and scarce complex clay supply activity, involving
carbonate fossils (mainly benthonic Foramini- perhaps the whole group of people. Such an
fera). Clasts of feldspars and iron oxides or activity might be distinct from individual and
hydroxides are also present. domestic tasks, and may suggest that local
XRF analyses showed that all samples are production was no longer domestic. In Middle
Ca-rich. The ceramic diagram (Fig. 5) shows Neolithic societies, pottery production, mainly
an almost complete overlap of the samples in of fine painted ware, probably evolved from a
the central part, corresponding to the chemical domestic mode of production to an incipient-
composition of Plio-Pleistocene Apulian silty specialization stage (Rice 1981; Van der
clays. A few samples from the village of Leeuw 1984). This stage would include an
Masseria Candelaro in the Tavoliere area are increasing standardization of paste composition,
characterized by very high quantities of calcite, reflecting greater exploitation of particular kinds
whereas others from the northern Murge sites of clays. In addition, a greater skill is more
of Pulo di Molfetta and Grotta Scanzano have evident in manufacturing and firing (up to
lower quantities. The former shows a more 1000 C ) technology.
Cal-rich fabric with carbonate fossil fragments Middle Neolithic black household pots, ana-
(mainly molluscs, such as bivalves and gastro- lysed in two Murge settlements (Setteponti and
pods), whereas the latter has a Qtz-rich fabric Santa Barbara), show a silicate matrix with
with very few carbonate inclusions. Also, trace angular to sub-angular coarse-grained alabastrine

SiO2&,

./
"v~.. i )...-"

"-/
! ', Ca-rich
,,f.
,>,' ~ ./ Ca-poor x
.// ',i f \

\
," ; An ,,
~,, , \

,I * \ , "">

•- .. ............ ),~ i :~ ...........


'.f-
~/"'~' , '\ "'/Gh
•/ ,

O
~__. ! L.f"
C a O + M a O r ' ~ . . . . ~ ..... " AI20 3
0 25 50 75 t00

Fig. 5. (CaO + MgO)-A1203-SiO 2 wt% diagram (Di, diopside; Gh, gehlenite; An, anorthite). Middle Neolithic fine
painted pottery samples (n = 127) from the Tavoliere plain (•), the Bradanic trough (grey dots), the northwestern (x)
and southeastern (D) areas of the Murge plateau, and the fields (whole sample) of Plio-Pleistocene silty clays (n = 89).
APULIAN POTTERY 57
(a)7°°] Non-calcareous clay (terra rossa) could be used
Ba / as a raw material, tempered with crushed
alabastrine limestone clasts.
!
600~ o

i o Late Neolithic (4400 or 4 2 0 0 - 4 0 0 0 Bc)


oo of the Murge plateau
6oo!
o o** •
Late Neolithic pottery (black and plain house-
o P* " 8 o *
hold wares) was sampled only from the Cala
. o
"
~.+.
o~ Scizzo cave (Bail province), located on the
400. Adriatic coast of the Murge plateau (Geniola
o
et al. 2005). As far as the ecological and techno-
oe.~..-
, c~°.
logical aspects are concerned, archaeometric
data suggest the use of two different (non-
300
calcareous and calcareous) clays for production

o o o
o @@
for the two archaeological wares. Raw material
variability is again evident (as in the Early
200 Neolithic pottery of the same area) mainly on a
200 400 600 800 10'00 12'00 14'00Sr
(b) 700- synchronous level.
Petrological and mineralogical data, and
Ba
chemical concentrations of SiO2, A1203 and
C a • allow the identification of two material
600- groups, with different dominant clastic constitu-
ents. In the black household pottery, the silicate-
rich matrix is dominant and non-plastic
inclusions are coarse-grained quartz and feldspar
500. clasts, with no carbonate rocks. These samples
• °

are also distinguished by the highest AlzO3 and


o o * * • o~
SiO2 values (Fig. 7a) related to clay matrix abun-
i ° •
dance. Terra rossa, which is very poor in carbon-
4004 j.: •'.., •
i • ate (Dell'Anna 1967; Dell'Anna & Garavelli
} ° 0, 111¢* . *. 1968; Dell'Anna et al. 1973), could be used as
] O • '4~'0 O0
* °° +
a raw material for this ware. Plain household
GO ° pottery shows an abundant sheet silicate matrix,
300~ •@~. "z~" • ,,
in which only the micas are recognizable; non-
i "; plastic inclusions are homogeneous fine-grained
minerals such as quartz and carbonate fossils
200 " • (planktonic Foraminifera). This ware is also dis-
6o 8'0 16o 1to 1~,o 16o 180 260 220 Zr tinguished by similar amounts of the three main
oxides. The Argille di Rutigliano, marly clays
Fig. 6. (a), Bav. Sr plot (ppm) for Middle Neolithic fine cropping out not far from the considered site
painted pottery samples (small dots) and the samples (Moresi 1990), are consistent with the sheet sili-
from the Bradanic trough (grey dots) and the cate clay matrix of plain household pottery
southeastern area of the Murge plateau (R); (b) Ba v. Zr
plot (ppm) for the Middle Neolithic fine painted pottery (Fig. 7a). As regards trace elements, rare earth
samples (small crosses) and the samples from the elements (REE), such as lanthanum (La) and
Tavoliere plain (e) and the Bradanic trough (grey dots). cerium (Ce), clearly show only two clusters
(Fig. 7b): the former contains plain household
pottery and the latter black household samples.
limestone clasts; quartz and Fe-oxides or hydrox-
ides as aggregates and pisoliths were also
observed as natural non-plastic inclusions. Preparation of bodies
PXRD analyses confirm the presence of pre- Preparation of raw materials has shown the
dominant calcite, accompanied by variable different choices followed by ancient potters in
amounts of quartz and feldspar. XRF analyses the preparation of bodies. Clays are usually
are consistent with the mineralogical data: more or less refined, and in some cases the use
SiO2, C a • and A1203 are the dominant oxides of mineral temper (such as fossiliferous sand,
(Geniola et al. 2005; Muntoni et al. 2006). alabastrine limestone and calcite), grog or
58 R. LAVIANO & I. M. MUNTONI

(a) c>Si02~ '

~'Argille di ~/'~
J Rutigt!ano ' ~'~-

,/ \\ "

/
\\\ /
/ \\
\
V Gh
;
; '\'\ /
/."~,.
\
-,/ \ ,- \ , \ /
/ \ i \ , \ , \
AI~ "/ \ , \ , \ , 'v"

CaO+MgOI ~ L , ~ I ~ ' ' J ' ' ~ ' 1 ' ' ~ ' IAI203
0 25 50 75 100

(b) 2oo

180

160

140

120

Ce too

8o _ _~ .......... " ~ - - - ~ _ . _ ~

6o
~.~Argille di Rutigliano
40

2o

0 J 1
10 20 30 40 50 80 70 80 90 100
La

Fig. 7, (a) (CaO + MgO)-A12Os-SiO2 wt% diagram (Di, diopside; Gh, gehlenite; An, anorthite; (b) Ce v. La plot
(ppm). Late Neolithic plain household (x) and black household (O) pottery samples (n = 19) from Cala Scizzo, and
the fields (whole sample) of Argille di Rutigliano (n = 5) and terra rossa (n = 25).

vegetable material has been found, with vari- Analytical data have shown that the main
ations in its incidence from sample to sample, degree of variation was in paste preparation
from site to site and from area to area. and grain-size (from 5 0 - 2 5 0 to 5 0 - 6 0 0 p~m)
The Tavoliere samples (Cassano et al. 2004) composition. Some Early Neolithic Qtz-rich
showed that clays were generally used as they samples from Pulo di Molfetta and Ciccotto
naturally occurred, as has been proven by the (Muntoni 2003) are characterized by the pre-
mineralogical component, which compares well sence of grog fragments (n = 9, mainly from
with that of local clays, although some degree Pulo) or by the presence of curvilinear and
of variation in grain size and percentage occurs. long pores probably derived from vegetable
Microscopic observation also revealed that fossi- material burnt during firing (n = 5, from Pulo).
liferous sand or crushed sparry calcite was The large amount of fossils, which characterized
occasionally (n = 18) employed as temper in the Cal-rich Early Neolithic coarse wares of
coarse ware in only three Early and Middle Pulo di Molfetta and Balsignano, is due to an
Neolithic settlements (Monte Aquilone, Santa intentional addition of a calcareous temper to
Tecchia and Masseria Candelaro). terra rossa. The presence of this particular
In the Murge area ancient potters followed ware in two different Neolithic villages could
different choices in the preparation of pastes. also indicate the same appreciable intra-group
APULIAN POTTERY 59

choice as a response to functional or/and social Mineralogical and chemical data show that
constraints. Only Middle Neolithic black house- Middle-Late Neolithic black household and
hold pots from the Murge settlements of Sette- Late Neolithic plain household pots were fired
ponti and Santa Barbara (about 90 km apart) at a temperature not exceeding 600-800 °C.
are systematically tempered by angular to sub- For Middle Neolithic fine painted pottery (the
angular coarse-grained alabastrine limestone so-called f i g u l i n a ) higher temperatures have
clasts (Geniola et al. 2005; Muntoni et al. been suggested, revealing a better firing control
2006). In this case three principal criteria have (temperature, rate of heating and oxidizing
been used to identify temper: (1) the hiatal dis- atmosphere) and the use of kilns. The absence
tribution of the inclusions; (2) a proportion of of a dark core and the low birefringence of the
inclusions _>30%; (3) the angular outlines of matrix confirm a high degree of sintering. Such
the grains. Such data could give some positive samples show gehlenite and pyroxene neoforma-
insight into the inter- and intra-group organiz- tions, only apparent by PXRD analysis, whereas
ation of the many Middle Neolithic communities clay minerals are absent (Table 2). In the same
of the Murge plateau, who shared so many other group one can see decreasing amounts of
common behavioural features (Cassano 1993). calcite, which, as microscopic observation on
thin section shows, was recrystallized in pottery
pores. On the basis of such data one can
Firing techniques suggest that temperatures between 850 and
Mineralogical and petrological data gave some 1050 °C were obtained.
insight concerning pottery firing temperatures: In some settlements (Masseria Candelaro in
the maximum temperatures reached during the Tavoliere plain and Pulo di Molfetta and
firing have been inferred to be usually between Ciccotto in the Murge plateau) a clear differen-
600-700 and 850 °C in both the considered tiation between Early and Middle Neolithic cera-
areas. As kaolinite, which is a common com- mics (the latter fired at higher temperatures)
ponent of the Apulian clays, has disappeared in has been found (Cassano et al. 2004; Muntoni
every sample, one could suggest that tempera- 2003). Unfortunately, in the Tavoliere and
tures exceeding 600 °C were always reached. Murge areas very few fire structures have
Early Neolithic pots are usually light buff been identified, probably because of a lack of
coloured; pottery was probably fired in pits and extensive archaeological excavations, and no
several factors determined the success or direct connection with ceramic firing (rather
outcome of the firing process (for some experi- then with baking or roasting) can yet be
mental tests, see Cassano et al. 1995a). established.
For Early Neolithic firing technology, miner- PXRD analyses of representative samples
alogical data show that maximum temperatures heat-treated at 1000 °C (Table 2) confirm that
did not exceed 800 °C. However, on the basis pyroxene and gehlenite synthesis is dependent
of the presence in X-ray patterns (Table 2) of on calcite and clay mineral abundance (Maggetti
very weak peaks of some clay minerals (illite 1982). The presence of a high quantity of neo-
plus muscovite and minor quantities of smec- formed pyroxene and gehlenite was detected in
tite), one could argue that some Early Neolithic Qtz + Cal-rich samples; their concentration
samples were fired at temperatures that could increases in Middle Neolithic fine painted pots
have reached 600-700 °C. The high peaks of and in Early Neolithic Qtz ÷ Cal-rich samples
primary calcite in Early Neolithic Cal-rich whereas they are initially absent. In Qtz-rich
samples (Table 2) show that these coarse pots samples, found only in Early (Pulo di Molfetta
also were fired at a temperature not exceeding and Ciccotto) and Late Neolithic (Cala Scizzo)
700 °C. Other samples, as the lower amount sites of the Murge region, characterized by very
of clay minerals, together with the presence low quantities of calcite, only hematite is the
of calcite, shows (Table 2), could have been secondary product of firing. Only in Cal-rich
fired at higher temperatures, but still not over heat-treated samples, characterized by coarse-
800 °C. grained carbonate fossils (Early Neolithic Pulo
In Middle and Late Neolithic villages, black di Molfetta and Balsignano coarse ware) and ala-
burnished and plain red and/or brown painted bastrine limestone clasts (Middle-Late Neolithic
pottery are associated in archaeological contexts. black household ware), was the co-occurrence of
For these pots, involving different firing struc- diopside, gehlenite and hematite observed. CaO
tures and techniques, greater efforts were made and a neoformed calcium silicate very similar
by ancient potters to control the amount of to larnite were also detected, probably formed
oxygen that entered the firing structures, to as a result of the high quantities of CaCO3 in
produce an oxidizing or reducing atmosphere. the paste.
T a b l e 2. Mineralogical composition (by PXRD) of representative pottery, samples ¢~
o
as-received heat-treated at 1000 C

Ware Sm I11 + Ms Qtz Feld Cal Px Gh Hem Qtz Feld Px Gh Hem

EarlyNeolithic
CN03 C XX XX XXXX X XXXX XXXX X XX X
MCI2 B XX X XXXX X XXXXX XXXX XX XXX XX
MM1 P XX XX XXXXX XX XX XXXXX XXX XX X
MA8 P XX X XXXXX X XXXXX XXX XXX XXX XX
MV8 P XX XX XXXX X XXXXX XXXX XX XXX XX
PU02 C XX XX XXXXX XXX XXXXX XXXXX XXX XXX XX
PU26 C XX XXX XXXXX XXX XXXXX XXXXX XXXX XXX XX
PUI6 C XX tr XXXXX XX tr X XXXX
PUI9 C X XX tr XXXXX XX tr X XXXX
BALS24 C X XX tr XXXXX XX tr X XXX
BALS30 C tr XXX tr XXXXX XXX tr X XXX
MCSI C tr X XXXXX XX XXXXX XXX XX XX XXX
MA4 P X X XXXXX XX XXXXX XXXX XXX XXX XX
MAI0 C tr X XXX XXXX XXXXX XXX XX XX XXXX
PU01 B XX XXXXX XXXX XXXXX XXXX XX XX
PU05 C XX XXXXX XXX XXXXX XXX X XX
CC27 B X XX XXXXX XXXX tr XXXXX XXX XX
Middle Neolithic
PU30 FP XXXXX XXXX XX X tr XXXXX XXXXX XX X XX
PU53 FP XXXXX XXX XX XXX X XXXXX XXXX XX XX X
MC23 FP tr XXXXX XXX X XX XX tr XXXXX X XXX XXXX tr
MC24 FP tr XXXXX XX X X XX X XXX X XX XXXXX tr
MC30 FP XXXXX XX X XX XX tr XXXXX XXX XXX XX tr
SP04 FP tr XXXXX XXX X XX XX X XXXXX XX XX XX X
GT02 FP XXXXX XX tr XX XX XXXXX XX XXX XX tr
GS09 FP XXXXX XXX tr XX XX X XXXXX XXX XX XX X
CC08 FP tr XXXXX XXXX XX XX XX tr XXXXX XXXX XXX X X
CC 18 FP X XXXXX XXXX XX XX XX tr XXXXX XXX XXX X tr
SPI4 BH X XXX XXXX X XXXXX XXXXX XX XX XX X
SPI5 BH X XX XXXX X XXXXX XXXXX XXX XX XX X
SP18 BH X XX XXXX X XXXXX XXXXX XX XX XXX tr
SB01 BH X X XXXXX X XXXXX XXXXX XXX X X XX
SB 11 BH XX XX XXXX XXX XXXXX XXXXX XX XX X XX
Late Neolithic
CSI0 BH tr XXXXX XXX XXXXX XXXXX XX
CS02 BH X X XXXXX X X XXXXX XX X tr XX
CS01 BH XX X XXXXX X tr tr XXXXX XX X XX
CSll PH tr tr XXXXX XX XXXX XXXXX XXX XXX XXXX
CSI2 PH X XXXXX X XXXXX XXXXX XXX XXX XX tr
CSI7 PH X tr XXXXX XX XXXX XXXXX XXX XXX XXX

Sm, smectite; I11, illite; Ms, muscovite; Qtz, quartz; Feld, k-feldspar and plagioclase; Cal, calcite; Px, pyroxene; Gh, gehlenite; Hem, hematite (symbols as in Kretz 1983); number of X is in relationship with
mineralogical phase abundance; tr, traces. Archaeological wares: C, coarse; B, burnished; P, painted; FP, fine painted; BH, black household; PH, plain household.
APULIAN POTTERY 61

Concluding remarks References


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Late La T~ne pottery from western Switzerland:
one regional or several local workshops?
MARINO MAGGETTI & GIULIO GALETTI
University of Fribourg, Department of Geosciences, Mineralogy and Petrography, Chemin du
Musde 6, CH-1700 Fribourg, Switzerland (e-mail: marino.maggetti@unifr.ch)

Abstract: A total of 203 pieces of fine ceramic and four clays from seven sites of western
Switzerland (Bern, Gen6ve, Grotte du Four, La T~ne, Matin, Saint-Triphon-Massongex and
Yverdon) were studied chemically and mineralogically to determine if there was local pro-
duction at each site and if trade links existed between the sites. Firing wasters from Bern and
the region of Gen~ve indicate local ceramic production. The sherds are often contaminated
with secondary phosphorus and, in the case of Bern, copper. Most of the fine ceramic is
CaO-poor, contrasting with the CaO-rich clays. Based on the chromium and nickel concen-
trations, it can be subdivided into two distinct groups. The majority of the sherd populations
from Gen~ve, Saint-Triphon and Massongex, as well as a few specimens from Bern, La T~ne
and Yverdon, have high Cr and Ni values. The remaining sherds have low Cr and Ni con-
centrations. The analyses show that: (1) the fine ceramic from each of the seven sites forms
an often inhomogeneous and widely dispersed group, distinct from the others; consequently,
it is most probably a local or regional product; (2) ceramic import is probable for one piece
from Grotte du Four (provenance Yverdon); (3) the Late La T~ne fine ceramic was manu-
factured mainly from silicate or silicate-carbonate, fat to lean clays.

Late La T6ne (LT D, c. 150-30 BC) ceramics significant enough difference among the seven
from the NW of Switzerland (locations: Basel- provenances would point to local ceramic pro-
Gasfabrik, Basel-Mtinsterhtigel, Sissach-Brtihl, duction, i.e. manufacture at different places sim-
Waldenburg-Gerstelfluh) were analysed by ultaneously, rather than large isolated workshops
Maggetti & Galetti (1981) and Maggetti et al. in the area of present-day western Switzerland,
(1988). They showed that the ceramic of with regional and national trade.
Basel-Gasfabrik and of the pottery centre of
Sissach-Brtihl is a CaO-poor fine ware, which
forms two well-defined, homogeneous chemical Samples
reference groups. It must therefore be assumed
A total of 203 grey to light grey fine ceramic
that pottery was produced not only in Sissach-
samples were provided by the archaeologists
Briihl, but also in Basel-Gasfabtik. The similar
involved in the project. They belong typologi-
chemical composition of some objects from
cally mainly to bottles and bowls and were
Basel-Mtinsterhtigel and Waldenburg-Gerstel- made with a wheel. Dating and archaeological
fluh to these reference groups suggests local
literature are as follows.
ceramic trade. This study focuses on 203 La
T~ne fine ceramic fragments from eight other Bern BE. Middle to Late La T~ne, LT C 1 - L T
sites in western and southwestern Switzerland, D2 (c. 250-c. 30 Bc): Mtiller-Beck (1963-
i.e. Bern, Gen~ve, Grotte du Four, La T6ne, 1964), St/ihli (1977), Bacher (1989), Mtiller
Matin, Saint-Triphon, Massongex and Yverdon (1990, 1996), Kohler (1991).
(Fig. 1). For further comparison, the four clays Genbve GE. Middle to Late La T~ne, LT C 2 -
excavated at the production sites were included LT D2 (c. 200-c. 30 ~c); Paunier (1981), Kaenel
in the study. Based on firing wasters, local pro- (1990), Bonnet (1997).
duction was indicated for the sites of Bern and Grotte du Four (Boudry NE). Middle to Late
Gen~ve only. As a result, it was necessary to La T~ne, LT C 2 - L T D2 (c. 2 0 0 - c . 30 BC);
determine if the remaining samples originated Kaenel ( 1991).
from these two production sites, or if they La Tkne (Marin-Epagnier NE). Middle La
formed different chemically, mineralogically T~ne, LT C (c. 2 5 0 - c . 150 BC); Schwab
and petrographically distinguishable groups. A (1989), MUller (1990), Egloff (1991).

From: MAGGETTI,M. & MESSlGA,B. (eds) 2006. Geomaterials in CulturalHeritage.


Geological Society, London, Special Publications, 257, 63-80.
0305-8719/06/$15.00 © The Geological Society of London 2006.
64 M. MAGGETrI & G. GALETTI

structure types was made, based on the matrix


(fat or lean). Clay pellets were not considered
in the determination of grain sizes, because
they dissolve during soaking.

X-ray diffraction (XRD). A total of 199 fine


ceramic samples were X-rayed under standard
conditions (Cu K~, 3-65°20, operating con-
ditions 30 kV and 40 nA) on a Siemens Kristallo-
flex D500 generator.
! X-ray fluorescence analysis. Determination of
major elements (Si, Ti, AI, Fe, Mn, Mg, Ca,
B~lrn Na, K, P) and trace elements (Ba, Cr, Cu, Ga,
Nb, Ni, Pb, Rb, St, Th, V, Y, Zn, Zr) was per-
Yverdon formed on all samples. Circular tablets (40 mm
diameter) of glassy material (calcined powder)
were used for the major elements. Circular
tablets of pressed powders (non-calcined) were
used for the trace elements. The preparation of
the glass tablets was carried out as follows:
Triphon after calcination of the powdered sample for
l h at 1000 ~C, 1.2 g of this calcined material
was mixed with 5.7 g of lithium tetraborate and
0.3 g of lithium fluoride. This mixture was then
placed in a P t - A u crucible and melted at
1150 °C before being poured into a preheated
mould and cooled with compressed air. The
preparation of the pressed tablets was carried
out as follows: 2.5-3.0 g of initial powder were
Fig. 1. Location of the studied sites. Gen~ve = Annecy mixed with < 0 . 3 m l of a moviol-saturated
(France), Dardagny-Brive, Gen~ve, Meinier, Momex aqueous solution. This was then added to a
and Vandoeuvre-Pressy. 32 mm mould and subjected to a pressure of
6 tons for at least 1 rain. The tablet was carefully
removed and placed on a bed of 7 g of boric acid
Marin (Marin-Epagnier NE). Late La T~ne,
in a 40 mm mould. This was again subjected to a
LT DI (c. 150-c. 80 BC); Arnold (1992).
pressure 6 tons for at least 1 min. The resulting
Massongex VS. Late La T6ne, LT D (c. 150-
tablet was dried in a vacuum for 24 h at room
c. 30 Bc): Haldimann et al. (1991), Curdy et al.
(1997). temperature. Analytical measurements were
performed using a Philips PW 1400 X-ray
Saint-Triphon (Ollon VD). Late La T6ne, LT
spectrometer with Cr anticathode. The conver-
D (c. 150-c. 30 BC); Kaenel (1990).
sion of the measured values to weight percentage
Yverdon (Yverdon-les-Bains VD). Middle to
concentrations utilized standardization curves
Late La T~ne, LT C 2 - L T D2 (c. 200-c. 30 BC);
established on reference samples (e.g. USGS,
Curdy et al. (1992, 1995), Brunetti (2005).
NIM, ANRT). The results of the measurements
of the major elements of the matrix were
Methods corrected with Philips alpha coefficients.

Powder preparation. For chemical analysis FeO. Determination of FeO was by the 2.2
and X-ray diffraction (XRD), 4 - 5 g per sample dipyridilic method (Lange & Vejdelek 1980),
were ground to a fine powder in a tungsten using a Philips Pye-Unicam PU 8650 at 528 nm.
carbide mill after abrasion of possibly contami-
nated surface areas. Statistics. Multivariate analyses were per-
formed using SPSS 11.0, neglecting P205 and
Optical microscopy. Thin sections were pre- Cu (contamination effects) as well as Pb and Th
pared when sufficient original material was (too many blank values) and FeO. For cluster
present. After microscopic analysis, an approxi- analysis, the raw data (20 elements), average
mate classification of the 97 samples into linkage and Ward linkage, and z-scores were
LATE LA TENE POTTERY 65

used. For the factor and the discriminant analyses and Zr values), BE 53 (lowest Na20, MgO and
log-transformed data (20 elements) were used. MnO, and highest TiO2, Y and Zr values), and
BE 26, 48, 71 (increased Cr and Ni contents).
There may be several possible explanations for
Chemical contamination the lack of compatibility between outliers and the
In contrast to the clays, which can contain a fine ceramic group. (1) The outlier may be of
maximum of c. 0.2 wt% P205 (Koritnig 1978), local origin but the amount of sampled material
ancient ceramics are often characterized by dis- per sherd is insufficient and not representative
tinctively higher concentrations. In most cases, of a single object; or the outlier may have been
this can be interpreted as a phenomenon relating affected by secondary contamination during use
to the contamination through migrating P-rich or burial; or there may be coincidental fluctuation
solutions during burial (see Collomb & Maggetti of the chemical composition of the otherwise
1996). However, with a concentration of up to homogeneous raw materials, i.e. fluctuations
11 wt%, most ceramic pieces from Bern greatly that were not eliminated during clay preparation.
exceed this value. To minimize this secondary (2) The outlier is not of local production. For fine
phosphorus contamination, all analyses shown ceramic, the population investigated here, the
in Table 1 were recalculated to 0 wt% P205, amount of material selected for a single analysis,
and standardized to a total of 100 wt%. These i.e. 4 - 5 g, is sufficient (Schneider 1989). Also,
values were used in the following paragraphs. the contamination hypothesis can be ruled out
Some Bernese samples show an increased because elements such as Zr,Y, Mg, etc. are
copper content up to a maximum of 2540 ppm. normally not affected by secondary processes.
This is due to the use of a Cu-bearing marker What about the last two possibilities?
for the annotation of these objects (i.e. BE 20, The use of an illitic-chloritic clay as raw
27, 58, 66, 74, 85 and 92). Copper was therefore material can be inferred from the negative
not taken into account for the multivariate stat- A1203-SIO2 (Fig. 3a) and the positive A1203-
istics. In addition to phosphorus, other elements TiO2 (Fig. 3b) and AlzO3-FezO3totcorrelations
may have been mobile, a possibility that is vir- (Fig. 3c). The amounts of calcite vary (Fig. 2a).
tually impossible to confirm. The discussion is This substantiates results obtained by XRD
therefore based on the assumption that no phase analysis, revealing relict primary clay
elements other than P and Cu were affected by phases such as quartz, illite, chlorite, plagioclase
secondary processes. and potash feldspar (+_calcite) in the samples
with the lowest firing temperatures of c. 500-
650 °C. Microscopic examination allows for
Pottery from the production sites allocation of the samples to three fabrics, as
of Bern and Gen~ve follows.
Fabric 1. Very fat, silicate to silicate-
Bern carbonate matrix. Small amounts of mostly sili-
A new reference group. A total of 87 samples cate non-plastic fragments with a maximum
were analysed (Tables 1 and 2), comprising 85 grain diameter of 2.52 mm (BE 7, 8, 10, 14, 15,
fine ceramic sherds from two neighbouring exca- 19-22, 24, 27-30, 34, 35, 39, 41-43, 46-48).
vation sites, Tiefenau/Heiligkreuz and Enge- Fabric 2. Lean, silicate matrix. Relatively
meistergut, as well as two clays, BE 40 from large amounts of silicate non-plastic fragments
the first excavation site, mixed with sherds, and (sandstone) with a maximum grain diameter of
BE 52 from a trench close to the first excavation 1.08 mm and a serial granulometry (BE 13, 17,
site and corresponding to the clayey substratum 26, 45).
of the Celtic settlement. The identification of Fabric 3. Carbonate-silicate matrix. Non-
four kiln wasters (BE 38, 44, 49, 73) indicates plastic constituents with a maximum diameter
local ceramic production. The products show a of 2.23 mm (clays BE 40, 52).
wide scatter in their CaO content, but the bulk CaO-poor as well as CaO-rich (e.g. BE 41 with
of the Bernese fine ceramic is relatively CaO- 13.6 wt% CaO) fine ceramic samples have been
poor, with a blurred transition to CaO-richer allocated to fabric 1, despite distinct variations
specimens (Fig. 2a). Both clays are very CaO- in CaO, because the matrix does not differ sig-
rich and belong therefore to marls rather than nificantly between the specimens. It can be con-
to clays (Table 1). Some pottery samples stand cluded that geologically similar material, with a
out markedly from the main body with regard considerable fluctuation in microcrystalline cal-
to one or several chemical parameters cites, has been used in the production of ceramics
(Fig. 2a-d). These are BE 28 (low Zr and Y con- belonging to fabric 1. The assumption that these
tents), BE 68 (highest CaO with lowest A1203 raw materials share a similar geological history
66 M. MAGGETTI & G. GALETTI

Table 1. Chemical analyses (wt% )

No. SiO2 TiO 2 AI203 Fe203* MnO MgO CaO Na,O K20 P205 Total FeO LOI H20-

Bern
BE 6 63.77 0.77 17.44 6.47 0.06 2.44 3.45 1.18 3.13 1.22 99.93 4.45 1.00 1.40
BE7 50.58 0.82 17.66 7.00 0.13 2.10 12.6 0.96 2.94 5.21 99.99 1.42 11.00 5.25
BE 8 52.22 0.88 19.32 7.73 0.15 2.41 7.31 0.85 2.58 6.36 99.81 1.89 5.32 6.30
BE9 59.05 0.91 20.81 7.98 0.10 3.18 0.90 0.92 3.14 3.01 100.00 2.98 2.84 3.84
BE 10 56.37 0.83 17.58 7.00 0.18 2.12 7.29 1.02 2.82 4.45 99.66 1.68 6.38 5.61
BEll 60.01 0.77 17.48 7.21 0.13 1.65 2.93 1.18 2.41 6.29 100.06 1.37 4.57 5.43
BE 12 63.18 0.89 18.80 7.39 0.17 2.41 1.43 1.09 2.48 3.05 100.89 0.58 2.93 3.52
BE13 56.30 0.93 20.66 8.37 0.14 3.45 2.14 0.99 2.55 5.01 100.54 3.14 2.88 3.78
BE14 51.84 1.00 22.43 9.48 0.14 3.35 2.01 0.89 3.10 6.15 100.39 2.81 3.89 5.10
BE15 51.41 0.83 19.60 8.50 0.17 3.85 8.25 0.93 2.82 3.45 99.81 1.66 4.77 4.39
BE16 57.15 0.93 19.23 7.65 0.17 2.66 3.67 0.92 2.15 5.63 100.16 4.00 2.77 4.41
BE 17 52.99 0.90 20.99 7.69 0.13 3.21 5.08 0.81 2.56 5.71 99.97 3.30 4.22 5.71
BE 18 64.51 0.80 18.68 6.07 0.t0 2.00 1.49 1.03 2.70 2.76 100.14 t.03 4.55 4.22
BE 19 55.50 0.93 20.77 8.25 0.19 1.99 2.05 0.93 3.27 6.25 100.13 1.64 5.11 6.72
BE20 62.11 0.84 19.47 7.88 0.12 2.45 1.18 1.06 3.30 1.80 100.21 1.13 4.16 3.69
BE21 51.78 0.95 21.03 8.17 0.17 2.67 4.97 0.76 2.26 7.80 100.56 2.55 4.63 7.42
BE22 60.60 0.86 18.56 7.49 0.18 2.14 2.16 1.13 3.09 4.02 100.23 1.03 4.70 4.94
BE23 47.62 1.02 22.41 8.84 0.15 2.67 3.58 0.62 2.25 10.40 99.56 1.89 5.61 8.59
BE24 56.33 0.90 20.10 7.97 0.14 1.97 2.16 1.00 3.15 6.51 100.23 1.59 4.71 6.14
BE25 57.70 0.90 19.79 8.01 0.13 2.51 1.94 1.25 3.32 4.67 100.22 1.49 3.49 4.15
BE 26 59.77 0.92 19.22 8.98 0.16 3.57 0.96 0.91 1.71 3.73 99.93 5.37 2.20 3.61
BE27 57.20 0.93 20.57 8.26 0.17 2.24 1.87 0.98 3.33 4.72 100.27 1.42 5.12 5.62
BE 28 62.21 0.86 18.42 7.46 0.09 1.98 1.80 1.30 2.89 3.19 100.20 0.60 4.87 4.32
BE 29 45.95 0.99 22.48 8.81 0.20 2.70 4.90 0.52 2.31 ll.00 99.87 1.59 5.90 9.32
BE 30 51.24 0.94 20.64 8.11 0.14 2.59 7.09 0.75 2.35 6.65 100.50 1.89 4.68 7.07
BE31 54.40 0.96 21.18 8.20 0.15 2.07 !.88 1.02 3.16 7.00 100.02 1.79 5.34 7.66
BE 32 51.42 0.84 18.57 7.29 0.13 2.82 11.50 0.91 2.48 3.54 99.47 3.24 2.35 3.58
BE33 53.12 0.97 21.39 8.22 0.17 2.69 3.52 0.77 2.36 6.64 99.85 3.17 5.04 7.16
BE 34 53.54 0.97 22.17 8.68 0.15 2.13 1.85 0.78 2.79 6.77 99.83 2.15 4.54 6.90
BE35 49.88 1.00 21.88 8.75 0.16 2.67 3.01 0.70 2.16 9.46 99.67 2.62 5.05 7.94
BE36 51.53 0.98 21.49 8.30 0.17 2.80 3.20 0.76 2.00 8.26 99.49 2.78 4.71 7.41
BE37 53.35 0.96 21.43 8.49 0.15 2.47 2.70 0.80 2.31 7.41 100.07 2.77 5.79 6.78
BE38 47.53 1.04 22.56 8.97 0.16 2.06 3.96 0.86 2.77 9.81 99.72 1.35 7.95 10.30
BE 39 56.70 0.92 20.29 8.18 0.15 2.64 5.05 0.88 2.79 2.21 99.81 1.44 5.77 7.79
BE40 56.35 0.70 14.23 5.61 0.12 2.02 16.50 0.96 2.45 0.66 99.63 1.09 12.5 4.56
BE41 44.70 0.91 20.23 7.95 0.15 3.04 12.60 0.75 2.17 7.25 99.73 0.99 4.43 5.87
BE42 50.77 0.97 21.36 8.59 0.18 2.62 3.85 0.78 2.34 8.48 99.94 3.02 6.09 7.69
BE43 47.79 0.97 21.17 8.43 0.16 2.51 6.59 0.56 2.10 9.48 99.76 1.98 6.94 8.49
BE 44 62.31 0.83 18.54 7.41 0.15 2.77 2.82 1.13 3.53 0.18 99.67 4.45 3.82 3.85
BE 45 57.78 0.91 20.89 8.32 0.16 3.18 1.42 0.95 2.62 3.50 99.73 2.85 2.97 3.23
BE 46 56.28 0.88 19.75 8.04 0.14 2.72 2.79 1.22 3.45 4.39 99.66 0.70 4.43 3.78
BE 47 60.31 0.87 18.93 7.32 0.16 1.75 1.67 1.22 2.62 5.23 100.08 0.55 4.09 4.75
BE48 58.34 0.84 18.69 8.03 0.21 2.69 2.31 1.09 2.84 4.83 99.87 1.74 4.56 5.12
BE49 55.39 0.93 20.78 8.16 0.22 2.01 2.20 0.99 3.08 5.84 99.60 0.31 4.72 5.53
BE50 64.80 0.78 17.47 6.75 0.13 1.91 1.40 !.27 2.98 2.53 100.02 0.19 3.23 3.36
BE52 49.12 0.64 12.98 5.12 0.11 3.67 23.70 1.03 2.59 0.14 99.13 1.96 18.70 1.46
BE53 59.09 1.15 19.15 7.56 0.06 0.75 2.41 0.20 2.41 7.19 99.98 0.34 6.96 8.37
BE 54 63.14 0.82 18.80 7.52 0.13 2.34 1.36 1.08 3.21 1.21 99.62 0.72 4.94 3.92
BE55 60.54 0.82 18.55 7.37 0.14 2.73 5.41 1.01 3.51 0.36 100.42 3.00 1.08 0.79
BE56 58.47 0.81 17.54 7.06 0.13 2.51 9.10 1.00 3.27 0.62 100.51 1.56 3.14 1.82
BE57 47.07 0.99 22.10 8.48 0.19 2.85 4.46 0.63 2.15 10.70 99.59 0.51 6.77 6.55
BE58 53.67 0.97 21.32 8.22 0.17 2.81 3.15 0.86 2.20 6.73 100.11 2.86 5.00 4.84
BE59 53.20 1.00 22.18 9.12 0.16 3.54 1.82 1.01 2.64 5.44 100.10 0.28 4.06 3.56
BE60 55.31 0.93 20.54 8.40 0.12 2.97 2.13 !.17 3.08 5.48 100.13 1.75 4.05 3.66
BE61 50.79 1.00 21.96 8.67 0.17 2.51 3.50 0.81 2.44 8.11 99.95 1.35 6.02 6.55
BE62 45.57 0.93 20.87 8.03 0.17 2.57 9.43 0.54 1.89 9.57 99.57 2.67 6.51 6.90
BE63 54.81 0.93 20.93 8.01 0.15 2.72 3.87 0.83 2.22 5.59 100.06 2.40 5.08 5.42
BE 64 61.59 0.88 19.22 7.61 0.14 2.57 1.74 1.07 3.34 2.25 100.40 0.77 4.71 4.15
BE65 49.38 0.97 21.00 8.16 0.19 2.51 5.57 0.79 2.56 8.64 99.78 1.68 7.05 7.59
BE 66 54.40 0.91 20.07 7.81 0.11 2.30 3.48 0.98 2.23 7.67 99.97 2.93 5.18 5.77
BE67 61.18 0.87 19.20 7.65 0.12 2.31 1.41 1.05 3.23 3.50 100.51 1.62 4.62 3.89
BE68 51.20 0.71 15.20 5.98 0.11 2.17 18.40 0.93 2.63 1.63 98.93 1.03 14.70 2.82
BE69 52.45 0.86 18.57 7.26 0.14 2.06 8.53 0.98 3.00 5.52 99.37 1.92 9.19 5.00
BE70 57.51 0.91 19.87 7.90 0.15 2.36 2.40 1.03 3.34 4.64 100.11 1.38 5.48 4.86

(Continued)
LATE LA TENE POTTERY 67

Table 1. Continued

No. SiO2 TiO2 A1203 Fe203* MnO MgO CaO Na20 K20 P20~ Total FeO LOI H20-
BE71 62.84 0.75 18.09 7.60 0.16 2.59 1.18 1.21 2.02 3.77 100.21 2.76 3.66 3.92
BE72 50.35 0.96 21.10 7.89 0.19 2.44 5.88 0.65 2.24 8.21 99.89 1.97 6.51 7.67
BE73 60.97 0.82 18.41 7.35 0.15 2.76 5.07 1.09 3.43 0.29 100.35 5.49 0.22 0.14
BE74 51.35 0.97 21.48 8.42 0.17 2.22 3.38 0.86 2.66 8.20 99.73 1.73 6.12 7.06
BE75 54.35 0.95 20.78 8.21 0.18 2.23 3.00 0.99 3.35 6.19 100.23 1.34 6.05 6.53
BE76 53.55 0.94 20.43 8.10 0.16 2.27 3.46 0.99 3.13 6.84 99.86 1.83 6.06 6.12
BE77 55.99 0.94 21.21 8.48 0.23 2.49 2.93 0.82 2.98 3.96 100.02 2.10 4.61 5.44
BE 78 51.89 0.88 19.45 7.64 0.15 2.71 8.53 0.87 2.51 5.17 99.80 2.63 3.24 4.18
BE79 62.24 0.84 18.57 7.14 0.10 1.68 1.59 1.16 2.66 4.38 100.37 1.45 3.73 4.03
BE 80 49.25 0.99 22.30 8.42 0.18 2.46 4.48 0.77 2.70 8.40 99.96 1.78 7.88 7.53
BE81 48.80 0.98 21.97 8.70 0.21 2.42 4.20 0.75 2.55 9.43 100.02 2.11 7.57 8.33
BE82 56.27 0.96 21.55 8.48 0.17 2.96 2.50 0.88 2.44 3.89 100.10 3.99 3.74 3.66
BE83 55.34 0.95 21.42 8.34 0.15 2.82 3.67 0.85 2.59 4.33 100.45 2.98 4.93 4.84
BE84 50.19 0.98 21.77 8.40 0.17 2.92 5.25 0.69 2.21 6.92 99.49 2.23 6.27 5.77
BE85 59.06 0.87 19.71 7.61 0.15 2.25 1.70 1.09 3.25 4.53 100.22 1.41 5.45 4.20
BE86 49.81 0.93 20.88 7.99 0.14 2.79 6.16 0.78 2.41 7.66 99.55 2.16 5.15 5.19
BE87 56.02 0.95 21.39 8.27 0.14 2.04 1.64 0.88 2.95 5.80 100.08 1.99 5.70 5.22
BE88 53.47 0.98 21.64 8.55 0.18 2.56 3.21 0.85 2.59 6.11 100.14 2.36 6.67 6.49
BE89 58.64 0.93 20.25 8.20 0.14 2.46 1.62 1.05 3.54 3.58 100.39 0.95 5.29 4.12
BE90 50.65 0.99 21.74 8.60 0.19 2.82 3.14 0.71 2.01 8.97 99.83 2.90 5.93 6.22
BE91 51.25 0.98 21.69 8.56 0.21 2.81 3.16 0.72 2.02 8.74 100.12 2.84 5.78 6.09
BE92 53.08 0.97 21.39 8.22 0.19 2.81 3.32 0.81 2.09 6.73 99.60 2.92 5.55 5.42
BE93 55.08 0.95 21.38 8.22 0.15 2.01 1.92 0.95 3.02 6.85 100.52 1.93 5.69 6.08
Gen~ve
GEl 64.92 0.79 17.88 7.51 0.19 3.34 0.85 1.14 3.24 0.18 100.05 5.46 0.02 0.11
GE2 66.12 0.78 17.35 7.23 0.19 3.35 1.01 1.19 2.97 0.18 100.37 5.75 0.04 0.10
GE 3 65.81 0.78 17.24 7.33 0.19 3.34 0.72 1.25 3.35 0.15 100.16 5.62 0.00 0.05
GE4 67.06 0.72 16.42 7.19 0.18 3.18 0.93 1.38 2.85 0.14 100.04 5.05 0.21 0.15
GE 5 64.38 0.82 18.31 7.69 0.19 3.72 0.87 1.13 3.15 0.20 100.46 4.66 0.34 0.19
GE6 64.63 0.80 18.13 7.61 0.18 3.46 0.79 1.14 3.22 0.12 100.07 5.87 0.00 0.12
GE 7 64.15 0.81 18.18 7.62 0.18 3.60 0.80 1.22 3.27 0.14 99.97 5.54 0.00 0.09
GE 8 64.96 0.80 17.91 7.51 0.18 3.42 0.79 1.08 3.12 0.11 99.88 4.24 0.39 0.20
GE 9 64.54 0.79 17.96 7.46 0.18 3.50 0.87 1.17 3.29 0.13 99.88 2.58 0.85 0.18
GE 10 65.66 0.80 17.86 7.45 0.18 3.50 0.85 1.10 3.18 0.15 100.73 5.38 0.35 0.18
GE 11 64.80 0.78 17.71 7.41 0.18 3.44 0.85 1.19 3.32 0.14 99.84 4.63 0.40 0.17
GE 12 65.15 0.79 17.62 7.40 0.17 3.33 1.01 1.10 3.31 0.22 i00.11 1.74 1.98 0.75
GE 13 64.84 0.79 18.01 7.54 0.18 3.53 0.79 1.11 3.17 0.10 100.07 3.14 0.51 0.20
GE 14 64.79 0.79 17.90 7.52 0.18 3.46 0.78 1.10 3.17 0.10 99.80 3.48 0.45 0.19
GE 16 65.07 0.79 17.77 7.47 0.18 3 . 4 1 0.83 1.22 3.24 0.12 99.63 3.95 0.68 0.18
GE 17 65.21 0.77 17.26 7.30 0.17 3.44 0.81 1.20 3.12 0.18 99.47 4.37 0.18 0.11
GE 18 64.76 0.81 18.18 7.62 0.18 3.39 0.75 1.01 3.18 0.10 99.98 4.39 0.44 0.19
GE 19 65.65 0.78 17.32 7.30 0.17 3.17 0.92 1.17 3.09 0.21 99.79 1.75 1.92 0.68
GE20 65.22 0.80 17.98 7.55 0.18 3.35 0.96 1.09 3.21 0.18 100.51 1.32 2.07 0.87
GE21 64.84 0.80 18.03 7.50 0.17 3.30 0.92 1.21 3.16 0.14 100.07 3.97 1.13 0.16
GE22 59.17 0.75 17.07 6.75 0.13 2.71 8.87 1.01 3.21 0.38 100.05 1.39 2.29 0.55
GE23 67.44 0.74 16.71 7.13 0.17 3.03 0.74 1.41 3.09 0.13 100.59 0.04 1.00 0.24
GE24 66.68 0.73 16.50 7.26 0.17 3.01 1.65 1.31 2.87 0.30 100.49 0.05 1.45 0.27
GE 25 64.60 0.78 17.20 7.21 0.14 3 . 3 1 2.08 1.27 3.37 0.41 100.36 0.10 2.88 1.05
GE26 66.76 0.77 16.94 7.23 0.18 3.33 0.81 1.32 3.05 0.11 100.51 1.06 0.45 0.10
GE27 67.45 0.74 16.77 7.18 0.17 3.04 0.78 1.21 2.96 0.13 100.43 3.75 0.47 0.20
GE28 68.34 0.70 16.37 6.95 0.16 2.79 0.88 1.23 2.89 0.18 100.51 3.93 1.36 0.33
GE29 67.47 0.74 16.65 7.02 0.17 2.84 0.82 1.32 3.00 0.16 100.19 3.76 0.99 0.27
GE 30 65.51 0.76 17.04 7.29 0.18 3.47 0.71 1.19 3.25 0.15 99.54 3.24 0.46 0.20
GE31 65.29 0.78 17.43 7.38 0.17 3.26 1.19 1.17 3.30 0.45 100.42 3.06 2.55 1.05
GE 32 65.44 0.76 17.05 7.25 0.20 3.62 1.12 1.20 3.07 0.21 99.92 2.94 0.77 0.26
GE 33 67.96 0.70 16.30 6.91 0.17 2.76 0.88 1.28 2.87 0.17 99.99 3.80 1.14 0.32
GE34 67.06 0.76 16.71 7.15 0.19 3.21 0.91 1.29 3.00 0.16 100.44 1.73 0.87 0.38
GE39 65.39 0.80 17.93 7.53 0.18 3.42 0.82 1.09 3.12 0.12 100.40 4.54 0.50 0.22
GE40 65.01 0.80 18.14 7.59 0.18 3.48 0.85 1.08 3.18 0.11 100.42 3.07 0.52 0.17
GE41 64.39 0.81 18.25 7.54 0.18 3.39 0.85 1.21 3.32 0.14 100.06 4.87 0.60 0.23
GE42 64.29 0.80 18.08 7.46 0.17 3.33 1.08 1.10 3.30 0.27 99.88 3.20 2.49 0.76
GE43 60.45 0.45 8.90 3.33 0.09 2.05 21.6 1.10 1.94 0.46 100.39 0.49 14.7 2.16
GE44 61.76 0.42 8.27 2.99 0.09 2.18 21.5 1.35 1.54 0.29 100.37 0.29 14.8 1.25
GE45 64.57 0.83 18.72 7.67 0.16 3 . 7 1 0.97 1.05 3.19 0.11 100.07 4.92 0.34 0.19
GE46 64.93 0.80 17.41 7.57 0.18 3.71 1.68 1.29 2.94 0.31 100.82 4.82 1.27 1.27

(Continued)
68 M. MAGGETTI & G. GALE'Iq'I

Table 1. Continued

No. SiO2 TiO2 A1203 Fe203* MnO MgO CaO Na20 K20 P_,Os Total FeO LOI H20-

GE47 65.09 0.82 18.06 7.63 0.18 3.67 0.88 1.18 3.09 0.15 100.74 5.23 0.13 0.13
GE 48 64.26 0.87 18.56 7.77 0.21 3.58 0.86 1.18 3.16 0.14 100.58 2.86 0.78 0.78
GE49 65.47 0.78 17.51 7.39 0.19 3.45 0.71 1.25 3.21 0.16 100.12 5.74 0.00 0.00
GE 50 64.79 0.81 18.11 7.58 0.19 3.62 1.02 1.04 3.10 0.16 100.42 4.88 0.19 0.19
GE51 64.20 0.82 18.67 7.81 0.18 3.47 0.79 1.06 3.20 0.10 100.31 6.9l 0.00 0.00
GE52 66.21 0.77 17.35 7.36 0.17 3.37 0.84 1.25 3.13 0.20 100.67 4.25 0.28 0.28
GE53 65.39 0.80 17.76 7.56 0.18 3.76 1.02 1.14 3.02 0.16 100.79 5.49 0.10 0.10
GE 54 67.35 0.76 16.98 7.13 0.20 3.02 0.76 1.29 3.12 0.21 100.82 3.69 0.57 0.57
GE 55 64.43 0.79 17.49 7.37 0.18 3.70 1.76 1.22 2.95 0.21 100.08 0.20 1.14 1.14
GE56 69.27 0.73 14.40 5.92 0.09 1.82 4.65 0.94 2.31 0.53 100.66 3.04 1.04 0.67
GE57 71.64 0.72 13.46 5.36 0.14 1.51 3.53 i.00 2.22 1.01 100.59 3.03 1.38 0.77
GE58 66.40 0.77 17.13 7.41 0.18 3.38 0.92 1.24 2.94 0.14 100.49 3.69 0.51 0.21
GE59 64.09 0.83 18.22 7.53 0.19 3.75 1.28 1.06 3.09 0.28 100.31 4.17 1.00 0.41
GE60 66.98 0.76 17.01 7.48 0.17 3.11 0.69 1.23 2.82 0.13 100.38 5.08 0.63 0.38
GE61 66.44 0.76 17.19 7.50 0.17 3.14 0.76 1.18 2.96 0.10 100.20 3.93 0.33 0.18
GE62 66.12 0.84 17.89 8.05 0.19 2.61 0.94 !.08 2.52 0.23 100.46 3.02 4.10 3.28
GE63 64.98 0.78 17.28 7.40 0.20 3.75 1.32 1.19 3.00 0.17 100.08 3.35 0.50 0.15
GE 64 66.92 0.70 15.35 6.65 0.17 3.51 1.68 1.37 2.79 0.41 99.54 3.88 0.51 0.23
GE65 66.78 0.76 16.56 7.15 0.18 3.39 0.98 1.28 3.01 0.30 100.40 4.16 0.59 0.28
GE 66 65.60 0.80 17.46 7.46 0.18 3.65 0.94 1.14 3.09 0.11 100.42 5.29 0.28 0.18
GE 67 63.65 0.81 18.25 7.52 0.17 3.44 1.46 0.96 3.16 0.15 99.59 5.65 0.36 0.21
Grotte du Four
GF 1 62.6 1 . 1 5 21.59 7.50 0.09 1.67 1.86 0.56 3.38 0.27 100.70 2 . 8 1 1 . 7 6 0.48
GF2 62.98 0.82 19.01 7.54 0.19 3.37 1.07 1 . 3 8 4.29 0.26 100.91 3.79 i.58 0.65
GF 3 69.97 0.72 15.71 6.17 0 . 1 1 2.18 1.51 1 . 3 5 2.68 0.17 100.57 4.06 0.59 0.21
La T~ne
LT 1 68.60 0.78 15.72 4.85 0.03 1.99 4.72 0.99 2.84 0.17 100.69 2.52 2.85 0.67
LT2 69.33 0.81 17.58 4.73 0.03 2.31 1.71 1.18 2.5 0.13 100.31 3.04 3.85 1.03
LT 3 63.74 0.83 18.10 7.79 0.25 3.41 1.80 0.83 3.22 0.17 100.14 4.45 0.91 0.38
LT4 61.07 0.76 16.77 6.21 0.09 2.32 8.50 1.12 3.I2 0. t9 100.15 2.85 5.45 1.27
LT5 62.58 0.98 20.99 5.60 0.06 2.73 3.51 0.90 2.41 0.75 100.51 2.98 4.07 3.42
LT6 64.68 0.85 18.60 5.32 0.06 2.59 3.53 1.09 3.27 0.15 100.14 2.61 1.76 0.68
LT7 65.06 0.82 18.34 6.94 0.10 2.90 1.45 1.45 3.23 0.17 100.46 3.77 0.84 0.25
LT8 67.15 0.79 16.78 6.89 0.16 2.60 1.52 1.30 3.13 0.19 100.51 3.29 0.67 0.31
Marin
ME 1 55.05 1.10 25.08 9.77 0.12 3.42 1.16 0.86 2.93 0.90 100.39 1.75 4.33 5.60
ME2 58.39 0.93 21.94 8.47 0.20 2.56 1.53 1.35 3.35 1.78 100.50 1.68 4.55 6.68
ME3 57.71 0.84 19.60 7.89 0.52 3.08 5.66 0.87 3.50 0.61 100.28 0.42 7.32 3.72
ME4 70.75 0.82 15.69 5.53 0.54 1.96 1.39 i.16 2.39 0.52 100.75 0.37 4.57 3.75
ME5 67.87 0.83 15.85 7.53 0.52 2.16 1.44 1.13 2.51 1.08 100.92 0.69 3.84 3.47
ME6 56.92 0.83 19.52 8.65 0.26 3.14 5.75 0.84 3.60 0.94 100.45 1.02 7.25 3.51
ME 7 56.09 1.05 23.96 9.67 0.15 3.66 1.28 1.25 2.76 0.58 100.45 4.61 3.67 6.45
ME8 55.41 1.00 23.94 10.00 0.23 2.69 1.34 1.26 3.65 1.32 100.87 1.19 5.52 6.61
ME9 55.50 0.92 21.66 9.53 0.34 2.97 1.81 1.68 3.87 2.13 100.41 1.77 4.40 5.74
ME 10 68.52 0.83 15.94 7.45 0.49 1.99 1.32 1.12 2.45 0.52 100.63 0.35 3.96 3.79
ME l l 60.56 0.94 21.85 8.04 0.15 2.85 2.00 0.94 2.00 1.31 100.64 3.43 4.21 7.64
St. Triphon-Massongex
TR 1 65.17 0.76 16.74 7.24 0.19 3.64 1.40 1.25 3.09 0.35 99.83 4.52 0.61 0.22
TR2 60.98 0.84 19.14 7.85 0.17 3.08 2.18 0.91 3.20 1.78 100.13 3.37 3.69 1.76
TR3 66.04 0.78 17.07 7.38 0.22 3.72 0.99 1.11 3.03 0.17 100.51 4.20 0.33 0.09
TR4 63.83 0.80 17.61 7.69 0.18 4.01 1.74 1.21 3.11 0.21 100.39 3.39 0.63 0.21
TR5 56.37 0.78 18.79 7.46 0.14 3.13 7.39 0.90 3.45 1.61 100.02 2.86 2.53 1.33
TR6 63.16 0.79 17.99 7.60 0.17 3.23 1.65 1.07 3.02 1.33 100.01 3.93 2.23 1.18
TR7 63.72 0 . 8 1 18.12 7.76 0.19 3.65 1.22 1.05 3.21 0.43 100.16 2.98 1.27 0.41
TR8 64.33 0.79 17.39 7.64 0.17 3.66 1.84 1.21 2.99 0.42 100.44 3.17 1.20 0.39
TR9 55.25 0.79 18.78 7.28 0.14 3.50 8.75 0.86 3.49 1.37 100.21 4.09 1.13 0.67
TR 10 59.57 0.71 16.32 6.82 0.14 2.35 8.08 1.32 2.95 1.64 99.90 3.09 3.13 1.65
TR 11 55.53 0.78 18.32 6.97 0.11 3.43 9.82 0.99 3.46 0.29 99.70 1.19 0.54 0.43
TR 12 68.72 0.74 16.01 5.97 0.05 2.14 1.82 1.40 2.75 0.18 99.78 0.21 0.62 0.39
TR 13 61.55 0.78 17.74 6.44 0.07 2.76 6.04 1.11 3.19 0.34 100.02 0.43 0.75 0.47
TR 14 66.84 0.82 15.94 4.79 0.04 !.66 5.42 0.73 2.31 1.27 99.82 0.24 4.38 1.34
TR 15 65.66 0.80 17.63 7.10 0.17 3.56 0.93 1.16 3.22 0.18 100.41 5.09 0.47 0.39

(Continued)
LATE LA TI~NE POTTERY 69

Table 1. Continued

No. SiO2 TiO2 Al203 Fe203* MnO MgO CaO Na20 K20 P205 Total FeO LOI H20-

Yverdon
YV 1 59.06 0.86 21.59 8.10 0.15 3.62 1.11 1.19 4.54 0.35 100.57 3.75 0.94 0.44
YV2 59.50 0.80 20.13 7.12 0.27 3.14 3.26 1.14 4.23 0.96 100.55 3.82 1.72 0.87
YV3 57.52 0.86 21.66 8.38 0.16 3.60 1 . 5 9 1.11 4.55 1.09 100.52 3.30 2.41 1.18
YV4 56.71 0.85 21.93 8.22 0.36 3.17 1.73 1.06 4.58 1.72 100.33 1.12 3.96 2.37
YV5 65.71 0.79 17.45 6.90 0.16 2.82 1 . 1 9 1.38 3.43 0.22 100.05 2.90 0.69 0.35
YV6 65.95 0.7l 15.83 6.65 0.13 2.I9 1.85 1.51 3.42 2.17 100.4l 0.91 3.67 2.28
YV7 60.80 0.80 18.98 6.98 0.18 2 . 9 3 3 . 3 5 1.23 3.91 0.90 100.06 4.08 2.07 0.86
YV 8 65.52 0.79 17.88 6.80 0.16 2.80 1 . 0 0 1.33 3.69 0.32 100.29 2.92 0.83 0.27
YV 9 67.46 0.74 16.55 7.01 0.32 2.83 1.05 1.35 2.82 0.51 100.64 3.85 0.99 0.57
YV 10 66.74 0.77 17.55 6.32 0.18 2.63 1.15 1.41 3.49 0.40 100.64 3.49 0.72 0.45
YV 11 58.42 0.87 22.08 8.38 0.14 3.76 1.15 1.00 4.57 0.28 100.65 3.08 1.17 0.27
YV 12 60.55 0.79 18.92 8.26 0.14 3 . 0 2 1 . 9 0 1.57 3.80 1.69 100.64 2.17 3.08 1.80
YV 13 60.08 0.80 19.02 7.13 0.29 2 . 8 5 3 . 3 6 1.21 3.94 1.55 100.23 4.01 1.93 1.05
YV 14 62.71 0.84 19.15 7.67 0.19 3.15 1.37 1.13 3.56 0.63 100.40 4.14 0.96 0.51
YV 15 65.60 0.89 18.04 7.21 0.17 2.64 1 . 2 9 1.18 3.30 0.19 100.51 2.54 0.68 0.23
YV 16 67.04 0.95 17.12 6.12 0.27 1.21 2 . 0 3 0.36 3.28 1.85 100.23 0.32 2.81 1.48
YV 17 61.13 0.81 19.40 7.35 0.16 2.94 1 . 8 3 1.38 4.14 1.58 100.72 0.42 2.38 1.47
YV 18 68.07 0.81 18.22 5.79 0.10 2.13 1.29 1.08 2.79 0.34 100.62 1.46 0.62 0.27
YV 19 67.01 0.66 14.80 7.00 0.08 1.81 2 . 5 2 1.26 2.51 2.60 100.25 1.02 4.50 2.93
YV20 67.24 0.79 16.76 6.18 0.07 2 . 8 8 1 . 4 9 0.87 3.30 0.81 100.39 2.29 4.20 2.30
YV21 59.46 0.87 20.72 8.07 0.16 3.53 1.64 1.35 4.37 0.14 100.31 3.93 0.56 0.26
*Total iron is givenas Fe203. LOI, loss on ignition.

is further substantiated by the observation of squared Euclidean distances, z-scores) shows


sandstone fragments as a characteristic non- that the wasters are distributed over the main
plastic phase. As marl BE 40 contains such sand- subgroups and that the two provenances cannot
stones, it appears that sandstone fragments must be differentiated. This argues for a single or
be a specific characteristic of the Bernese clays. different local workshops using chemically vari-
The non-plastic elements of fabric 2 differ able clay deposits.
quantitatively from those of fabric 1. Chemically,
the samples belonging to this fabric cannot be Selection and processing of the raw materials.
distinguished from the ceramic population of BE 40 and BE 52 are marls and therefore
fabric 1. The samples are not unusual with cannot be the starting material for the bulk of
regard to their archaeological typology, either. the fine ceramic. This is because microscopic
Furthermore, the microscopic image does not examination reveals that the CaO occurs as
indicate any temper addition during manufactur- finely distributed calcite in the matrix, and not
ing. Consequently, it may be assumed that the as coarse particles in a siliceous clay, which
clay used to produce these samples originated could have been eliminated mechanically
from a lean layer embedded in the otherwise fat during treatment. However, the two marls may
clay deposit of Bern. well have been used in the production of the
In conclusion, it may be possible for BE 26, CaO-rich samples. Raw material BE 40 contains
28, 48, 53 and 71 to have been manufactured hardly any non-plastic material and completely
either from a local clay with a different compo- resembles the CaO-rich ceramics in this
sition from that of the fine ceramic main group, respect. This is probably because natural, fatty
or to have been imported to this La T~ne settle- raw materials were used without much proces-
ment from a geologically similar or different sing in the Bernese La T~ne ceramic. The wide
region. BE 68, on the other hand, can be inter- range of CaO, SiO2 and A1203 concentrations
preted as being of local manufacture, because shows that the clay deposit was heterogeneous
its chemical composition corresponds well to in its chemical composition, and this hetero-
that of the marl BE 40. However, to reduce the geneity was not eliminated by specific material
size of the reference group, BE 26, 28, 48, 53, preparation. However, as is to be expected, the
68 and 71 are excluded from the Bernese La fluctuation range is significantly lower in single
T~ne reference group, which comprises therefore objects than in the whole population. Five ana-
79 specimens. Cluster analysis of the reference lyses of the same specimen (BE 36, 58, 9 0 - 9 2 )
group (Ward method, not log-transformed data, show that the variations of the major and trace
70 M. MAGGETTI & G. GALETTI

(a) (b)
30 , , , 1.2 I

o
53
1.1

0
0
o
%
o ° do.9
o
~ 2o~ ~8 ~"o.8 o ~OoC~
o
o

o o o
o
15 © 0.7 to
0 5 10 15 20 0 2
CaO (wt%) MgO (~°/o)
(c) (d)
300 , 1 1 , , , 500
' 0 26

0 071
400
250 53
A

E 300
t,~ 0 48
o..
.....- 200 -
0 0 0 0

200 o~
150
100

~8 0 68
100 I Oi t = I I I J I
10 20 30 40 50 60 70 80 050 1 O0 150 200 250 300

Y (ppm) Ni (ppm)

Fig. 2. Correlation diagrams of selected oxide and element pairs for 85 fine ceramic samples from Bern.

elements, with the exception of Ba and Cr, lie sherds, of which c. 30% are made up of pottery
within the normal range. As there appears to be waste from the Four Rue du Cloi'tre kiln, partly
no correlation between archaeological type and consisting of 13 firing waste fragments (GE
chemical composition, a purposeful selection of 1-8, 49-53). The firing waste GE 67 was
a particular raw material for specific objects found in Annecy (France).
seems unlikely. As can be observed from the A1203-CaO cor-
relation diagram (Fig. 4a), the fragments are
mainly CaO-poor (Table 1). In contrast, both
Genkve clays and the fine ceramic samples GE 22, 56
A new reference group. Sixty-two samples and 57 are characterized by very high or at
were examined, originating either from the least increased CaO concentrations. Considering
town of Genrve (four excavation sites) or from the SIO2-A1203 diagram (Fig. 4b), all these
the surrounding area (five excavation sites). samples stand out from the densely packed
They include two clays (GE 43, found adjoining field of the remaining 57 specimens. This is cor-
the kiln Four Rue du Cloffre; GE 44, cob from roborated by the C r - N i correlation diagram
the cathedral excavations) and 60 fine ceramic (Fig. 4c), where these outliers plot in isolation
LATE LA TI~NE POTTERY 71
(a) (b)
26 r T 26 I I
' ' "oo
24- 24

22-

20-
BE 41
0
O0 0

ooO °O8o
22

2o
J
0 0 ~(~)0 -
0 O
o oOo o,i1 _ N
18- 18

16 16
• Geneve • Geneve
14 O Bern 14 I I I I I O Bern
4O 50 60 70 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3
Si02 (wt%) T i 0 2 (wt%)

(d) 500 I I I I I

(c)
400
26 T 1 l ~~T---
©
24 -

o o "~300
e~
22 O..
A
O0

~
--
20

18
200

100
16

14
6
~ ~

7
j ~

8
l

9
• Geneve
© Bern
10 11
0
0
I
50
I
100
I
150
I
200
O Geneve
© Bern
250 3013
F e 2 0 3 tot ( w t % ) Ni ( p p m )

Fig. 3. Correlation diagrams of selected oxide and element pairs for the reference groups of Bern (n = 79, O) and
Gen~ve (n = 57, • ). (a), (b) and (c) The Bernese outliers are otherwise not different enough to postulate a foreign
origin. The trends suggest the use of illitic-chloritic clays; (d) The Genevan pottery is Cr- and Ni-richer than the
Bernese ceramic.

from the bulk. The samples of the subgroup (GE samples form a homogeneous, CaO-poor group;
5 8 - 6 7 ) with slightly lower Cr and higher Ni than (4) three fine ceramic specimens are CaO-rich
the main Genevan body belong to finds from (GE 22, 56, 57).
outside the town itself (Annecy, D a r d a g n y - It now needs to be determined if the CaO-poor
Brive, Meinier, Mornex and Vandoeuvre- specimens form a homogeneous group when
Pressy). The following conclusions can be examined by themselves, or if the various speci-
drawn: (1) most of the analysed samples were mens from the town and its surroundings differ in
manufactured from CaO-poor clays; (2) neither terms of their chemical composition. A second
of the two analysed marls corresponds chemi- question arises with regard to the relationship
cally to the fine ceramic; (3) 57 fine ceramic between the three outliers and the 57 samples.
72 M. MAGGETI'I & G. GALE'Iq'I
(a) (b) 80
20

~8 ' @12 75

15
@4 57 @
@ 56 o~" 7O @
@
57
v 64 @
0 (:~ 65
=~
10 ¢,/)
44 @44@
60
43 43
22

I I I 55 I I
10 15 20 25 5 10 15 20
CaO (wt%) A I 2 0 3 (wt%)

(c) 500

400

E 300
O.

0 200
@22
56_057
100 ~43
44

0 I I I I
0 50 100 150 200 250
Ni (ppm)

Fig. 4. Correlation diagrams of selected oxide and element pairs for fine ceramic samples from Genbve (n = 60) and
two clays (GE 43 and 44).

Cluster analysis shows that some samples from no evidence of secondary contamination for out-
outside Gen~ve (GE 5 8 - 6 7 ) group together. liers GE 22, 56 and 57, because their aberrant
This group contains the waster from Annecy. elements belong to the so-called immobile
On one hand, this proves that we are dealing elements. It remains unclear, however, if the
with different groups or different local pieces were imported or produced from local
production centres, but, on the other hand, that clay with a different composition than that of
a similar type of raw material was used in the the fine ceramic main group. Because of the pre-
production of all analysed fragments. Factor sence of marls, GE 22, 56 and 57 may possibly be
analysis corroborates this statement, despite the local, despite the fact that they do not correspond
fact that the sample number is statistically suffi- to the raw materials GE 43 and 44. This could be
cient for the kiln population only. As the explained by chemical fluctuations in the clay or
number of analysed sherds is high and the main marl pit. Based on the previous discussion, a
group homogeneous, the outliers cannot be local to regional production of La T~ne fine
explained by a non-statistically representative ceramic by more than one workshop in the area
sampling of the Genevan production. There is of Gen~ve is indicated and allows for the
LATE LA TENE POTTERY 73

definition of a new reference group of 57 CaO- 800 °C), the association of quartz, illite, plagio-
poor samples. clase and K-feldspar. According to Figure 3a-c,
chlorite could be inferred as a further primary
Selection and processing of the raw materials. The constituent in addition to illite. Furthermore, kao-
reference group is characterized by a lean, sili- linite cannot be ruled out, because of the proxi-
cate matrix containing fine-grained non-plastic mity of the excavation site to the Jura mountain
elements, i.e. predominantly quartz and rare, belt.
but characteristic ultramafic grains (serpentinite
and actinolitic or chloritic-actinolitic fels or Pottery from other sites
schist). The maximum diameter of the non-
Grotte du Four
plastic elements is 0.71 mm, but coarse single
grains can be as large as 3.99 ram. Both clay The three analysed fine ceramic specimens
and cottage plaster also show a lean, but belong to the CaO-poor ceramic (Fig. 5a). They
carbonate matrix containing many silicate and vary very significantly in their A1203 concen-
carbonate non-plastic fragments up to 2.65 mm trations and differ in matrix as well as appearance
diameter. of their non-plastic elements. GF 1 has a fatty
Given the chemical and microscopic simi- matrix (it has the highest A1203 value) and
larities, it is possible that a very CaO-rich raw stands out because of the use of grog, whereas
material similar to GE 43, present in the immedi- GF 3 has a lean clay similar to GF 2. It contains
ate proximity of the Rue du Clo~tre kiln, was used more and coarser non-plastic elements than the
as cob (GE 44). For the production of fine pottery, latter (consequently less aluminium). The use
however, a different raw material, poor in CaO of at least two clays (fat and lean) therefore
and of local but still unknown provenance, was appears likely, whereby an admixture of temper
employed. Both analysed marls are extremely to GF 3 is probable, considering the hiatal struc-
rich in CaO, and there may have been too many ture as well the presence of grog.
risks associated with their use (lime spalling). A
CaO-richer clay than the one employed for the La TOne
reference group may have been used very spora- Of the eight analysed fine ceramic specimens,
dically for the production of some fine ceramic four are very poor in CaO (LT 2, 3, 7 and 8),
objects (GE 22, 56, 57). Similar to the example three poor in CaO (LT 1, 5, 6), and only one,
from Bern, this kind of clay may be an inhom- LT 4, is rich in CaO (Fig. 5a). LT 3 stands out
ogeneity within the local clay deposit, because from the rest of the CaO-poor group because of
the fabric of these three samples is identical to its increased Fe203tot, MgO, Cr and Ni concen-
that of the CaO-poor samples. As shown by trations (Tables 1 and 2). There is no evidence
microscopic analysis, the Genevan fine ceramic of a relationship between typology and chemical
is characterized by a homogeneous structure. Its composition.
high Cr and Ni concentrations can be linked to
the presence of ultramafic non-plastic grains. In
the reduced parts of the samples, these have a Marin
light brown to beige colouring, whereas in the The majority of the 11 analysed fine ceramic
oxidized parts they are red to auburn. The non- specimens are CaO-poor, except for ME 3 and
plastic fragments of the Genevan fine ceramic 6 (Fig. 5b). The CaO-poor specimens show, for
therefore point to a hinterland with acidic, grani- instance in their A1203 content, a twofold cluster-
tic to gneissic, as well as ultramafic rock types. ing. All these features can be interpreted as evi-
This is compatible with the catchment area of dence for the use of three different clay sources.
the Rh6ne and Arve rivers and their glaciers,
respectively. In selected correlation diagrams,
the Genevan products are significantly more Saint-Triphon and Massongex
homogeneous and, because the use of a lean Of the 15 analysed fine ceramic samples, TR
raw material, markedly poorer in aluminium 1-14 were found at Saint-Triphon and TR 15
(less clay minerals) but richer in silicon (more was found at Massongex. Six of them (TR 5, 9,
quartz) than the Bernese reference group 10, 11, 13, 14) are CaO-rich (Fig. 5c) and
(Fig. 3a-c). The Bernese raw material may show, in contrast to the nine CaO-poor
have contained more chlorite (higher TiO2 and samples, low Cr and Ni concentrations
FezO3tot concentrations, Fig. 3b and c), but sig- (Table 2). Sample TR 12 differs from the other
nificantly less chromium and nickel (Fig. 3d). CaO-poor specimens by its low Cr and Ni con-
All this is supported by the XRD results tents. Microscopic analyses reveal that the
showing, for lightly fired samples (i.e. below samples were manufactured from two different
74 M. MAGGETTI & G. GALE'Iq'I
(a)
25 (b) 25 +
+
23 23
-h4-
A
21 1 ~ 21
[]6

(3 19 3,6
0 19 -
i
O4 []
<¢ 7~]3 5
[]2
17 - [] 17
•8 4
[] 1 -~ 4,5,10
3 •
15 I I I = 15 = 1 I
0 2 4 6 8 0 0 2 4 6 10
CaO (wt%) CaO (wt%)

(c) (d)
25 25

23 23
A

•~ 21 °•"
v
21
X
X 2
O3
0
19
• 5 9 0
~.o , I 19
~7
/ 13

17 11~
! •13
17
• n14 10
15 I I I I 15 I I I
0 2 4 6 8 10 0 2 4 6 8 10
CaO (wt%) CaO (wt%)
Fig. 5. AI203-CaO correlation diagrams of fine ceramic samples from (a) Grotte du Four (n = 3, II) and La T~ne
(n = 8, [~); (b) Matin (n = 11); (c) Saint-Triphon-Massongex (n = 15); (d) Yverdon (n = 21).

raw materials, a lean and a fatty one, as Ni values detected can be correlated with the
evidenced by two fabrics. serpentinite grains. XRD analysis reveals that
Fabric 1. Lean, silicate matrix. The silicate the three fabrics are correlated with ill•tic raw
non-plastic elements are characteristic serpenti- materials. Chlorite may have been present
nite grains, with a diameter of up to 0.7 mm, initially, but would have been destroyed during
and coarse single grains up to 5.6 mm (TR 1, 3, firing. It appears therefore that the clays were
4, 8, 12, 13). TR 10 and 11 show hardly any initially very inhomogeneous, an assumption
non-plastic elements. that is substantiated by varying CaO values.
Fabric 2. Fat, silicate matrix. Few silicate non-
plastic elements occur as characteristic serpenti-
nite grains with a maximum diameter of 1 mm Yverdon
and coarse single grains up to 2.1 mm (TR 2, 5, With the exception of a few samples (YV 2, 7,
6 , 7 , 9 , 14). 13), most of the 21 analysed fine ceramic
Under the microscope, the samples appear objects are very poor in CaO. YV 9 has increased
very heterogeneous, with grain size and temper Cr and Ni values and thus stands out from the rest
content varying significantly. The high Cr and of the ware, which seems homogeneous in its
LATE LA TI~NE POTTERY 75

Table 2. Chemical analyses (ppm)

No. Ba Cr Cu Ga Nb Ni Pb Rb Sr Th V Y Zn Zr

Bern
BE 6 634 168 26 24 19 100 18 146 134 5 150 43 114 166
BE 7 775 147 26 19 18 80 15 121 393 3 106 34 104 135
BE 8 1023 185 28 25 18 94 19 95 427 0 117 41 121 151
BE 9 638 188 27 28 19 96 23 121 87 8 192 42 129 179
BE 10 834 166 21 20 21 86 21 113 320 15 109 39 116 156
BE 11 832 174 16 20 17 82 14 101 366 8 130 45 110 192
BE 12 701 187 33 24 22 97 13 100 132 6 121 42 112 191
BE 13 965 209 23 28 20 105 23 80 270 12 163 45 149 192
BE 14 834 238 25 34 21 120 30 116 303 8 182 51 165 175
BE 15 1037 249 26 27 15 133 16 83 226 0 109 40 130 149
BE 16 901 194 29 25 23 108 18 65 323 6 163 54 142 197
BE 17 978 189 41 27 19 95 27 92 356 5 169 38 117 161
BE 18 1356 170 88 20 19 84 31 127 177 24 156 35 149 146
BE 19 1174 203 25 21 17 99 27 114 225 15 157 47 112 145
BE 20 1065 195 2540 24 20 102 37 146 137 22 183 38 137 146
BE 21 1694 198 35 22 21 101 30 63 264 18 147 43 135 147
BE 22 1676 118 60 23 21 98 34 135 256 22 140 47 164 151
BE 23 1918 143 25 24 21 107 35 62 334 23 119 49 152 151
BE 24 1571 129 32 26 21 104 17 134 303 9 166 45 150 158
BE 25 967 125 26 25 19 98 21 142 280 2 149 42 154 188
BE 26 961 480 29 24 18 271 30 56 150 20 183 32 138 199
BE 27 1236 187 152 22 18 103 29 124 201 22 146 46 132 139
BE 28 1272 166 24 10 7 75 0 93 132 0 144 17 109 111
BE 29 1250 192 36 29 20 118 19 70 405 0 135 46 160 157
BE 30 1356 170 23 22 19 98 8 62 297 1 107 43 108 156
BE 31 1548 170 26 22 20 97 29 113 189 22 156 41 139 144
BE 32 1010 136 40 20 15 94 0 89 328 0 136 39 101 143
BE 33 1217 191 23 24 23 108 15 78 276 6 155 49 134 168
BE 34 1113 211 34 27 20 118 19 108 227 6 188 51 144 163
BE 35 1575 204 568 22 20 103 28 57 308 22 157 45 148 150
BE 36 1577 206 30 26 22 115 20 56 305 1 151 53 146 176
BE 37 1213 209 29 26 22 108 20 80 261 8 171 49 130 169
BE 38 1587 187 18 23 21 92 29 86 303 27 83 39 125 149
BE 39 521 165 24 24 22 106 8 107 165 5 128 46 119 155
BE 40 370 110 13 10 16 59 2 94 288 1 70 28 84 134
BE 41 1153 159 15 27 17 97 0 72 393 0 86 36 119 149
BE 42 1347 194 27 25 22 99 37 74 272 27 151 41 118 152
BE 43 1453 215 23 25 18 97 9 59 325 0 112 44 124 156
BE 44 520 191 39 29 19 107 23 179 117 6 161 46 118 147
BE 45 885 177 27 30 18 92 27 95 175 11 163 44 134 182
BE 46 1107 207 33 25 19 93 32 157 258 23 143 38 173 152
BE 47 913 175 31 22 22 85 35 93 216 26 107 39 124 181
BE 48 1128 285 57 24 16 236 8 142 288 0 176 34 137 164
BE 49 1501 184 40 26 21 98 33 107 191 26 106 47 118 160
BE 50 905 129 40 16 19 79 20 124 147 23 128 39 123 162
BE 52 267 73 21 6 13 52 0 99 325 0 85 25 72 103
BE 53 802 165 18 14 18 67 0 57 172 7 89 70 50 263
BE 54 1080 167 35 21 22 111 0 169 145 7 179 36 138 151
BE 55 511 152 23 20 18 100 0 178 174 4 162 44 94 133
BE 56 450 132 17 15 15 88 0 154 233 0 134 39 78 128
BE 57 1220 184 25 20 19 103 8 61 330 9 113 44 113 145
BE 58 961 163 238 20 21 105 0 71 251 12 166 51 124 161
BE 59 864 169 30 22 19 105 0 90 242 8 99 50 153 174
BE 60 848 161 17 20 20 98 3 118 302 10 165 48 153 176
BE 61 1107 165 26 t9 21 11I 0 82 277 5 111 52 140 163
BE 62 1789 149 24 13 17 97 0 41 414 1 155 38 100 139
BE 63 957 171 20 18 19 103 0 68 221 5 152 48 127 166

(Continued)
76 M. MAGGETTI & G. GALETI'I

Table 2. Continued

No. Ba Cr Cu Ga Nb Ni Pb Rb Sr Th V Y Zn Zr

BE 64 1264 147 57 19 20 108 0 166 177 5 179 37 212 142


BE 65 935 151 20 16 16 90 5 80 321 9 115 39 120 140
BE 66 1132 151 221 16 20 95 0 71 282 8 154 45 124 179
BE 67 1172 164 34 18 18 102 0 149 182 9 178 43 151 152
BE 68 579 87 19 6 14 73 0 121 349 2 106 27 106 103
BE 69 900 139 23 13 17 87 0 120 306 3 120 37 126 141
BE 70 1433 175 26 17 13 98 0 126 233 2 138 32 161 133
BE 71 784 420 24 17 14 251 I 69 139 4 181 35 106 140
BE 72 1228 166 26 20 21 103 0 73 302 2 140 44 116 152
BE 73 462 155 34 23 17 102 0 175 145 1 156 46 116 138
BE 74 1205 171 218 21 19 108 0 100 316 8 147 47 148 155
BE 75 919 178 24 21 18 109 3 143 302 7 126 44 138 150
BE 76 1513 121 22 16 17 93 1 113 289 9 141 34 138 135
BE 77 714 131 23 20 19 106 0 125 158 7 161 46 146 146
BE 78 1031 105 23 18 18 98 0 79 294 3 144 43 99 141
BE 79 896 111 33 18 20 86 0 113 171 7 127 38 101 170
BE 80 1447 179 34 20 24 106 0 101 281 3 127 44 150 151
BE 81 1424 188 33 18 19 98 0 91 296 5 149 40 161 151
BE 82 792 173 20 21 19 115 3 96 183 3 194 53 134 161
BE 83 965 175 23 22 21 111 0 96 190 6 166 49 112 150
BE 84 1047 170 17 19 22 112 0 68 336 5 131 51 144 156
BE 85 1301 155 345 21 19 110 0 154 241 6 174 48 161 144
BE 86 1868 146 22 15 14 96 0 51 278 7 133 39 117 136
BE 87 1079 172 88 20 22 106 0 114 201 7 192 49 135 163
BE 88 1091 163 20 19 21 106 0 95 220 8 159 47 137 156
BE 89 1053 156 23 18 22 108 0 166 194 5 143 50 135 152
BE 90 1294 151 38 19 17 100 4 47 301 9 154 42 126 149
BE 91 1268 159 37 20 27 114 0 61 350 6 164 57 159 171
BE 92 992 159 1302 20 24 113 0 66 283 5 164 54 142 169
BE 93 1237 152 22 19 20 109 2 123 216 8 182 48 129 159
Genbve
GE 1 445 377 41 20 13 201 6 156 72 2 180 29 ll6 159
GE 2 494 420 50 19 14 183 7 151 79 3 167 35 124 168
GE 3 455 357 45 20 14 204 8 149 67 5 172 31 114 168
GE 4 371 384 29 19 14 205 9 133 77 9 159 31 104 166
GE 5 505 423 44 20 14 210 3 158 82 4 192 29 187 160
GE 6 438 361 38 22 19 204 9 158 73 12 176 33 118 165
GE 7 451 368 50 22 16 210 8 161 74 11 182 32 121 166
GE 8 437 387 34 21 16 210 8 157 76 7 182 30 120 170
GE 9 471 393 33 20 16 208 6 158 76 3 190 29 121 164
GE I0 446 374 25 22 16 201 13 152 80 9 I84 32 123 167
GE 11 458 365 43 21 16 206 11 156 80 9 177 32 119 163
GE 12 533 352 47 2l 16 200 10 152 82 7 193 29 123 160
GE 13 453 363 43 22 15 209 9 153 74 9 192 32 115 162
GE 14 449 382 41 21 17 208 12 157 75 10 179 32 120 169
GE 16 460 368 38 22 14 206 8 154 76 9 186 27 117 165
GE 17 424 386 41 21 16 206 13 151 74 11 171 32 118 175
GE 18 451 376 43 20 13 207 6 156 74 6 187 29 119 160
GE 19 494 376 41 19 16 198 6 147 80 10 191 28 118 163
GE 20 506 392 40 20 16 207 2 155 91 0 186 27 119 159
GE 21 479 367 36 21 17 204 11 157 81 12 197 30 120 163
GE 22 463 212 35 17 12 136 2 149 235 4 145 30 97 143
GE 23 391 376 51 19 13 184 7 140 73 7 157 25 104 166
GE 24 370 353 51 18 15 196 10 133 86 10 165 29 107 174
GE 25 513 381 48 19 16 190 9 143 156 7 169 31 125 153
GE 26 465 347 47 19 14 205 10 145 71 2 172 28 117 165
GE 27 366 364 25 18 15 187 10 137 74 7 161 29 113 169

(Continued)
LATE LA TI~NE POTTERY 77

Table 2. Continued

No. Ba Cr Cu Ga Nb Ni Pb Rb Sr Th V Y Zn Zr

GE 28 430 387 40 19 13 174 6 133 79 14 164 22 101 151


GE 29 390 364 33 19 15 174 11 143 77 12 171 21 108 159
GE 30 425 385 37 19 15 213 6 140 67 6 170 27 108 164
GE 31 532 372 38 19 13 196 9 151 82 10 189 25 114 158
GE 32 473 420 38 20 16 219 10 146 82 14 178 32 118 161
GE 33 430 365 35 17 13 176 8 133 80 7 162 23 101 153
GE 34 456 351 33 19 15 200 8 139 80 11 178 29 117 167
GE 39 454 370 34 21 15 202 12 154 76 13 180 29 117 166
GE 40 455 386 37 22 17 210 6 153 74 8 192 31 122 168
GE 41 482 377 39 22 14 202 6 160 78 2 184 29 126 160
GE 42 499 366 41 21 16 204 7 161 94 7 191 30 129 160
GE 43 206 107 22 6 8 55 0 58 301 2 39 21 110 155
GE 44 185 95 25 5 8 50 0 50 301 1 42 17 48 145
GE 45 395 351 40 23 17 196 7 161 73 10 188 30 118 160
GE 46 479 438 49 20 14 226 18 144 90 6 177 28 119 151
GE 47 503 427 49 22 18 212 8 157 73 9 190 35 125 167
GE 48 496 411 42 21 15 209 6 156 81 5 191 28 117 172
GE 49 452 379 46 22 16 217 13 154 71 19 184 32 120 174
GE 50 510 423 49 23 17 198 13 160 81 10 183 32 124 166
GE 51 471 345 53 23 16 211 11 163 71 9 189 30 121 162
GE 52 434 404 36 20 15 206 11 149 72 8 177 28 111 170
GE 53 485 401 42 21 13 211 7 146 75 7 182 31 117 159
GE 54 486 373 39 19 14 195 11 142 80 9 171 32 117 161
GE 55 517 475 53 20 14 215 5 147 95 1 175 30 119 157
GE 56 371 140 17 10 7 66 0 94 149 0 130 22 71 164
GE 57 499 122 13 9 7 55 0 87 173 1 123 23 74 169
GE 58 448 325 33 17 11 225 1 125 70 7 166 27 97 147
GE 59 505 302 35 18 12 228 0 138 89 3 182 28 114 145
GE 60 406 321 34 19 14 234 0 135 63 2 180 27 101 151
GE 61 385 306 30 18 12 220 0 140 65 3 168 25 100 148
GE 62 496 332 32 17 17 220 0 108 66 6 188 32 109 170
GE 63 502 342 37 17 15 246 0 146 80 2 175 30 110 145
GE64 425 299 23 14 14 224 0 126 92 7 146 32 105 164
GE 65 467 329 35 16 13 229 0 141 83 2 171 31 111 160
GE 66 459 304 35 17 16 235 0 153 76 4 174 30 115 151
GE 67 399 316 35 19 14 244 0 159 85 3 172 35 110 145
GroneduFour
GF 1 430 152 27 24 19 63 25 133 123 19 180 35 117 218
GF 2 660 137 46 25 16 83 34 172 74 18 161 32 120 150
GF 3 735 183 26 19 15 98 14 137 93 8 145 28 104 198
LaTkne
LT 1 467 121 25 14 18 62 7 141 152 18 135 30 99 187
LT 2 804 171 28 17 19 90 10 116 111 24 166 30 102 171
LT 3 488 380 53 20 15 379 1 149 75 15 196 35 106 146
LT 4 681 120 27 17 17 77 0 140 178 15 132 35 97 140
LT 5 593 170 33 20 21 100 10 96 121 28 174 38 119 182
LT 6 667 146 32 19 18 86 9 157 120 19 157 31 108 156
LT 7 555 168 28 18 17 93 2 159 86 17 164 38 116 161
LT 8 505 185 26 16 18 116 2 139 93 15 151 40 98 168
Ma Hn
ME 1 642 212 27 26 22 115 30 97 85 39 146 38 149 161
ME 2 1128 208 23 22 19 122 4 125 106 19 177 46 128 168
ME 3 1293 122 35 17 14 119 0 149 123 7 166 31 136 134
ME 4 1321 206 29 17 17 121 35 101 94 24 141 31 116 227
ME 5 1637 175 19 13 16 131 0 104 105 10 166 38 104 206

(Continued)
78 M. MAGGETTI & G. GALE'Iq'I

Table 2. Continued

No. Ba Cr Cu Ga Nb Ni Pb Rb Sr Th V Y Zn Zr

ME 6 1053 121 37 17 16 96 0 151 132 2 156 41 ll8 138


ME 7 427 173 20 29 23 112 18 83 75 21 209 65 150 175
ME 8 671 199 28 23 20 147 16 124 82 9 154 60 146 161
ME 9 1480 107 21 24 19 79 16 168 139 10 165 48 149 141
ME 10 1144 176 20 15 18 140 9 103 80 25 161 33 102 207
ME 11 591 153 25 21 21 81 12 56 95 23 202 44 114 191

St. Triphon-Massongex
TR 1 500 323 42 19 12 232 8 142 103 7 167 28 126 159
TR2 818 283 39 22 12 197 7 157 306 8 187 30 156 144
TR 3 456 311 42 21 17 222 15 149 85 7 170 31 124 169
TR 4 473 325 46 19 15 244 7 147 98 0 178 29 118 160
TR 5 717 144 34 21 14 88 9 158 422 2 151 25 144 135
TR 6 795 326 36 22 15 229 9 147 242 6 175 27 134 151
TR 7 648 333 34 22 15 234 7 153 122 5 192 28 134 163
TR 8 577 328 39 20 12 224 2 140 121 5 173 27 129 159
TR 9 627 137 29 21 14 90 14 166 314 5 156 30 146 124
TR 10 923 141 27 17 15 81 7 135 388 5 125 33 120 138
TR 11 545 136 35 22 15 91 7 163 340 5 143 30 127 136
TR 12 643 185 28 19 14 96 5 149 131 3 135 29 107 203
TR 13 607 170 32 20 15 101 0 165 216 1 138 26 120 160
TR 14 638 129 26 16 11 72 14 113 243 11 126 25 118 145
TR 15 519 353 43 19 17 247 0 157 80 0 179 33 126 156
Yverdon
YV 1 760 144 28 27 16 86 16 215 93 11 192 32 151 |29
YV 2 882 139 29 24 17 85 21 188 177 13 169 35 146 138
YV 3 946 153 25 27 14 94 18 208 182 10 199 34 176 127
YV4 1194 151 30 25 14 94 16 210 234 9 192 24 220 115
YV5 561 125 26 22 14 75 12 153 82 6 144 33 121 171
YV 6 1192 108 27 17 14 70 15 142 236 13 143 25 128 177
YV7 917 133 25 21 15 82 23 176 180 12 164 38 143 150
YV 8 60I 131 35 22 |6 81 15 161 83 10 161 33 123 173
YV 9 711 318 26 19 12 205 8 134 116 5 177 23 130 154
YV 10 605 125 29 20 15 80 18 156 95 11 152 36 117 181
YV 11 724 154 29 27 15 94 15 215 76 6 202 32 144 125
YV 12 1004 143 31 22 13 84 18 174 249 9 160 27 147 139
YV 13 1027 134 22 21 15 81 24 173 237 9 166 34 164 146
YV 14 842 212 38 22 9 102 20 161 123 11 176 30 132 132
YV 15 562 166 31 23 18 104 13 167 98 3 170 29 116 168
YV 16 1085 128 21 19 19 69 18 120 251 5 136 53 114 286
YV 17 1149 129 47 22 8 67 31 168 189 12 149 21 165 129
YV 18 604 139 27 21 17 77 18 158 125 12 171 31 130 154
YV 19 1552 177 36 17 12 109 12 121 289 12 151 33 170 180
YV 20 990 139 31 19 15 78 14 145 179 11 172 33 114 175
YV 21 614 129 23 25 13 76 16 195 70 0 160 30 128 134

chemical composition. Microscopically, two occur, with a m a x i m u m d i a m e t e r o f 1 m m (YV


fabric types can be identified, indicating the use 1, 2, 3, 4, 6, 7, I l, 12, 13, 14, 17). As expected,
o f two different clays. the samples belonging to fabric 1 are mostly
Fabric 1. Lean, silicate matrix. Silicate poorer in a l u m i n i u m than those o f fabric 2. Micro-
non-plastic e l e m e n t s occur, with a m a x i m u m scopic analysis reveals large fluctuations in non-
d i a m e t e r o f 0.9 m m and as single coarse single plastic e l e m e n t s and carbonate contents, as well
grains up to 1.2-2.1 m m (YV 5, 8, 9, 10, 15, as in granulometry. A c c o r d i n g to X R D results,
16, 18, 19, 20 and 21). the use o f illitic clays is most likely. Chlorite
Fabric 2. Fat, silicate matrix. Silicate, as well m a y have been present and was d e s t r o y e d
as carbonate (YV 2, 7, 13) non-plastic e l e m e n t s during firing.
LATE LA TENE P O T T E R Y 79

Discussion and conclusions compared with the centroid of the Genevan


The chemical analysis has revealed clearly that group, range from 0.005 to 1.118. This argues
the majority of the sherds are CaO-poor. A for a provenance of these objects from the
further chemical and geographical subdivision Genevan region. Microscopic analysis provides
can be obtained based on the chromium and further evidence of such a origin, because the
nickel concentrations. The studied 70 samples thin-section specimens TR 1, 3 and 4 show a
from the Rh6ne Valley and Gen~ve, i.e. the pro- lean matrix with serpentinite non-plastic
ducts from Gen~ve (without GE 22, 56, 57), elements (but not the actinolitic or chlotitic-
Saint-Triphon-Massongex (without TR 12), as actinolitic fragments characteristic of some
well as the samples BE 26, 48, 71, LT 3 and Genevan samples). Because of their different
YV 9, are distinguishable from the rest of the chemical composition, the other Cr- and Ni-rich
ceramic because of their high Cr and Ni values. samples, BE 26, 48, 71, LT 3 TR 2, 6, 7, 8 and
The question is therefore whether in the Rh6ne YV 9, cannot be attributed to the Genevan area
Valley-Lake Geneva corridor ceramic was and probably belong to different production
produced in several places or exclusively in sites. Their provenance remains unknown,
one place, i.e. Gen~ve, and if ceramic was because the known Swiss reference groups
exported from this region to Bern, La T~ne, are all Cr- and Ni-poor and cannot be used as a
Saint-Triphon-Massongex and Yverdon. A tool for comparison. However, based on the
similar question can be asked for the Cr- and microscopic analysis (sandstone fragment) it is
Ni-poor pottery, concentrated in the region possible that BE 26 originates from Bern. This
between the three lakes and Bern: is there evi- sample would consequently have been manu-
dence of imports from Bern or of several pro- factured from local clay, rich in Cr and Ni.
duction centres?
Cr- and Ni-poor pottery: one or several
Cr- and Ni-rich pottery: ceramic import from
workshops?
Genkve to Bern, La Tkne, Saint-Triphon-
Discriminant analysis of 130 Cr- and Ni-poor
Massongex and Yverdon ?
fine ceramic La T~ne products shows, apart
According to the factor analysis, the specimens from a wide scatter, a relatively clear separate
from Bern, La Tbne and Yverdon differ from grouping of the 79 Bernese reference samples
the Genevan population, whereas the samples from the specimens from Genbve, Matin,
from Saint-Triphon-Massongex can be inte- Yverdon and the other sites (Fig. 7). Attempts
grated into this group, with the exception of TR to solve the overlap of the samples from La
2, 6, 7 and 8 (Fig. 6). Mahalanobis distances of T~ne, Grotte du Four and Saint-Triphon-
the Genevan reference group (n = 57), calculated Massongex on the Yverdon scatter are prevented
by discriminant analysis, range from 0.000 to by the wide spread of the Yverdon samples,
4.579. The distances of the Saint-Triphon-Mas- which rules out the possibility of establishing a
songex specimens TR 1, 3, 4 and 15, when statistically valid reference group of this pottery

BEo48
TR=2
"(b
- 2

o oo R~o ,.,.9 +¢÷ + +


t~_0 T..7 o o~O 7 ~ oO
,- 1 -- BE 71 -I-
o O
• %-•
TRs• • omO=I~ZiI~= --2 liB ~ • •~ Yverdon
e,. 0 ot °
l-- 01 • St Triphon/Mass.
u.I Y~° . .'.," X Yverdon
YV 14
-,X- a La Tene
-1 Y~7
• St Triphon/Mass. + Marin
• I [ ] La T~ne --6 41.° • Grotte aux E
-2 ill
• Geneve • Geneve

-3 O Bern --8 I I I I O Bern


..-z n3 t2 11 1 n
- - - 0 1 --4 -2 0 2 4
REGR factor score 2 Discriminant Scores from Function 2

Fig. 6. Factor analysis of 70 Cr- + Ni-rich potteries Fig. 7. Discriminant analysis of 130 Cr- + Ni-poor
from five sites in western Switzerland. potteries from seven sites in western Switzerland.
80 M. MAGGETTI & G. GALETFI

production. Only GF 2 is chemically similar stratigraphique /l Yverdon-les-Bains VD, Parc


enough to the majority of the Yverdon samples Piguet, 1992. Jahrbuch Schweizerische
for a provenance from this region to be likely. Gesellschaft fiir Ur- und Friihgeschichte, 78, 7-56.
Summarizing, the chemical patterns of these EGLOFF, M. 1991. L'artisanat celtique d'apr6s les trou-
ceramics samples argue for geographically dis- vailles de La T~ne. Celti 1991, 369-371.
HALDIMANN, M.-A., CURDY, PH., GILLIOZ, P.-A.,
tinct pottery workshops. These cannot be KAENEL, G. & WIBLI~, F. 1991. Aux origines
described in more detail because of a lack of ana- de Massongex VS. Jahrbuch Schweizerische
lyses from the studied sites as well as of clearly Gesellschaft fffr Ur- und Friihgeschichte, 74,
defined CaO-poor reference groups in this 129-182.
region. KAENEL, G. 1990. Recherches sur la p6riode de La
T/me en Suisse occidentale. Analyse des s6pultures.
Cahiers d'archdologie romande, Lausanne, 50.
Conclusion KAENEL, G. 1991. La Grotte du Four (Boudry, canton
In conclusion, most of the samples from each de Neuchfitel): "temple helv~te" ou habitat-refuge
site differ in their chemical composition from de la fin de La T/me? Les Celtes dans le Jura,
MusSes de Pontarlier, Yverdon-les-Bains, Lons-
the pottery of the other sites. It is therefore
le-Saunier et Lausanne, Lausanne, 111 - 113.
likely that the Late La T6ne ceramic of western KOHLER, P. 1991. Bern-Heiligkreuzkirche. Eine
Switzerland correspond to one or several local mittel- und spiitlatbnezeitliche Siedlungsstelle.
pottery productions, as was demonstrated by Diploma thesis, University of Bern.
Maggetti & Galetti (1981) and Maggetti et al. KORITNIG, S. 1978. Phosphorus. hT: WEDEPOHL,K. H.
(1988) for the Late La T/me ceramic production (ed.) Handbook of Geochemistr)." 11-2. Springer,
in northwestern Switzerland. The number of Berlin, 15 k 1-15 k 5.
sherds analysed from the sites of Bern and LANGE, B. & VEJDELEK, Z. J. 1980. Photometrische
Gen~ve is statistically sufficient; consequently, Analyse. Verlag Chemie, Altenberg.
two new Swiss reference groups can be defined. MAGGETTI, M. & GALETTI, G. 1981. Arch~iometrische
Untersuchungen an sp/itlatenezeitlicher Keramik
von BaseI-Gasfabrik und Sissach-Briihl. Archiio-
We thank Ph. Curdy, G. Kaenel, P. Kohler and D. Paunier Iogisches Korrespondenzblan, 11(4), 321-328.
for their help in providing the material and for helpful MAGGETTi, M., GALETTI, G. & SCHNEUWLY, R.
discussions. 1988. Die sp/itlat6nezeitliche feinkeramische
Referenzgruppe Sissach-Bri.ihl. Archiiologie und
Museum, Liestal, 13.
References MAGGETTI, M., GALETTI, G. & PAUNIER, D. 1989.
ARNOLD, B. 1992. Le site hallstattien et l'enceinte R6ntgenographische Phasenanalyse schweizer-
quadrangulaire lat6nienne de Marin-Les Bour- ischer antiker Keramik. In: SCHWEIZER, F. &
guignonnes (canton de Neuchhtel). Cahiers VILLIGER, V. (eds) Methoden zur Erhaltung yon
d'archdologie romande, 57, Lausanne, 309-315. Kulturgiitern, P. Haupt, Bern, 209-214.
BACHER, R. 1989. Bern-Engemeistergut 1983. Staatli- MULLER, F. 1990. Der Massenfund vonder Tiefenau
cher Lehrmittelverlag, Bern. bei Bern. Antiqua 20.
BONNET, C. 1997. Le d~veloppement urbain jusqu'au MI~ILLER, F. 1996. Lat~nezeitliche Grabkeramik aus
dfbut du Bas empire. La Gen~ve sur l'eau. Monu- dem Berner Aaretal. Jahrbuch Schweizerische
ments d'art et d'histoire du Canton de Genbve, 1, Gesellschaft fiir Ur- und Frtihgeschichte, 76,
24-30. 43 -66.
BRUNETTI, C. 2005. L'oppidum d'Yverdon-les-Bains MI~LLER-BECK, HJ. 1963-1964. Die Erforschung der
au ler si~cle av. J.-C. Cahiers d'archdologie Engehalbinsel in Bern bis zum Jahre 1965. Jahr-
romande, 101, Lausanne, 19-27. buch Bernisches Historisches Museum, 43-44,
COLLOMB, P. & MAGGETTL M. 1996. Dissolution des 375 -400.
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n6es. Revue d'Archdomdtrie, 20, 69-75. Gen~ve. Mdmoires et Documents, X.
CURDY, P., KAENEL, G. & ROSSl, F. 1992. Yverdon- SCHNEIDER, G. 1989. Chemische Zusammensetzung.
les-Bains (canton de Vaud) h la fin du Second age In" SCHNEIDER, G. (ed.) Naturwissenschaftliche
du Fer: nouveaux acquis. In: L'6ge du Fer dans Kriterien und Verfahren zur Beschreibung von
le Jura, 285-300. Keramik. Acta Praehistorica et Archaeologica, 21,
CURDY, P., BESSE, M. & MARIETHOZ, F. 1997. Le 28-29.
rituel fun~raire en territoire s6dune (fin du 2~me SCHWAB, H. 1990. Les Celtes sur la Broye et la
fige du fer). Nouveaux acquis. Bulletin d'dtudes Thielle. Arch~ologie de la 2e correction des eaux
prdhistoriques et archgologiques alpines, 5 - 6 du Jura, 1989. (Arch~ologie fribourgeoise, 5).
(1994-1995), Soci6t6 Vald6taine de pr6histoire et Editions Universitaires, Fribourg.
d'arch~ologie, Aoste, 169-187. ST,~.HLI, B. 1977. Die Latbnegriiber yon Bern-Stadt.
CURDY,P., FLUTSCH,L., MOULIN,B. & SCHNEITER,A. Schriften Seminar fiir Urgeschichte, Universit/it
1995. Eburodunum vu de profil: coupe Bern.
Characterization of Maltese pottery of the Late Neolithic, Bronze Age
and Punic Period by neutron activation analysis
H. M O M M S E N 1, A. B O N A N N O 2, K. C H E T C U T I B O N A V I T A 2, I. K A K O U L L I 3,
M. M U S U M E C I 4, C. S A G O N A 5, A. S C H W E D T 1'6, N. C. V E L L A 2 & N. Z A C H A R I A S 7
1Helmholtz-Institut fiir Strahlen- und Kernphysik, University of Bonn,
Nussallee 14-16, 53115 Bonn, Germany (e-mail: mommsen@hiskp.uni-bonn.de)
2Department of Classics and Archaeology, University of Malta, Tal-Qroqq MSD 06, Malta
3The UCLA/ Getty Archaeological and Ethnographic Conservation Program, A410 Fowler,
Los Angeles, CA 90095-1510, USA
4Academic Division, MATSEC Support Unit, University of Malta, Tal-Qroqq,
Msida MSD 06, Malta
5School of Fine Arts, Classical Studies and Archaeology, University of Melbourne,
Melbourne, Vic. 3010, Australia
6present address: Equip de Recerca Arqueomktrica de la Universitat de Barcelona,
Departament de Prehistbria, Histbria Antiga i Arqueologia, C/de Baldiri Reixac,
s/n, 08028 Barcelona, Spain
7Laboratory of Archaeometry, Institute of Materials Science, NCSR Demokritos,
Aghia Paraskevi, 15310 Attiki, Greece

Abstract: A set of 41 samples from Tas-Silg, Malta, has been analysed by neutron
activation. It contained nine ware groups formed by visual examination covering the Late
Neolithic, Bronze Age and Punic Periods (c. 3000-218 Be). Despite this diversity and
long time range, seven of these ware groups, including the 'Thermi Ware', all have a
similar chemical composition and, therefore, have been made from the same clay. This
points most probably to a local origin. One group from the Punic Period, containing only
Bricky Red cooking ware, is chemically separate and represents a second distinct pattern
probably assignable to a local production. Five amphora sherds also from the Punic
Period, and consisting of a micaceous fabric, all have different chemical characteristics
and are probably imports from overseas production sites of unknown location.

Since 1996 the University of Malta, through the are available in a preliminary report (Bonanno
Department of Classics and Archaeology, has et al. 2000), where a detailed description of the
conducted archaeological excavations at the various types of pottery, its fabrics, styles and
ancient sanctuary site at Tas-Silg, Malta. A sub- decorations is given by C. Sagona.
stantial amount of ancient ceramics from strati- The next stage in the pottery study was the
fied deposits has been recovered in the course chemical classification of the various types of
of these excavations. From the outset, one of wares using neutron activation analysis (NAA).
the principal aims of the project has been to As is well known, the minor and trace element
identify ceramic ware types at the site, ranging concentrations in pottery reflect mainly the com-
from its prehistoric origins (c. 3000 Be) into position of the clay paste prepared by the potters,
the Punic Period, and beyond to more recent which depends mainly on the geochemical com-
periods. In 2001, after five seasons of scientific position of the clay beds exploited (e.g. Perlman
excavations and rigorous extensive analysis, a & Asaro 1969; Jones 1986; Mommsen 2001).
point has been reached at which the range of Therefore, the concentration patterns in pottery
wares at the site had been classified at the macro- point to their production places, assuming that
scopic level by visual inspection. Details about the raw clays available in the region have been
the site at Tas-Silg and its archaeological context used by the potters to prepare their pastes and

From:MAGGETTI,M. & MESSIGA,B. (eds) 2006. Geomaterialsin CulturalHeritage.


Geological Society, London, Special Publications, 257, 81-89.
0305-8719/06/$15.00 © The Geological Society of London 2006.
82 H. MOMMSEN E T AL.

that clays have not been traded. The aim of this Early Bronze Age Period by the 'Thermi Ware'
study was to determine if the pottery ware sherd Silg 43, and the Late Bronze Age Borg
types were produced from the same or different in-Nadur phase by sherds Silg 1-5. One
clay pastes and, if possible, if types of local pro- sample, Silg 42, is from an early modern tile
duction could be distinguished from imported and was included as a possible reference piece.
types from foreign, overseas workshops. It was The remaining 30 sherds all belong to the
anticipated that this might give some insight Punic Period and comprise the following ware
into Malta's trade relations, especially during types: Crisp Ware (Silg 6-10), Soft Brown
the Bronze Age and the Punic Period. Ware (Silg 11-15), Biscuit Ware (Silg 21-25),
Bricky Red Ware (Silg 31-35), Drab Coarse
Ware (Silg 36-40), and Micaceous Wares (Silg
Sample choice and description 26-30), which have been described by Sagona
An initial set of 40 pottery sherds has been in Bonanno et al. (2000). Although clay deposits
selected for chemical analysis by NAA. Having with a rare scattering of biotite (brown mica) are
identified visually and haptically a number of found on the island (M. Pedley, pers. comm.;
ware types, C. Sagona, responsible for the Tas- Digeronimo et al. 1981), the five amphora
Silg typology, proceeded to select eight of the sherds (Silg 26-30) have muscovite (transparent
most common or characteristically distinct ware mica) inclusions, each one having a characteristi-
type groups excavated at Tas-Silg for further cally distinct fabric. This, together with the fact
comparative analyses. Five sherds of vessels of that only a small number of Micaceous sherds
different shapes from each ware type were excavated at Tas-Silg can be identified, suggests
selected as being representative of that ware that they are imports.
type and examined with the aid of a magnifying
glass. Details of the fabric, shape, inclusions,
surface treatment and colour were noted for Analytical procedure and data evaluation
each sherd. In addition, one sherd of a 'Thermi Neutron activation analysis (NAA) is a method
Ware' bowl as a ninth ware type excavated at very well suited to classify pottery by chemical
Tas-Silg was available for NAA (Sagona in means, as it is multi-elemental, sensitive down
Bonanno et al. 2000, p. 87, fig. 9.4). This ware to the trace element level, and precise (e.g.
is assigned to the Early Bronze Age of the Perlman & Asaro 1969; Mommsen 2004). At
Aegean. Identified as 'Thermi Ware' are bowls the Helmholtz-Institut ftir Strahlen- und
and pedestal bowls with an internally thickened Kernphysik, University of Bonn, only 80 mg
lip decorated with dot-filled incised triangles, of pottery powder are needed for an analysis.
for which a close parallel was identified in The sample is taken by drilling with a pointed
Early Bronze Age Thermi (Lesbos). Tradition- sapphire-drill of 10 mm diameter, usually on
ally thought to be imported from the east, it the internal surface of the sherds, leaving only
occurs also in Castelluccio levels in eastern a shallow depression. The neutron irradiations
Sicily. Matters are further complicated by the are carried out at the research reactor in
fact that some sherds were discovered in Geesthacht. The analytical procedure has been
Temple Period contexts. described by Mommsen et al. (1991). It is a
An overview of the sample set is given in modified version of that given by the former Ber-
Table 1. Although all the ware type groups keley group (Perlman & Asaro 1969). As the
classified by visual examination are distinct Bonn pottery standard is calibrated against the
from other ware types, there are notable differ- Berkeley standard, our concentration data can
ences between sherds within any one group, be compared directly with the values of this
such as extent and nature of inclusions, i.e. group. A calibration to other standards in use
vessels of the same ware type were produced has been given by Hein et al. (2002).
from clays with different non-plastic admixtures. The comparison of the measured elemental
This is particularly the case for the Temple data and the formation of groups of samples
Period Wares, Borg in-Nadur Wares, and mica- having a similar composition are done by a
ceous Wares. But because such inclusions are multivariate statistical filtering procedure devel-
usually poorer in trace elements compared with oped in Bonn (Beier & Mommsen 1994a,b)
the higher concentrations in clays, NAA could using a Mahalanobis distance search (Harbottle
reveal if the same clay bed was exploited for 1976). In contrast to the common statistical
the preparation of these different pastes. methods such as cluster analysis or principal
The nine ware types selected are attributed to component analysis, it is able to take into con-
five time periods. The Late Neolithic Temple sideration two important features: (1) individual
Period is represented by sherds Silg 16-20, the experimental errors; (2) a possible constant
CHARACTERIZATION OF MALTESE POTTERY 83

Table 1. List of sherds from Tas-Silg, Malta, studied by NAA


Sample Excavation Ware type name, Fabric description:
number inventory number time period fabric texture/surface
treatment/inclusions
Silg 1 TSG96/2112/5 Borg in-Nadur Ware, Bronze Age Coarse/burnish/quartzite grit
Silg 2 TSG96/2112/15 Borg in-Nadur Ware, Bronze Age Coarse/burnish/sparse grog
Silg 3 TSG96/2097/6 Borg in-Nadur Ware, Bronze Age Fine/burnish/moderate grog
Silg 4 TSG96/2101/5 Borg in-Nadur Ware, Bronze Age Coarse/quartzite grit
Silg 5 TSG96/205/47 Borg in-Nadur Ware, Bronze Age Fine/burnish/moderate grog
Silg 6 TSG96/2019/28 Crisp Ware, Punic Period Fine/slip/moderate grog
Silg 7 TSG96/2061/24 Crisp Ware, Punic Period Fine/slip/moderate grog
Silg 8 TSG96/1010/14 Crisp Ware, Punic Period Coarse/slip/grog
Silg 9 TSG96/2097/17a Crisp Ware, Punic Period Fine/slip
Silg 10 TSG96/29/32 Crisp Ware, Punic Period Fine/thick slip/brown rock? grit
Silg 11 TSG96/2054/15 Soft Brown Ware, Punic Period Fine/self-slip/grog specks
Silg 12 TSG96/210/4 Soft Brown Ware, Punic Period Fine/self-slip/Ca specks
Silg 13 TSG96/23/8 Soft Brown Ware, Punic Period Refined/self-slip
Silg 14 TSG96/2077/14 Soft Brown Ware, Punic Period Coarse/self-slip/grog, Ca grit
Silg 15 TSG96/2092/33 Soft Brown Ware, Punic Period Fine/slip/grog specks
Silg 16 TSG96/9/1 Temple Period Ware, Late Neolithic Coarse drab/slip/moderate grog
Silg 17 TSG96/11/63 Temple Period Ware, Late Neolithic Fine/burnish/red specks
Silg 18 TSG96/11/57 Temple Period Ware, Late Neolithic Refined/burnish
Silg 19 TSG96/210/9 Temple Period Ware, Late Neolithic Refined/burnish/Ca specks
Silg 20 TSG96/220/27 Temple Period Ware, Late Neolithic Refined/burnish/Ca specks
Silg 21 TSG96/34/26 Biscuit Ware, Punic Period Coarse/slip/Ca grit
Silg 22 TSG96/205/19 Biscuit Ware, Punic Period Fine/slip/Ca grit
Silg 23 TSG96/205/49 Biscuit Ware, Punic Period Fine/slip/Ca specks
Silg 24 TSG96/105/9 Biscuit Ware, Punic Period Fine/slip/Ca specks
Silg 25 TSG96/2016/54 Biscuit Ware, Punic Period Coarse/slip/Ca grit
Silg 26 TSG96/205/54 Micaceous Ware, Punic Period Refined/muscovite mica
Silg 27 TSG96/204/28 Micaceous Ware, Punic Period Refined/slip/muscovite mica
Silg 28 TSG96/220/29 Micaceous Ware, Punic Period Refined/ mica-dusted/muscovite
mica
Silg 29 TSG96/220/23 Micaceous Ware, Punic Period Refined/self-slip/muscovitemica
Silg 30 TSG96/34/42 Micaceous Ware, Punic Period Refined/slip/muscovite mica
Silg 31 TSG96/34/36 Bricky Red Ware, Punic Period Coarse/cream slip/Ca grit
Silg 32 TSG96/34/33 Bricky Red Ware, Punic Period Coarse/self-slip/Ca grit
Silg 33 TSG96/34/37 Bricky Red Ware, Punic Period Coarse/self-slip/Ca grit
Silg 34 TSG96/2026/22 Bricky Red Ware, Punic Period Fine/self-slip/sparse Ca grit
Silg 35 TSG96/34/34 Bricky Red Ware, Punic Period Coarse/self-slip/Ca grit
Silg 36 TSG96/1033/1790 Drab Coarse Ware, Punic Period Coarse/slip/frequent grog
Silg 37 TSG96/1033/1375 Drab Coarse Ware, Punic Period Very coarse/slip/frequent grog
Silg 38 TSG96/1033/800 Drab Coarse Ware, Punic Period Coarse~slip~frequent grog
Silg 39 TSG96/1033/1229 Drab Coarse Ware, Punic Period Very coarse/slip/frequent grog
Silg 40 TSG96/1033/1291 Drab Coarse Ware, Punic Period Coarse/slip/moderate grog
Silg 42 - Tile of structure, Early Modern
Silg 43 TSG96/2061/9 Thermi Ware, Early Bronze Age Thickened lip with dotted
decoration

shift of the data caused by diluting compounds in For these elements, only isotopes excited by
the samples. Examples of this evaluation fast neutrons have long enough half lives to be
procedure have been presented by Mommsen measurable 5 days after the irradiations as done
(2001) and Akurgal et al. (2002). The neglect in Bonn. As a result of a substantial reduction
of experimental errors during the group- of the fast neutron fraction in the irradiating
forming procedure is dangerous in the case of neutron beam since an upgrading of the reactor
elements measurable only with a large margin in Geesthacht in the year 2000, these elements
of error and might lead to wrong classifications. are currently determined only with large errors.
With regard to NAA as performed at Bonn, this However, consideration of errors allows their
mainly concerns the elements Ca, Ti and Ni. inclusion during grouping. In addition, possible
84 H. MOMMSEN ET AL.

constant shifts of all concentration values should sherds, sampled as Silg 1, is shown in Figure 1
be corrected during group formation to reduce (top). Silg 1 and 4 both have a high Ca content
the spreads of the average concentration values (18.7% and 19.9%, respectively), which points
of the pottery groups obtained. Levigating the to Ca as at least one of the diluents. By visual
raw clays or adding tempering material such as examination, both samples were noted for their
sand or calcite in varying amounts will enrich moderate amount of coarse quartzite inclusions;
or dilute the clay fraction of the paste, often this also may account for their strong dilution.
changing all the concentration values by a con- On the other hand, the concentrations for three
stant factor. Besides such pottery-making prac- of the oldest samples from the Temple Period
tices, experimental errors, e.g. weighing errors (Silg 18-20) have to be lowered by more than
and/or neutron flux heterogeneities, may also 20% to match the group mean values; these
be the cause of such constant shifts. Therefore, samples have the highest concentrations of trace
constant shifts should be corrected by either and minor elements in the whole group of
using concentration ratios (Buxeda i Garrigos samples. The cross-section of sherd sampled as
1999) in statistical cluster analyses or, to be inde- Silg 18 is also shown in Figure 1 (bottom) for
pendent of the single concentration value chosen comparison. All three samples belong to thin-
as denominator, performing a best relative fit of walled vessels having a fine-textured fabric, in
the individual datasets to the group mean contrast to sample Silg 16, which is a typical
values (Harbottle 1976). The reduction of the example of the Temple Period coarse ware with
spreads of the elemental patterns observed in the usual concentrations of group SILA (fit
all our studies considering dilutions demon- factor-----0.99). Therefore, it may be concluded
strates that it is mainly the clay part of the that samples Silg 18-20 are made from a
paste that determines the provenance. The refined clay paste compared with sample Silg
element concentrations of As, Ba, Ca and Na 16, where some non-plastic parts with low
are found to scatter strongly in pottery groups element concentrations have been taken out,
made at the same workshop (see Table 1) and giving no contribution to the measurable NAA
should be considered with care during the data obtained at Bonn. Despite this unusually
group-forming procedure (Mommsen 2004). In large range of fit or dilution factors, all
particular, As and Na are not and should not be members of the group SILA can be assumed to
included in the filtering procedure, as they are have been made from clay of the same geological
measured with small errors (see Table 4). There- formation, which was refined by different
fore, they will strongly influence the value of the 'recipes', resulting in different absolute compo-
calculated dilution factor and may result in an sitions. Their common origin is confirmed by
inappropriate factor. the dilution-corrected NAA compositional data.
Unexpectedly, also the 'Thermi Ware' sample
Silg 43, diluted by 16%, belongs to group SILA.
Results and discussion The fact that all these different wares are
Some of the results of this study were rather members of group SILA would not have been
unexpected. The evaluation of the NAA data obtainable using standard statistical cluster analy-
revealed that most sherds of the set of samples sis without corrections for possible inclusions.
from Tas-Silg have a well-defined and similar As group SILA contains vessels of different
chemical composition, forming a group here time periods (Temple Period, Bronze Age,
named SILA. Its average concentrations M and Punic Period) and of different archaeological
spreads o-(root mean square deviations) are types and shapes, the probability that this group
listed in Table 2. For many elements (Ce, Eu, represents the local workshop(s) in the region of
Fe, La, Sc, Th, Yb) spread values < 5 % are Tas-Silg is very high. Therefore, the pattern
found; nine more elements (Co, Cr, Hf, Lu, Nd, SILA can be taken as a reference pattern for a
Rb, Sin, Ta, Tb) scatter by < 10% around their pottery production centre possibly in the area of
mean values M. This result was obtained by Tas-Silg, Malta. The possibility that all these
employing the method of a best relative fit of different ware types during this long time period
the concentrations of each sample to the group were imported from the same workshop some-
mean values with the fit factors given in where overseas is extremely remote, but cannot
Table 3. Very high factors are found for the be totally excluded, especially as, on the basis
two Bronze Age samples Silg 1 and 4 (1.55 and of plate tectonics, the southern part of Sicily and
1.68, respectively), i.e. the concentrations of Malta belonged to the same Pelagian sea basin
these samples have to be increased by 55% and during the Miocene. More light will be shed on
68%, respectively, to match the mean group this issue only once reference material from the
pattern. A cross-section of one of the two Sicilian coast facing Malta has been analysed.
CHARACTERIZATION OF MALTESE POTTERY 85

Table 2. Element concentrations of groups SILA (most probably Malta),


SILB (probably Malta) and Seg2 (Segesta, Sicily)

SILA SILB Seg2


27 samples 5 samples 5 samples fit
M _+ tr (%) M + ~r (%) factor 0.93
M +_ or (%)

As 7.50 15 11.2 9.9 4.33 42


Ba 250 20 389 7. I 228 44
Ca % 10.2 23 3.49 6.0 7.33 16
Ce 89.9 2.4 112 1.0 89.8 2.1
Co 13.7 8.9 17.5 2.3 15.1 9.7
Cr 111 7.4 110 2.2 117 4.1
Cs 5.98 13 6.24 7.6 7.42 4.0
Eu 1.44 3.2 2.03 2.3 1.40 1.6
Fe % 4.34 4.6 5.11 1.7 4.65 2.2
Ga 25.6 15 27.3 10 27.1 8.8
Hf 4.59 6.7 9.45 4.5 5.07 13
K% 2.44 13 2.48 5.9 2.30 8.2
La 42.0 4.4 54.2 1.3 43.3 2.7
Lu 0.38 5.3 0.60 2.9 0.41 6.2
Na % 0.56 40 0.97 5.3 0.43 52
Nd 30.5 6.4 43.8 4.0 29.2 11
Ni 92.0 40 104 34 81.2 37
Rb 108 6.9 124 6.7 124 3.2
Sb 0.56 14 0.71 5.2 0.49 8.8
Sc 15.4 3.0 17.6 0.5 16.8 1.4
Sm 5.50 7.1 8.10 7.1 5.18 6.5
Ta 1.21 6.1 1.93 2.1 1.26 3.1
Tb 0.79 6.1 1.20 7.5 0.77 9.1
Th 11.8 2.5 15.2 1.3 12.5 2.6
Ti % 0.55 17 0.63 12 0.43 14
U 2.97 12 2.49 4.1 3.05 11
W 1.75 13 2.42 16 2.17 12
Yb 2.63 3.5 4.28 2.0 2.79 2.7
Zn 125 15 100 4.8 118 8.0
Zr 106 25 286 9.9 243 13
Average concentrationvaluesM in ~g g-~ (ppm). if not indicatedotherwise,and spreads tr in
% of M; group Seg2 correctedfor dilution with respect to SILA.

W h e n the databank of patterns in Bonn is c o m m o n wares from a H e l l e n i s t i c - R o m a n kiln


searched for groups of similar compositions, site at Segesta and, therefore, m a d e there
the closest group to SILA is a group from locally with a high probability, form this group,
Segesta, Sicily. This is m e n t i o n e d here to stress n a m e d Seg2 (Montana et al. 2003). If the
again the importance of high precision. Five values of group Seg2 are adjusted by a fit
sherds, all kiln wasters of amphorae and factor of 0.93, group SILA is very close to

Table 3. List of group members and their individual fit factors (in parentheses) to the mean group values
calculated by using all elements given in Table 2 except As, Ba, Ca and Na (see text)

Group SILA, 27 samples


Silg 1 (1.55) 3 (1.07) 4 (1.68) 5 (0.93) 6 (0.95) 7 (0.95) 8 (0.86) 9 (0.95) 11 (1.21)
12 (1.06) 13 (1.03) 14 (1.14) 15 (1.13) 16 (0.99) 18 (0.71) 19 (0.79) 20 (0.72) 21 (1.08)
22 (0.89) 23 (0.96) 24 (0.84) 25 (0.88) 37 (1.05) 38 (1.02) 39 (1.03) 40 (1.06) 43 (1.16)
Group SILB, 5 samples
Silg 31 (0.98) 32 (1.00) 33 (0.98) 34 (1.03) 35 (1.00)
Chemical singles, 10 samples
Silg 2 10 17 26 27 28 29 30 36 42
86 H. MOMMSEN ET AL.

three elements measured with high precision, Cs,


Rb and Sc, differ by slightly more than 2o'.~ve,
the two patterns can be chemically separated.
Without this high precision of the chemical pat-
terns, which is obtained here only by the correc-
tion of the unusually large dilution effects, the
groups of Tas-Silg, Malta, and Segesta, Sicily,
could not have been distinguished. The local
wasters from Segesta are obviously made using
a clay formation that can be distinguished from
the clay of group SILA only by using appropriate
evaluation procedures on the data.
A second chemical group SILB is formed by
five sherds of the type Bricky Red Cooking
Ware, dated to the Punic Period. The mean
values and spreads are also listed in Table 2.
This group has a very different chemical compo-
sition from group SILA with on average 21%
higher concentrations in nearly all elements
except for Ca, Cr, U and Zn. This may be due
to the fact that the local potters, in considering
the special requirements for cooking ware, have
produced a different paste deliberately by using
different clays or clay mixtures for the pro-
duction of these wares (see Kilikoglou et al.
1998). In this case, pattern SILB may form a
second local pattern for the site at Tas-Silg.
This assumption is strengthened by the compara-
tively large presence of this ware and by its typo-
logical similarity to the local Biscuit Ware of
group SILA (Bonanno et al. 2000). However,
as only five pieces with pattern SILB were ident-
ified, the assumption of a local production is not
very conclusive; all five vessels of this group
might have been imported from a production
site with this as yet unknown pattern. On
the other hand, several sherds of this ware type
carry inscriptions to Ashtart, which were
inscribed before firing. It is most unlikely that
this was done abroad for Maltese consumption.
No other pattern in our databank in Bonn is
close to SILB.
During a chemical classification of pottery
Fig. 1. Cross-sections of the coarse Borg in-Nadur several chemically single samples are usually
sherd (sample Silg 1, above) and of the fine-textured
sherd of the Temple Period (sample Silg 18, below). found. One cannot conclude much about these
Both are made from the clay with pattern SILA. The outliers. A chemically single sample might
concentrations of sample Silg 1 and Silg 18 have to be have been contaminated in the laboratory,
corrected by a fit factor of 1.55 and of 0.71, respectively, during burial or already in the production work-
to match pattern SILA. shop, or it might represent the first member of a
still unknown production series with a different
paste. The individual NAA data for all singles
group Seg2, as can be seen from Table 2. found in this study are listed in Table 4. In the
Figure 2 shows a graphical comparison set of non-micaceous wares from Tas-Silg five
between groups SILA and Seg2 made by plotting such singles (Silg 2, 10, 17, 36, 42) were ident-
the concentration differences for all 30 elements ified. Silg 42 is the Early Modern tile. Its compo-
in units of the average spread values o'ave as a bar sition does not help to localize any of the patterns
diagram. The only clearly differing element is Zr, found at Tas-Silg. By visual inspection Silg 17
which is difficult to measure at Bonn, but because has been noted as having a unique fabric
CHARACTERIZATION OF MALTESE POTTERY 87

SILA - Seg2 (factor 0.93)


qo

z_

O.
(R

>

O
p,
t~
W
. m

"O

-2

-4

-6

-8

elements
Fig. 2. Normalized differences (in units of average spread value) of average concentrations of the 30 elements given
in Table 2 of the pottery groups SILA (27 samples) and Seg2 (5 samples). The concentrations of group Seg2 are
multiplied by a fit factor of 0.93 to obtain an optimal agreement.

differing from that of the other Temple Period of vessels from different production sites in this
sherds. As such, it has been given the name group. As the five patterns of the amphorae are
Sandy Pink Ware because of its fine-textured unknown to us, we are not able to assign them
red clay with small red inclusions. Its well- to production workshops. More work on vessels
burnished exterior surface, however, is typical from different overseas sites is necessary to
of the Temple Period. This may point towards a locate the origin of these chemical outliers.
different production group. With regard to Silg
10, whereas Crisp Ware fabrics are known to
have a number of inclusions such as calcium Conclusion
grit or grog, Silg 10 is unusual for its matt NAA of 41 sherds excavated at Tas-Silg consist-
brown, coarse inclusions, which may account ing of nine ware types was able to show the unex-
for its unique chemical characteristics. Finally, pected result that only one characteristic clay
the whole group of Micaceous amphorae of the with a well-defined, sharp concentration pattern
Punic Period (Silg 26-30), believed to be of many elements, SILA, was used for seven of
imported to Malta, consists of chemical singles; these ware types, including the 'Thermi Ware'.
they all have different compositions. The The dating of these ware types defines the time
element analysis permits the conclusion that all range of the use of this clay as beginning with
five pieces were produced with different pastes, the Late Neolithic Temple Period (about 3000
presumably in different workshops. These Be) and lasting through the Bronze Age
amphorae seem to have been used as transport (Tarxien Cemetery and Borg in-Nadur phases,
containers, which would explain the presence 2 5 0 0 - 7 0 0 BC) until the Punic Period (550-218
T a b l e 4. Unchanged (fit factor = 1) element concentrations C in tzg g - l (ppm), if not indicated otherwise, and average errors, also in % of C,
for the nine ungrouped samples (chemical singles)
Sample Fit factor As Ba Ca % Ce Co Cr Cs Eu Fe % Ga

Silg 2 1.0 10.6 271 3.53 77.1 12. I 122 6.19 1.23 4.88 27.2
Silg 10 1.0 14.4 345 6.77 97.8 11.2 10l 5.62 1.77 4.02 21.7
Silg 17 1.0 29.7 116 21.9 53.6 9.44 90.8 3.03 1.19 4.22 13.4
Silg 26 1.0 39.7 400 3.96 97.0 24.4 300 8.69 1.47 4.81 23.7
Silg 27 1.0 19.2 217 8.48 29.1 36.4 685 3.59 0.79 5.34 18.9
Silg 28 1.0 15.1 666 1.93 109 23.1 148 8.19 1.60 5.66 36.7
Silg 29 1.0 8.89 286 12.9 80.4 I 1.4 59.0 7.80 1.19 3.22 24.9
Silg 30 1.0 25.6 377 3.94 82.5 29.2 283 8.76 1.40 5.70 30.4
Silg 36 1.0 8.15 310 8.07 93.8 15.2 103 5.61 1.67 4.37 23.4
Silg 42 1.0 7.34 632 4.91 82.6 17.8 57.0 5.43 1.26 3.45 26.6
Av. meas. error 0.12 30 0.19 0.80 0,12 1.2 0.087 0.026 0.017 2.4
in % 0.7 8.3 2.5 1.0 0.6 0.6 1.4 1.9 0.4 9.9
Sample Fit factor Hf K % La Lu Na % Nd Ni Rb Sb Sc
Silg 2 1.0 4.58 3.01 34.8 0.36 0.65 27.4 128 I 18 0.83 16.3
Silg 10 1.0 8.48 2.41 44.2 0.46 0.62 37. I 47.7 I 15 (I.52 14.4
Silg 17 1.0 2.10 1.03 22.9 0.25 0.23 19.0 54,7 54.0 1.49 8.74
Silg 26 1.0 9.02 2.22 38.9 0.56 0.72 30.0 125 120 1.21 20.5
Silg 27 1.0 2.26 0.86 17.2 0.36 I. 14 14.3 544 36.6 0.40 22.2
Silg 28 1.0 6.83 3.03 40.4 0.60 1.23 32.6 43.9 159 1.31 21.4
Silg 29 1.0 5.14 2.16 39. I 0.38 0.40 24.9 I(X) I 14 I. 15 I 1.8
Silg 30 1.0 4.82 3.18 38.7 0.46 0.31 31.2 312 179 3.05 18.6
Silg 36 1.0 5.69 2.01 46. I 0.47 0.48 34.8 142 103 0.74 15.3
Silg 42 1.0 4.52 3.18 40.7 0.37 2.19 32.5 37.4 141 0.48 12.5
Av. meas. error 0.065 0.032 0.15 0.016 0.005 1.5 34 2.4 0.020 0.022
in % 1.2 1.4 0.4 3.8 0.6 5.4 23 2.1 1.8 0. I
Sample Fit factor Sm Ta Tb Th Ti % U W Yb Zn Zr
Silg 2 •0 5.40 1.31 0.76 11.7 0.45 2.52 1.67 2.57 154 1(15
Silg 10 .0 6.96 I. 19 1.10 12.8 0.49 3.39 1.48 3.29 98.2 239
Silg 17 •0 3.90 0.59 0.72 7.38 0.54 2.69 1.05 1.79 1() I 34.2
Silg 26 •0 5.69 1.34 0.96 15.2 0.53 2.81 2.63 3.72 80.3 265
Silg 27 •0 2.67 0.30 0.43 5. I 0 0.30 1.09 1.12 1.83 82. I 83.3
Silg 28 •0 6.33 1.01 1.05 17.2 0.68 2.76 2.16 3.79 112 144
Silg 29 1.0 4.62 0.97 0.77 13.3 0.59 2.68 2.12 2.70 86.4 10 I
Silg 30 1.0 5.71 1.20 0.90 17.1 0.56 4.83 4.08 3.04 108 90.7
Silg 36 1.0 6.60 1.32 1.01 12.3 0.48 2.74 1.69 3.28 111 122
Silg 42 1.0 5.88 1.03 0.71 13.5 0.59 2.66 2.13 2.54 130 182
Av. meas. error 0.018 0.032 0.049 0.068 0.073 0.093 0.16 0.053 2.4 27
in % 0.3 3. I 5.9 0.5 14 3.3 7.9 1.8 2.2 20
CHARACTERIZATION OF MALTESE POTTERY 89

BC). This large time span together with the pre- BUXEDAI GARRIGOS,J. 1999. Alteration and contami-
sence of different ware types in the group nation of archaeological ceramics: the perturbation
argues for a local production of all these problem. Journal of Archaeological Science, 26,
pottery vessels, although, because of the lack of 295- 313.
reference material, no definite proof is obtained. DIGERONIMO, I., GRASSO, M. & PEDLEY,H. M. 1981.
Palaeoenvironment and palaeogeography of
A second paste with pattern SILB was in use
Miocene marls from southeast Sicily and the
during the Punic Period for the Bricky Red Maltese Islands. Palaeogeography, Palaeoclima-
cooking ware and was probably also locally pro- tology, Palaeoecology, 34, 173-189.
duced. In contrast, the group of five Micaceous HARBOTTLE, G. 1976. Activation analysis in archaeol-
amphorae found in Tas-Silg all have different ogy. In: NEWTON,G. W. A. (ed.) Radiochemistry 3.
chemical patterns and are most probably Chemical Society, London, 33-72.
imports from five different workshops outside HEIN,A.,TSOLAKIDOU,A., ]LIOPOULOS,L MOMMSEN,H.,
Malta. BUXEDA ! GARRIGOS, J., MONTANA, G. &
KILIKOGLOU, V. 2002. Standardisation of elemen-
tal analytical techniques applied to provenance
We would like to thank the staff of the research reactor at
studies of archaeological ceramics--an interla-
Geesthacht, Germany, for the neutron irradiations, and
boratory calibration study. Analyst, 127, 542-553.
Y. Taniguchi (formerly of the Malta Centre for Restor-
ation) and M. H. Pedley (University of Hull, UK) for JONES, R. E. 1986. Greek and Cypriot Pottery. British
their advice and comments. School at Athens, Fitch Occasional Papers, 1.
KILIKOGLOU, V., VEKINIS, G., MANIATIS, Y. t~z DAY,
P. M. 1998. Mechanical performance of quartz-
References tempered ceramics: Part I, Strength and toughness.
Archaeometry, 40, 261-280.
AKURGAL, M., KERSCHNER, M., MOMMSEN, H. &
MOMMSEN, H. 2001. Provenance determination of
NIEMEIER, W.-D. 2002. TSpferzentren der
pottery by trace element analysis: problems, sol-
Ostdgdis, Archdometrische und archiiologische
utions and applications. Journal of Radioanalytical
Untersuchungen zur mykenischen, geometrischen
and Nuclear Chemistry, 247, 657-662.
und archaischen Keramik aus Fundorten in Westk-
Ieinasien (mit einem Beitrag yon S. Ladstdtter). MOMMSEN, H. 2004. Short note: provenancing of
3. Erg~inzungsheft der Jahreshefte des Osterrei- pottery--the need for an integrated approach?
chischen Archiiologischen Institutes, Wien Archaeometry, 46, 267-271.
BEIER, TH. & MOMMSEN, H. 1994a. Modified MOMMSEN, H., KREUSER, A., LEWANDOWSKI, E. &
Mahalanobis Filters for grouping pottery by chemi- WEBER, J. 1991. Provenancing of pottery: Status
cal composition. Archaeometry, 36, 287-306. report and grouping. In: HUGHES,M. COWELL, M.
BEIER, TH. & MOMMSEN, H. 1994b. A method for & HOOK, D. (eds) Neutron Activation and
classifying multidimensional data with respect Plasma Emission Spectrometric Analysis in
to uncertainties of measurement and its applica- Archaeology. British Museum Occasional Papers,
tion to archaeometry. Naturwissenschaften 91, 82, 57-65.
546-548. MONTANA, G., MOMMSEN, H., ILIOPOULOS, I.,
BONANNO, A., FRENDO, A. J. t~z VELLA, N. C. (eds) SCHWEDT, A. ~z DENARO,M. 2003. Petrography and
2000. Excavations at Tas-Silg, Malta: a prelimi- chemistry of thin-walled ware from a Hellenistic-
nary report on the 1996-1998 campaigns con- Roman site at Segesta (Sicily). Archaeometry, 45,
ducted by the Department of Classics and 375-389.
Archaeology of the University of Malta. Mediter- PERLMAN, I. t~ ASARO, F. 1969. Pottery analysis by
ranean Archaeology, 13, 67-114 neutron activation. Archaeometry, 11, 21-52.
Cobalt blue painted pottery from 18th Dynasty Egypt
A. J. S H O R T L A N D l, C. A. H O P E 2 & M. S. TITE 3
1Centre for Archaeological and Forensic Analysis, Department of Materials and Medical
Sciences, Cranfield University, Shrivenham, Swindon SN6 8LA, UK
2Centre for Archaeology and Ancient History, Building 11, Clayton Campus, Monash
University, Clayton, Vic. 3800, Australia
3Research Laboratory for Archaeology and the History of Art, 6 Keble Road, Oxford OX1 3QJ,
UK (e-mail: Michael. tite @rlaha.ox.ac, uk)

Abstract: Cobalt blue painted pottery was produced in New Kingdom Egypt, with the
heyday for its production being from about 1400 BC tO 1200 BC. Previous scientific exam-
ination has established that the cobalt blue pigment was a CoAl-spinel, which it was
suggested was produced from cobaltiferous alums from the Western Desert of Egypt. In
the present paper, quantitative analyses of a range of cobalt blue painted pottery have
confirmed the Western Desert as the source of the cobalt blue pigment but suggested that
the cobaltiferous alums used for the pottery differed in composition from those used in
the production of contemporary cobalt blue glass. The pottery bodies were produced
using either non-calcareous Nile silt or calcareous clay. Before being painted, the Nile
silt bodies were first coated with pale firing calcareous clay slip to which gypsum had prob-
ably been added.

Throughout the course of the dynastic period common from the third millennium BC
(c. 3000-332 Bc) ancient Egyptian pottery was onwards. Part of the reason for the rarity of
predominantly undecorated. Intermittently dec- blue painted pottery is undoubtedly technical.
oration did occur (Arnold 1993, pp. 9 5 - 1 0 0 ; Glazes and glasses are usually coloured blue by
Aston 1998, pp. 5 3 - 5 7 ) but not in significant the deliberate addition of copper, but compounds
quantities. An exception to this occurred of this element are very difficult to apply as a
during the New Kingdom, 18th-20th Dynasties paint to a ceramic in such a way that the resultant
(1550-1087 BC), when a wide range of forms ceramic will be robust enough for regular use.
received decoration prior to firing in which the Very rarely, the man-made pigment Egyptian
dominant colour was a pale blue, supplemented blue was applied to ceramics in Egypt, but this
by red and reddish-brown to black. The ware is flakes off readily. Instead of copper, the colorant
now commonly termed blue painted pottery, used on the great majority of Egyptian blue
the most detailed study of which remains the painted pottery is cobalt. The technology for
unpublished PhD thesis of Hope (1980). using cobalt colorants in glass, glaze and cer-
However, quantification of its frequency within amics was apparently discovered in the reign of
an assemblage studied at one site (Malkata in the Egyptian king Tuthmosis III (1479-1425
Thebes) showed that it accounted for less than BC), when it is used first in dark blue glasses
4% (Hope 1989a, p. 12). Despite this, because (Lilyquist & Brill 1993). It becomes fairly
of its limited period of occurrence and the evol- common during the reigns of his son, Amenhotep
ution of design features, it can be used as a con- II (1427-1400 BC), and grandson, Tuthmosis IV
venient dating tool. In addition, it provides an (1400-1390 Be). However, it is during the reigns
indicator of Egyptian taste in decorative arts of his successors Amenophis III and Akhenaten
during the New Kingdom, can show the probable (1390-1336 BC) that cobalt blue in glass, glaze
existence of specialist workshops or potters and ceramics is most abundant (Kozloff &
responsible for its manufacture, and is a tool Bryan 1992). In this period, especially at the
for use in gauging those potters' technological palace site of Malkata and city of Amarna
achievements. (Fig. l), it is a frequent part of the glass and
In contrast to blue painted pottery, faience ceramic assemblage; indeed, walking now over
glazes and glasses in brilliant blues are either site, it is only a matter of minutes before

From: MAGGETTI,M. & MESSIGA,B. (eds) 2006. Geomaterialsin CulturalHeritage.


Geological Society, London, Special Publications, 257, 91-99.
0305-8719/06/$15.00 © The Geological Society of London 2006.
92 A.J. SHORTLAND ET A L

suggested that the first step in the production of


the pigment was to convert the sulphates to
hydroxides by the precipitation from an
aqueous solution of the cobaltiferous alum
through the addition of an alkali such as the
natron, a complex evaporite consisting mostly
of sodium carbonate. He thus suggested that the
CoAl-spinel was not a natural mineral but was
formed by firing the hydroxide mixture in the
range 800-1000 °C.
Warachim et al. (1985) investigated the
co-precipitation of cobalt, aluminium and
magnesium hydroxides, and their use in the
subsequent production of cobalt spinels. Using
highly alkaline ammonia, they achieved com-
plete precipitation of all three hydroxides.
T o/ However, Rehren (2001) suggested that, with
the less strongly alkaline natron, differential
precipitation would occur, with aluminium and
transition element hydroxides precipitating
Fig. 1. Map of Egypt showing location of places before magnesium hydroxide. Subsequently, in
mentioned in text. laboratory experiments using sodium carbonate
as the alkali, Shortland et al. (2006) confirmed
that aluminium hydroxide precipitated first,
several sherds of blue painted pottery or cobalt followed by cobalt and manganese hydroxides,
blue glass or faience can be collected. The last and then magnesium hydroxide. Warachim
examples of cobalt colorants both in glazes and et al. (1985) also established that the blue
glasses and in blue-painted pottery appear to be (Mg,Co)Al-spinel was formed by heating the
dated to the 20th Dynasty (1186-1069 BC), hydroxide mixture in the range 900-1200 °C.
after which it ceases to be used (Arnold & However, when fired below about 900°C,
Bourriau 1993). The fact that it appears to cease various cobalt oxides (COO, Co203, Co304)
to be used simultaneously in all forms might and MgCo-spinel were instead formed, resulting
suggest that perhaps there was a problem in the in a dark grey to black pigment.
supply of the cobaltiferous alum, which, as dis- The aim of the research reported in the present
cussed below, was used to make the colorant. paper has been to obtain quantitative data on the
Previous scientific investigations of cobalt blue compositions of the cobalt blue pigment layer
painted pottery (Riederer 1974; Noll & Hangst and the underlying slip for a range of cobalt
1975; Bachmann et aI. 1980; Noll 1981) blue painted pottery from New Kingdom
established that the cobalt blue pigment was in Egypt, and so to extend our understanding of
the form of a CoAl-spinel containing significant production and application of the pigment.
amounts of zinc and nickel, and that the
pigment was applied over a thin slip containing
gypsum. On the basis of scanning electron photo- Archaeological context
micrographs, Noll (1981) showed that the There are two main categories of Egyptian blue
pigment was a loose aggregate of roundish par- painted pottery, the heyday for the production
ticles with diameters typically less that about of which was during the reign of Amenhotep
0.5 ~m. III (1390-1352 Be) in the 18th Dynasty until
Bachmann et al. (1980) first suggested that that of Ramesses II (1279-1213 Be) in the
the cobaltiferous alums from the Kharga and 19th Dynasty. In one the forms and decoration
Dakhla Oases of the Western Desert in Egypt differ from the classic blue painted pottery and
were the possible source of the cobalt pigment. the blue is not dominant (Hope 1987). Examples
Kaczmarczyk (1986) subsequently presented come from Thebes (modern Luxor) but are
analyses of alums collected from the Dakhla mostly without provenance. The decoration has
Oasis, which established them as being mag- several features in common with examples
nesium aluminium sulphates with trace of pottery decorated in bi-chrome red and
amounts of cobalt, zinc, nickel, manganese and brown/black from the same period; this latter
iron, and thus echoing the trace elements type, along with monochrome decoration in red
present in the cobalt blue pigment. Noll (1981) or brown/black, has its antecedents in the
COBALT BLUE PAINTED POTTERY 93

earlier 18th Dynasty and late Second Intermedi- and there was a growing tendency to use bands
ate Period. The other category is characterized of blue without elaboration (Hope 1989b,
by the dominant use of blue, with examples p. 56-57; Aston 1998, p. 57).
from Giza possibly indicating that the style was As previously indicated, Memphis may have
an innovation of the potters of the capital at led the way in the development of blue painted
Memphis (now under modern Cairo; Hope pottery, and of the little well-provenanced and
1997). The greatest quantity was produced dated material that survives for the period prior
during the 18th Dynasty, with some reduction to Amenhotep III, Thebes is another early find
during the early 19th Dynasty; following spot. Thereafter, during the 18th Dynasty the
Ramesses II there was significant reduction largest deposits occur at Thebes (Malkata,
until manufacture ceased during the reign of Karnak), Amarna and in the Memphite region
Ramesses IV in the 20th Dynasty (Aston 1998, to the Fayum (Hope 1989a, 1991). For the 19th
p. 56; Hope 1989b, p. 56). Dynasty, Qantir, Memphis and its environs, the
It may be noted that contemporary with its Fayum and Thebes (Deir el-Medineh) have
manufacture was a post-firing decorative tech- yielded the most substantial quantities, but poss-
nique most commonly found upon amphorae, ibly less than earlier; the latest well-dated
which employed a wider colour palette that material of the 20th Dynasty derives from
included the copper-based Egyptian blue rather Thebes (Valley of the Kings). It can be seen
than cobalt blue pigment (Bell 1987; Hope clearly that, if find spot and quantity indicate
1989c, 1991). This may be termed polychrome place of manufacture, the production centres
or post-firing decorated pottery and it appears to coincided with the major administrative or
have been manufactured from a slightly earlier royal residence sites, whence distribution on a
date within the reign of Thutmose III (1479- smaller scale to a greater number of locations
1427 Bc; Hope 1987). It occurs at some settlement occurred. Blue painted pottery has been found
sites (Malkata, Amarna) but mostly in cemeteries throughout the Nile Valley in Egypt, and some
(Deir el-Medineh (near Malkata) and Gurob). also in Nubia to at least the Third Cataract, in
The decoration upon blue painted pottery the Eastern Desert, the Oases of Dakhla and
during each of the two major phases of its pro- Kharga in the Western Desert, and in the Levant,
duction, the late 18th Dynasty (1390-1295 Bc) where the quantity is greater in the 19th Dynasty,
and the early 19th Dynasty (1295-1213 Bc), with the most northerly find at Tell Nebi Mend
shows a remarkable homogeneity of layout and (ancient Kadesh-on-the-Orontes).
composition irrespective of provenance. In the The largest quantity of blue painted pottery
former, motifs are laid out within panels that was used within a domestic context by the
emphasize the characteristics of the vessel elite, and some appears to have had a distinctly
profile and are dominated by floral elements ornamental value. It was also included within
(Hope 1989a, 1991). The compositions range their burials on a smaller scale; such contexts
from those with simple repeat motifs to extre- have produced a more limited range of forms
mely elaborate ones with numerous elements than the former but they include types rarely, if
and complex structures. The floral elements, pre- at all, found within houses or palaces, sometimes
dominantly based upon the blue lotus flower but in sets. This indicates specialist production of
with numerous other sources of inspiration, are mortuary wares; the most distinctive examples
supplemented with faunal, human, divine, hiero- derive from the tomb complexes of Horemheb
glyphic and abstract motifs. Most commonly the and Maya at Saqqara (near Memphis; J. D.
decoration is over a pale background coating, Bourriau, pers. comm.). The products of the
either cream or pinkish-orange; rarely is it on a reigns of Amenhotep III and his son Akhenaten
red ground or directly upon the uncoated from Thebes (Malkata and Karnak) and
surface, except when the vessel is made from Amarna are remarkably similar, prompting the
marl (calcium-rich) clay. This light coating suggestion that the same potters might have
upon vessels made in Nile alluvial silt clay, been responsible for their manufacture. Contem-
which was most regularly utilized, provides a porary and slightly later material from Memphis
suitable contrast to the blue pigment and high- shows significant differences in detail whereas
lights the design. In terms of techniques, painting the general aspect is very similar. Access to
is the most common, but modelling from the limited quantities was gained by those of lesser
vessel wall, application of finger-modelled or rank for whom it may have been a desirable
mould-made elements, incision, impression and product, a status marker. The quality of blue
fenestration also occur. This range of techniques painted pottery varies, and although that from
continued into the next phase as did the variety elite contexts is often of a higher standard of
of motifs, but the designs became less complex execution, this is not always the case. In addition
94 A.J. SHORTLAND ETAL.

to finds from domestic and funerary contexts are Details of the shape, fabric and decoration of
those from temples. These are far fewer, but the the associated vessels are given in the Appendix.
material discovered at the temples of Karnak Polished cross-sections through the cobalt blue
proves the use of blue painted pottery within pigment layer, slip and body were prepared and
ritual contexts, something confirmed by rep- examined in a scanning electron microscope
resentations in temple reliefs. The manufacture (SEM; JEOL JSM-840A) at the Department of
of this material is characteristic of the taste for Earth Sciences, University of Oxford. The
the luxurious and elaborate that is a feature of a pigment layers were analysed using wavelength-
more wealthy, New Kingdom society. dispersive spectrometry (WDS) associated with
a JEOL 8800 SEM at the Department of
Materials, University of Oxford, which had
Experimental procedures been calibrated using appropriate primary stan-
Eight sherds of blue painted pottery were dards. This machine was run at 15 kV and
selected for analysis; four from Malkata and 10 nA, with a spot size of 5 Ixm and 20 s count
four from Amarna. All the samples were time per element, giving a detection limit of
surface finds, those from Malkata dating to the around 0.05 wt% and a relative error on analyses
later part of the reign of Amenhotep III, and of minor elements of the order of 5%. Analyses
those from Amarna to between post the fifth were made on between three and five points on
year of the reign of Akhenaten and the early each pigment layer and the results averaged. In
years of the reign of Tutankhamun. The majority the case of PAL 4, the pigment layer was too
of the sherds are from necked jars of various weathered to obtain valid analyses. As a result
sizes (Fig. 2) with the decoration occurring on of porosity, the analytical totals were typically
the exterior. All showed blue paint with in the range of 6 0 - 7 0 wt%, and therefore, for
varying degrees of preservation from quite ease of comparison, the analytical data were nor-
fresh to rather eroded, plus the presence in malized to 100% totals. The body and slip compo-
places of black, red and white paints or slips. sitions were determined by energy-dispersive
spectrometry (EDS) associated with the JEOL
JSM-840A SEM using Oxford Instruments Isis
300 software in conjunction with appropriate
primary standards. This second machine was
run at 20 kV and 6 nA, giving a detection limit
for most elements heavier than silicon of around
0.05-0.10 wt%, and 0.10-0.30 wt% for lighter
elements. Typically the error on analyses of
major elements is of the order of 1.0 wt%. The
areas analysed were associated with magnifi-
cations of x 100 for the bodies, and with x2000-
x4000 for the slips. Again, as a result of low
analytical totals resulting from porosity, the
analytical data were normalized to 100% totals.
Small samples that, because of the thinness of
the layers, tended to contain both pigment and
slip were taken from selected sherds, and the
mineral phases present were identified by X-ray
diffraction (XRD). This was carried out at the
Department of Materials, University of Oxford,
using a fully automated Siemens D500 powder
diffractometer employing CuK~ radiation (wave-
length 0.15406 nm) and a secondary monochro-
mator. The samples were continuously spun
during data collection and scanned using a step
size of 0.05 ° 20 in the range of 5 - 7 5 ° 20 and a
count time of 8 s per step.

Results and discussion


Fig. 2. Large water container in blue painted ware,
currently in the Agyptisches Museum, Berlin. Vessel is Examination of the cross-sections through the
about 70 cm in height. cobalt painted pottery in the SEM indicated
COBALT BLUE PAINTED POTTERY 95

~ p ~ z ~ ~ ~ -

..... ~ . . ~ % ~ . ~

Fig. 3. Scanningelectron photomicrograph of a cross-


section through a typical vessel, showing pigment layer
(1), slip (2) and body (3). Phases present in the body
include quartz (Q), biotite (B), potassium feldspar (P)
i
and iron oxides (bright backscatter contrast). The
apparent backscatter contrast observed in the pigment
layer reflects surface irregularities, which are the result ddddddd~ddddodd
of difficulties in polishing this soft, friable layer, rather
than being due to the presence of different phases. Scale
bar represents 50 ~m. iddddd2~dd~d~MN

E
ddddddddddd~d£
that, except for the Malkata sherds, PAL 4 and
PAL 5, the pigment layer overlies a slip layer
(Fig. 3). The pigment layer can be as much as d2dd2~22~M2~d~
30 p~m in thickness but, as a result of weathering
and abrasion during burial, the surviving pigment <
layer is frequently as little as 10 txm thick.
Compared with the bodies, which are coarse
textured with abundant quartz, potassium feld-
spar and biotite inclusions, some of which are ..=
e..

up to 50 Ixm across, the slip layers, which are


some 8 0 - 1 0 0 p~m in thickness, are much finer
textured. On the basis of the interconnecting vitr- . . . . . . . . . . . . . . .

eous phase linking the inclusions in the slip layer


and body, a firing temperature in the range of ~"
about 9 0 0 - 9 5 0 °C can be inferred (Maniatis &
Tite 1981). .~
The compositions of the cobalt blue pigment .~
layers are characterized by high aluminium, ~
magnesium, nickel, zinc, iron and manganese "~
contents (Table 1). This result is as previously
observed (Bachmann et al. 1980; Noll 1981), ~
ce
and, therefore, again consistent with the use of
the cobaltiferous alums from the Dakhla and
Kharga Oases (Kaczmarczyk 1986; Shortland ~.
et al. 2006). The bulk of the silica, lime, soda ~,
and potash contents of the pigment layers is
most probably the result of interaction with and
contamination from the underlying slips or, .~ 2~
when no slip layer is present, the underlying ~.
bodies. In addition, because the iron oxide '~
b~
contents of the slips or bodies were higher than
©<
those of the pigment layers, it is possible that a [- . -4--
96 A.J. SHORTLAND ETAL.

proportion of the iron oxide in the pigment layers and the glass plus flits, the magnesium, manga-
was similarly the result of interaction with and nese, iron, nickel and aluminium to cobalt
contamination from the underlying slips or bodies. ratios for the pottery from Malkata tend to be
The XRD analyses confirmed that Al-spinels, lower than those for the pottery from Amarna.
such as the CoAl-spinel previously identified Lower magnesium to cobalt ratios in the
by Noll (1981), were present in the pigment pigment layers might be expected in comparison
layers. Because the XRD spectra for Al-spinels with the glass, as there will be a contribution to
tend to be very similar and because only very the total magnesium content of the glass from
small samples were available for analysis, it the plant ash, which it has been suggested was
was not possible to identify specific spinels added to a frit plus quartz mixture in its pro-
with any certainty. However, on the basis of duction (Tite & Shortland 2003). However, this
the bulk compositions of the pigment layers, it is not the case for the frit itself, where natron is
is possible that Al-spinels incorporating cobalt, the probable source of the alkali (Tite &
zinc, magnesium, iron and nickel were present. Shortland 2003). Because, on the basis of labora-
In addition, the calcium sulphates gypsum and tory experiments, it has been shown that mag-
anhydrite were identified in the slip layer that nesium is the last hydroxide to precipitate
was sampled together with the pigment layer, (Shortland et al. 2006), the lower magnesium
again both these phases not always being present. to cobalt ratios in the pigment could be the
Comparison of the compositions of the pig- result of the precipitation reaction not being
ments with those of contemporary cobalt blue taken to 100% completion. However, in view
glass and of the coarse-textured cobalt blue of the fact that the manganese, iron and zinc to
frits found at Amarna in association with the cobalt ratios for the pigments also differ from
shallow 'fritting pans', first described by Petrie those for the glass and flits, it seems probable
(1894) and further studied by Tite & Shortland that the compositions of the alums used to
(2003), reveals both similarities and differences. produce the pigments differed from those used
Thus, the aluminium and nickel to cobalt ratios in the production of the glasses and frits.
for the pigments are comparable with those for The compositions of the body clays fall into
both the glass and the frits. However, the mag- two groups (Table 2). The first group, consisting
nesium, manganese and iron to cobalt ratios for of two Malkata bodies (PAL 1 and PAL 2) and all
the pigments are all lower than those for both the Amarna bodies, were made using non-
the glass and the flits, whereas the zinc to calcareous clays that are similar in composition
cobalt ratios are higher. Furthermore, in the to Nile silt which, other than changes as a result
case of iron, because of a possible contribution of pre-treatment, tends to be uniform in com-
to the pigment layer from the underlying slip or position throughout the Nile Valley (Bourriau
body, its ratio to cobalt in the original pigment et al. 2000, pp. 133-135). Thus, the compo-
could have been even lower. In addition to sitions of this first group are similar to those of
these differences between the pigment layers the two previously analysed Nile silt samples

Table 2. Body compositions (oxides in wt%)

Sherd no. Site SiO2 A1203 CaO MgO Na20 K20 FeO TiO2 MnO SO3

Non-calcareous clays--NC
PAL 1 Malkata 58.4 16.4 4.4 3.3 3.1 2.8 8.8 1.8 0.2 0.8
PAL 2 Malkata 60.2 16.2 3.8 3.4 3.3 2.3 8.6 1.4 0.1 0.6
PAL 6 Amarna 65.1 13.3 4.2 3.0 2.6 2.8 7.2 1.3 0.1 0.4
PAL 7 Amarna 61.9 15.9 3.7 2.7 2.2 2.8 8.9 1.4 0.2 0.4
PAL 8 Amarna 62.6 15.8 3.7 3.3 2.4 1.8 8.4 1.5 0.2 0.3
PAL 9 Amarna 62.7 14.7 4.6 2.8 3.1 2.2 7.7 1.6 0.1 0.6
Average--NC 61.8 15.4 4.1 3.1 2.8 2.5 8.2 1.5 0.1 0.5
PN 6A* Nile silt 59.7 14.2 5.2 3.4 1.6 1.2 12.0 2.8
PN 13A* Nile silt 62.8 15.8 3.3 3.1 1.1 1.0 11.2 1.7
Calcareous clays--C
PAL 4 Malkata 57.9 1 4 . 2 10.5 3.9 3.3 1.8 6.8 1.2 0.1 0.5
PAL 5 Malkata 50.8 1 1 . 8 17.8 5.2 2.5 1.6 8.1 1.9 0.1 0.3
Average--C 54.3 1 3 . 0 14.1 4.5 2.9 1.7 7.5 1.5 0.1 0.4
*Analyses taken from Shortland (2000).
COBALT BLUE PAINTED POTTERY 97

from Amarna (PN6A and PN13A) (Shortland two bodies (PAL 4 and PAL 5) on which no
2000), the principal differences being the slips were detected were made using calcareous
high,Jr iron oxide and lower soda contents of clays (10-18% CaO), and therefore are them-
the Nile silt samples. The second group, consist- selves buff firing.
ing of the remaining two Malkata bodies (PAL 4 The origin of the calcium sulphates in the
and PAL 5), were made using calcareous clays slips is not entirely clear. It is possible that, as
containing 10-18% CaO (i.e. marls). suggested by Bachmann et al. (1980), the
The slip layers have the composition of calcar- calcium sulphates are the result of contamination
eous clays containing variable amounts of during burial and are, therefore, secondary.
sulphur (Table 3). On the basis of the XRD ana- However, if this was the explanation, one would
lyses, the sulphur is most probably associated expect to observe similar SO3 levels in the
with calcium sulphates (i.e. gypsum and anhy- pigment layers and the bodies whereas, compared
drite). However, the amounts of calcium sulphate with the 2 - 2 4 % SO3 contents in the slips, EDS
are not sufficient to account for all the lime analyses of the pigment layers indicate SO3 con-
present in the clays, and after subtraction of the tents in the range 2 - 3 % , and the SO3 contents of
calcium sulphate and renormalization to 100% the bodies are less than 1% (Table 2). Therefore,
totals, the slip clays, with the exception of PAL 2, it seems probably that at least a significant pro-
are still calcareous. Compared with the calcareous portion of the calcium sulphate in the slips was
clays used for two Malkata bodies (PAL 4 and added as gypsum, perhaps to make the slip layer
PAL 5), the silica contents of the slip clays are even paler. Firing the pottery would have resulted
lower, but the alumina, lime and magnesia con- in dehydration of the gypsum but the resulting
tents are higher. This difference is consistent anhydrite will survive as its decomposition
with the fact that the slip clays are much finer tex- requires temperatures in excess of 1100 °C even
tured with no large non-plastic inclusions (Fig. 3). in the presence of clay and silica (Searle &
In the case of the calcareous slip clays, the iron Grimshaw 1959). The gypsum observed in
oxide will be incorporated into silicate phases, some pigment layers could then be the result of
and therefore will fire to a pale buff colour, rehydration during burial.
rather than the red colour of the non-calcareous
Nile silt. These slips will therefore provide the
pale background wash appropriate for the Conclusions
cobalt blue painted decoration. The PAL 2 slip The new quantitative analyses of the cobalt blue
with the lowest lime content (5% CaO as com- painted pottery have confirmed that the cobalt
pared with 17-22% CaO) also has the lowest pigment was almost certainly produced using
iron oxide content (2% FeO as compared with cobaltiferous alums from the Dakhla and
6 - 1 0 % FeO), and therefore will again be paler Kharga Oases in the Western Desert of Egypt.
than the underlying Nile silt body. Finally, the However, it appears that the alums used for the

Table 3. Slip compositions (oxides in wt%)


Sherd no. Site SiO2 A1203 CaO MgO Na20 K20 FeO TiO2 CoO MnO SO3
As measured
PAL 1 Malkata 41.3 13.8 23.0 4.9 2.3 0.9 9.7 1.9 0.1 0.3 1.9
PAL 2 Malkata 48.1 12.1 11.2 5.3 9.0 1.4 1.9 1.2 0.1 0.1 9.8
PAL 6 Amarna 43.3 16.4 23.1 5.0 2.4 0.4 5.9 0.7 0.1 0.4 2.3
PAL 8 Amarna 29.0 13.2 24.2 4.3 4.3 1.5 5.2 0.7 0.6 0.3 16.6
PAL 9 Amarna 23.3 12.2 27.8 4.7 2.4 1.2 3.6 0.4 0.1 0.3 24.1
Average 37.0 13.5 21.8 4.8 4.1 1.1 5.3 1.0 0.2 0.3 10.9
After subtraction of 'calcium sulphate'
PAL 1 Malkata 42.6 14.3 22.4 5.1 2.4 0.9 10.0 2.0 0.1 0.3
PAL 2 Malkata 57.7 14.4 5.2 6.3 10.8 1.7 2.3 1.4 0.1 0.1
PAL 6 Amarna 45.1 17.1 22.3 5.2 2.5 0.4 6.1 0.7 0.1 0.5
PAL 8 Amarna 40.4 18.4 17.5 6.0 6.0 2.0 7.3 0.9 0.9 0.4
PAL 9 Amarna 39.4 20.7 18.4 8.0 4.1 2.0 6.2 0.6 0.1 0.4
Average 45.1 17.0 17.2 6.1 5.1 1.4 6.4 1.1 0.3 0.4
Body--C* Average 54.3 13.0 14.1 4.5 2.9 1.7 7.5 1.5 0.1 0.4
*Analytical data for calcareous clay body taken from Table 2.
98 A.J. SHORTLAND ET AL.

pigments were somewhat different in compo- Fabric: marl A4; the thin cream surface on the
sition from those used in the production of exterior resembles a distinct coating.
cobalt blue frits and glasses. This may be due Decoration: blue overlapping petals outlined
to a different alum source being used for different with thick black lines--gap--blue band with
materials, or may instead suggest a sorting of an upper black line.
alum from one source into grades, each, in the
mind of the worker, more suitable for one use
than another. There were also differences in com- P A L 5: Malkata
position between the alums used at Malkata and Shape: shallow bowl with very short convex
Amarna, but these latter differences are signifi- sides, compare Hope (1989a, fig. 5f); rim
cantly less than those between the cobalt blue fragment.
paint and the glass and frit, and when the differ- Fabric: marl A4.
ent states of preservation of the pigment layers Decoration: blue inside and outside.
are taken into account, may not be significant.
Both non-calcareous Nile silt and calcareous
clay (i.e. marl) were used in the production of P A L 6: Amarna
the pottery bodies, the former being used for all Shape: a medium-sized jar, type unknown; frag-
the analysed pottery samples from Amama ment from the upper body.
whereas both clays were used for the analysed Fabric: Nile silt B2 with whitish-cream surface
samples from Malkata. Prior to painting, the coating outside.
Nile silt bodies were first coated with a calcar- Decoration: part of a frieze of blue petals taper-
eous clay slip to which gypsum had probably ing downwards, outlined in brown, the upper
been added. In contrast, no slip was applied to part over a blue band outlined in brown.
the calcareous clay bodies, the pigment being
painted directly onto the body.
P A L 7: Amarna
Shape: a medium-tall- to tall-necked jar with
Appendix: Description of pottery samples ovoid body, compare Hope (1991, fig. 6e).
The designations of pottery shape and fabric Fabric: Nile silt B2, with a pinkish-orange
employed here are those of the so-called surface coating outside.
Vienna System, which has been discussed by Decoration: gap---two bands of blue outlined in
Nordstrrm & Bourriau (1993) and Bourriau reddish brown, the upper with a red line,
et al. (2000, pp. 130-132). over which is a frieze of blue petals tapering
downwards outlined in reddish-brown, with
thin red strokes (stamens) between the lower
P A L 1: Malkata part of the petals, which terminate at a
brown line.
Shape: medium to large jar, type unknown.
Fabric: Nile silt B2, with a cream surface coating
outside. P A L 8: Amarna
Decoration: narrow black and broader blue hori-
Shape: short- or medium-tall-necked jar with
zontal bands.
ovoid body, compare Hope (1991, figs 5j and
6c); part of neck and upper body extant.
P A L 2: Malkata Fabric: Nile silt B2, with a pinkish-orange
surface coating outside.
Shape: a very tall necked jar with ovoid body Decoration: a single wide blue band from base of
(see Hope 1989a, fig. 1 la); rim fragment. the neck over upper body, over which details
Fabric: Nile silt B2, with a cream surface coating in red and brown are added to produce a
inside rim top and outside. design of overlapping petals below an upper
Decoration: wide blue petals tapering upwards composite band, and below which is a brown
outlined in red, with red intervening strokes line--gap.
(stamens).

P A L 9: Amarna
P A L 4: Malkata Shape: a short-necked jar, compare Hope (1991,
Shape: medium to large jar, type unknown but fig. 5j); fragment from the upper body.
possibly compare Hope (1989a, fig. 6a); frag- Fabric: Nile silt B2, with cream surface coating
ment from the upper body. outside.
COBALT BLUE PAINTED POTTERY 99

Decoration: fugitive; traces of blue with the out- KACZMARCZYK, A. 1986. The source of cobalt in
lines of overlapping petals terminating at a ancient Egyptian pigments. In: OLIN, J. S. &
brown line. BLACKMAN, M. J. (eds) Proceedings of the 24th
International Archaeometry Symposium. Smithso-
nian Institution Press, Washington, DC, 369-376.
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ARNOLD, D. 1993. Techniques and traditions of manu- zling Sun: Amenhotep III and his World. Cleveland
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ARNOLD, O. & BOURRIAU,J. (eds) An Introduction LILYQUIST, C. & BRILL, R. H. 1993. Studies in Ancient
to Ancient Egyptian Pottery. Philipp von Zabern, Egyptian Glass. Metropolitan Museum of Art,
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BELL, M. R. 1987. Regional variation in polychrome alogische, Monatshefte, 209-214.
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BOURRIAU,J. D., NICHOLSON,P. T. & ROSE, P. J. 2000. BOURRIAU, J. (eds) An Introduction to Ancient
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HOPE, C. A. 1980. Blue-painted pottery of the XVlllth Co., London.
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The ceramic technology used in the manufacture of
Iron Age pottery from Galilee
S H L O M O S H O V A L 1, P I R H I Y A H BECK 2'* & ESTHER Y A D I N 2
1Geology Group, Department of Natural Sciences, The Open University of Israel, The Dorothy
de Rothschild Campus, 108 Ravutski Street, Raanana, Israel (e-mail: shoval@openu.ac.il)
2lnstitute of Archaeology, Tel-Aviv University, Tel-Aviv, Israel (*deceased)

Abstract: The Iron Age ceramic technology used in the manufacture of functional pottery
from Galilee was studied. Applied methods included petrography, X-ray diffraction, infrared
spectroscopy and chemical analyses. The results demonstrate that the potters in biblical
times had knowledge of raw materials and manufacturing technologies, enabling them to
select suitable ones, according to their advantages, for the manufacture of cooking pots,
storage jars and tableware vessels. The paper describes the petrography of the pottery, the
composition of the ceramic matrix, the firing temperature, the tempering of the cooking
pots, the processes that allow consolidation of the ceramic and the origin of the pottery.
The results are placed in an archaeological context.

Iron Age pottery was excavated at Tel-Hadar, on potters usually used local raw materials suitable
the eastern shore of the Sea of Galilee. The exca- for pottery production. Two main types of raw
vations were carried out in the framework of materials were used, calcareous and noncalcar-
The Land of Geshur Archaeological Project, of eous clays (Maniatis & Tite 1981; Shoval
The Institute o f Archaeology, Tel Aviv Univer- 2003), each of which has different advantages
sity (Kochavi 1989). A large pillared building for pottery production (Maggetti 1981; Maggetti
from the 1 lth century BC was excavated on the et al. 1984). Improvements in the properties of
site. The ground floor of the building was used the local raw materials, in terms of forming,
for storage and marketing and included storage firing and the resultant physical properties of
rooms, granary rooms and a columned hall the ceramic were obtained by sorting, tempering
(Kochavi 1989). Many storage and tableware by adding non-plastic coarse particles, and
vessels and some cooking pots were found in mixing of clays (Hein et al. 2004). The firing
the storage rooms. The pillared building was process can be assessed from the phase assem-
destroyed by conflagration at the end of the blage in the ceramic (Maggetti 1982; Shoval
l lth century BC and the site was subsequently 1994, Mirti et al. 1999). The reactions that
abandoned. The extreme intensity and high occur during firing of clay follow two main
temperature of the conflagration demonstrate mechanisms: continuous reactions producing
that it was the grain-filled granary rooms that only compositional variations of phases, and dis-
bumed (Shoval et al. 1989). No signs of any continuous reactions leading to nucleation and
unusual intensity of conflagration were observed growth of new mineral phases (Duminuco et al.
in the storage rooms containing the pottery 1998; Riccardi et al. 1999). The evolution of
(Kochavi 1989). As the event occurred in the the phase assemblages depends on the mineral-
late eleventh century Bc, it may have happened ogy and chemistry of the raw material, their
during the wars of King Saul against enemies particle-size distribution, maximum firing
of the Israelite settlers in Gilead (II Samuel temperature, heating rate, duration of firing,
2:9). A small agricultural and fishing village and the oxygen fugacity of the kiln atmosphere
was built on the destroyed site in the ninth (Moropoulou et al. 1995; Livingstone Smith
century BC (Kochavi 1989). 2001).
A study of the production technology of Different newly formed phases are observed
ancient pottery using mineralogical and petro- when firing typical raw materials (Maggetti
graphic methods can focus on the type of raw 1981, 1984; Shoval 1988). The firing of noncal-
material and on the firing process (Maggetti careous material can be approximated by firing
1982, 1994; Maggetti et aI. 1984). The ancient of kaolinitic clay. Kaolinite dehydroxylates at

From: MAGGETTI,M. & MESSIGA,B. (eds) 2006. Geomaterialsin CulturalHeritage.


Geological Society, London, Special Publications, 257, 101-117.
0305-8719/06/$15.00 © The Geological Society of London 2006.
102 S. SHOVAL ETAL,

400-650 °C and a pseudo-amorphous phase, and thus the amount of the newly formed
metakaolinite, is formed (Mackenzie & Rahman calcite. It should be noted that Ca-silicate
1987; Mackenzie et al. 1988). The thermal trans- phases may contain some carbonate, although it
formation from metakaolinite to mullite starts is not so likely in dense ceramic material.
with short-range ordered material. According to The purpose of the present research is to study
Freund (1974), at about 900 °C the metakaolinite the Iron Age ceramic technology used in the
transforms into a cubic phase described as spinel, manufacture of functional pottery (cooking
which is poorly crystallized. Gualtieri & Belloto pots, storage jars and tableware vessels) from
(1998) stated that after the loss of the residual Galilee.
hydroxyls, metakaolinite transforms into three
phases: ",/-alumina (which has a spinel structure),
mullite (AlgSiOs) and silica. Well-crystallized E x p e r i m e n t a l methods
phases of mullite and cristobalite (SiO2) are Ceramics
observed at about 1200 °C (Dong-Li &
Thomson 1991; Belloto et al. 1995). On firing The studied pottery was excavated by archaeolo-
smectitic (montmorillonitic) clay, the smectite gists at Tel Hadar from strata of the eleventh and
dehydroxylates at 600-800 °C, and with increas- the ninth centuries BC (Kochavi 1989). The
ing temperature meta-smectite is formed (Shoval pottery from the 1 lth century BC stratum was
1988). The major phases formed by the heating excavated from a large pillared building and was
of smectite have been identified as meta- found in storage rooms located on the ground
smectite, spinel, mullite, cordierite and cristoba- floor of the building. Pottery from the ninth
lite (Seyama & Soma 1986). After firing to century BC stratum was excavated from the site
800 °C, some rehydroxylation of the clay min- of a small village built on the destroyed site.
erals may take place within the fired material in
ambient conditions (Heller et al. 1962; Shoval R a w materials
et al. 1991).
When firing calcareous raw materials, the dehy- Some alluvia and soils, which are equivalent to
droxylation of the clay stimulates earlier decarbo- the raw materials used for the production of the
nation of calcite (Heller-Kallai et al. 1986, 1987). investigated pottery, were also analysed. These
The microcrystalline calcite of the calcareous raw raw materials include basaltic soil of Golan,
material decomposes above 600 °C (Shoval et al. Terra Rossa of Galilee, alluvium from Wadi
1993), Carbon dioxide gas (CO2) is released, and Samakh, alluvium soil of the Jordan Valley and
quicklime (CaO) is formed. Above 900 :C, the rendzina soil of Galilee.
quicklime reacts with amorphous phases resulting
from the dehydroxylation of clays and Ca-
Methods
silicates; gehlenite (Ca2AI2SiOT), plagioclase
anorthite (CaAl2Si208) and pyroxene The pottery was investigated using the following
wollastonite-diopside (CaSiO3) are formed methods.
(Maggetti 1981, 1982; Maggetti et al. 1984;
Shoval 1988). Under ambient conditions, newly Petrography. Thin sections of the pottery were
formed calcite may crystallize from non-reacted analysed under a polarizing microscope.
quicklime (Shoval et al. 1993, 2003; Shoval
2003). During this process, the hygroscopic Fourier transform infrared FTIR spectro-
quicklime picks up moisture from the air, scopy. A Nicolet FTIR spectrometer and
forming calcium hydroxide (Ca(OH)2) (Shoval 'Omnic' software were used. Spectra from pow-
1988; Shoval et al. 1993). The Ca(OH)2 slowly dered samples of the ceramic matrix (excluding
reacts with atmospheric CO2 and calcite is the temper particles) were obtained. Samples of
formed. Some calcite may also crystallize the bulk pottery (including the temper particles)
during cooling (Deutsch & Heller Kallai 1991). were also analysed. The powders were diluted
Newly formed calcite is usually characterized in KBr and pressed into discs. These were
by small grain size and a low degree of crystalli- heated to 110 °C and 350 °C to remove water
nity (Maciejewski & Relier 1989). The formation bands. Before measurement, the discs were re-
of microcrystalline calcite during the recarbona- pressed to improve the resolution of the spectra.
tion process may lead to cementation of the
material, like the process in lime-based plasters X-ray diffractometry (XRD). XRD was per-
and mortars (Kingery 1988; Moropoulou et al. formed on powder samples with a Philips PW-
2005). On firing above 900 °C, the formation of 3710 diffractometer using C u I ~ radiation at
Ca-silicates reduces the amount of free lime 35 kV and 40mA, and a curved graphite
CERAMIC TECHNOLOGY OF IRON AGE POTTERY 103

monochromator. Diffractograms from powdered amounts of iron oxide and quartz silt in the
samples of the ceramic were obtained. For the ceramic matrix are an indication of soil-derived
identification of the types of clay minerals in raw material. The soils are enriched in quartz
the raw materials, oriented clay fractions, after silt because of the contribution of dust. On the
carbonate removal with diluted HC1, decantation other hand, clayey sediments usually lack
and glycolation, were employed. coarse particles that could act as temper and
therefore require the addition of temper particles
Chemical analyses. The major element con- from some other source. The potter obviously
tents in the ceramic matrix (excluding the preferred to add coarse particles of a local
temper particles) were determined by energy dis- material, as was corroborated in ethnological
persive spectrometry (EDS) using a LINK-10000 studies (Maggetti 1982).
EDS system (Oxford ISIS) attached to a JEOL
(JSM-840) scanning electron microscope Petrographic groups of cooking pots. The
(SEM) and ZAF4/FLS program. The reference cooking pots were divided into three major petro-
standard for X-ray microanalyses of Microana- graphic groups.
lyses Consulted Ltd. (Registered standard 1691) Group 1: manufactured from basaltic soil
was used for the EDS analysis. The analyses and tempered with calcite crystals. This group
were carried out on 'fresh' sections of the consists of cooking pots from the l lth and
pottery. The samples were carbon coated. At ninth century BC strata. The presence of some
least three measurements were obtained from basalt fragments within a noncalcareous or
each sample. For deeper penetration an 18 kV slightly calcareous blackish or dark matrix, rich
electron beam was used. The beam width was in iron oxide and quartz silt (Fig. 2a), indicates
15 nm and the resolution 1 Ixm. Accumulations that the raw material was basaltic soil. No lime-
of 6 0 s ( 3 - 5 iterations) were applied. The stone particles are found. The pots were
analytical error is _+2%. The ceramic matrix tempered with broken pieces of large calcite
area to be analysed was marked by scratching
crystals.
around it, and was located using the SEM. A Group 2: manufactured from Terra Rossa and
back-scattered electron (BSE) detector attached tempered with calcite crystals. This group con-
to the SEM was used to ensure that calcite sists of cooking pots from the 1 lth and ninth
temper was far from the analysed area. century BE strata. The presence of some lime-
stone fragments within a noncalcareous or
Results and discussion slightly calcareous brownish-red matrix, rich in
iron oxide and quartz silt, indicates that the raw
Petrography of the pottery material was Terra Rossa. No basalt particles
Petrographic groups of the pottery, types of are found. Similar to Group 1, the pots were tem-
pottery and a list of the investigated pottery are pered with calcite crystals.
shown in Table 1. Examples of cooking pots Group 3: manufactured from basaltic soil not
and storage jars are shown in Figure 1. The tempered with calcite crystals. This group con-
pottery was divided into petrographic groups sists of cooking pots from the ninth century BE
according to the characteristics of the ceramic stratum. Similar to Group 1, this group was man-
matrix and the nature of the temper particles. ufactured from basaltic soil, but not tempered
The groups differ in the type of raw material with calcite crystals (Fig. 2b).
used in their manufacture.
Petrographic groups of storage jars and table-
Identification of the raw materials. Potential ware vessels. The storage jars and tableware
raw materials available in the region are clayey vessels were divided into six major petrographic
soils, alluvia and sediments. Each raw material groups. The pottery in these groups was exca-
has typical petrographic characteristics, which vated from the l lth century B¢ pillared
allow unambiguous identification. Alluvia and building.
soils usually contain attached coarse particles Group 4: manufactured from calcareous allu-
and thus the use of these raw materials does not vium. This group consists of storage jars, pithoi,
require tempering with particles from an kraters, bowls, jugs, a chalice, a lamp, and
additional source. Various types of unsorted amphora. The presence of unsorted and
and rounded grains are an indication that calcar- rounded grains of basalt, chalk, and limestone
eous alluvium was used as raw material, whereas and quartz sand within a calcareous light
a single type of fragments attached to the raw matrix (Fig. 3a) indicates that the raw material
material indicates that soil was used. High was calcareous alluvium.
104 S. SHOVAL ET AL.

Table 1. Petrographic groups of the pottery, types of pottery and list of the investigated Iron Age pottery
excavated from Tel-Hadar

Group Types of pottery List of pottery


Group 1: manufactured from basaltic soil and tempered with calcite crystals
la Cooking pots, 1lth century Bc 1574/1 (TH-7) 1574/3 (TH-27) 1778/1 (TH-37)
1783/3 (TH-31) 1834/2 (TH-8) 1844/3 (TH-42)
lb Cooking pots, 9th century Bc 110/158 (TH-118) 119/158 (TH-117) 1117/256 (TH-105)
Group 2: manufacturedfrom Terra Rossa and tempered with calcite crystals
2a Cooking pots, 1lth century Bc 1734/1 (TH-2) 1756/1 (TH-6) 2021/1 (TH-5)
2264/1 (TH-259)
2b Cooking pots, 9th century Bc 166/181(TH-110) 1115/252 (DTH-9) 1115/252 (TH-113)
1117/256 (TH-103) 1127/252 (DTH-12) 1227/256 (TH-107)
1250/256 (TH-104) 1672/295 (TH-47) 1672/295 (TH-50)
1672/295 (TH-51) 1244/248 (TH- 124)
Group 3: manufacturedfrom basaltic soil but not tempered with calcite crystals
Cooking pots, 9th century Bc 11/106 (TH-115) 171/185 (TH-119) 1108/252 (DTH-I1)
1115/252 (TH-112) 1177/256 (TH-106) 1244/248 (TH-126)
1244/248 (TH-127) 1244/248 (TH-125)
Group 4: manufactured from calcareous alluvium
Storage jars 1277/1 (TH-202) 1562/1(TH-24) 1734/2 (TH-3)
1757/1 (TH-20) 1783/2 (TH-28) 1809/1 (TH-4)
1810/1 (TH-18) 1823/1 (TH-11) 1828/1 (TH-33)
1834/1 (TH-200) 1864/1(TH-35) 1865/1 (TH-209)
1873/1 (TH-16) 2139/1 (TH-309) 2148/1 (TH-308)
Pithoi 1302/1 (TH-15) 2238/1 (TH-264)
Kraters 1740/1 (TH-14) 1828/2 (TH-32) 2108/1 (TH-13)
Bowls 1746 (TH-98) 1844/2 (TH-40)
Jugs 1790/1 (TH-9) 2105/1 (TH-261)
Lamp 1868/2 (TH-44)
Chalice and amphora 2149/1 (TH-36) 2217/2 (TH-251)
Group 5: manufactured from calcareous alluvium soil
Storage jars 1783/1 (TH-30) 2039/1 (TH-313) 2044/1 (TH-324)
1866/1 (TH-43) 1867/2 (TH-204)
Krater 1267/1 (TH-250)
Jug and amphora 1861/1 (TH-315) 2340/1 (TH-265)
Group 6: manufactured from calcareous rendzina soil
Storage jar 2060/1 (TH-302)
Bowl and amphora 2152/1 (TH-310) 1803/1(TH-303)
Group 7: manufactured from calcareous marl
Storage jars 2105/2 (TH-326) 2217/1 (TH-263)
Jugs 1565/1 (TH-206) 2207/1 (TH-317) 2374/1 (TH-99)
Group 8: manufactured from calcareous sediment of the coastal plain
Storage jars 2225/1 (TH-301) 2220/1 (TH-270)
Jugs 1702/1 (TH-316) 2348/1 (TH-260)
Group 9: manufacturedfrom calcareous sediment from a foreign coastal area
'Greek' bowl 1842/1 (TH-325)
The listof pottery includesthe excavationsymbol(e.g. 1574/1)and the samplenumberusedfor the experiments(e.g. TH-7,whereTH
indicatesTel Hadar).

Group 5: manufactured from calcareous Group 6: manufactured from calcareous


alluvium soil. This group consists of storage rendzina soil. This group consists of storage
jars, kraters, jugs and amphora. The temper par- jars, amphora and a bowl. The presence of
ticles are smaller and rounder than those in chalk fragments within a calcareous matrix rich
Group 4 and consist of highly weathered basalt in quartz silt (Fig. 3b) indicates that the raw
grains and some iron oxide concretions. The material was calcareous rendzina soil. The
matrix is richer in iron oxide and quartz silt. matrix contains relicts of basaltic soil in the
This composition indicates that the raw material form of mud balls, as well as a few basalt frag-
was calcareous alluvium soil. ments (Fig. 4a), indicating that the calcareous
CERAMIC TECHNOLOGY OF IRON AGE POTTERY 105
(a)

Fig. 2. Thin-section photomicrographs of cooking pots.


(a) Group 1: manufactured from basaltic soil and
tempered with calcite crystals, and characterized by the
presence of some basalt fragments within
noncrystallized blackish or brownish-red noncalcareous
matrix (a basalt fragment is observed at the upper
right corner, and a rhombohedral calcite crystal in
the middle). (b) Group 3: manufactured from
basaltic soil but not tempered with calcite crystals (a
basalt phenocryst with ophitic texture is observed in
the middle). (40x magnification, cross-polarized light.)

Fig. 1. Examples of 1lth century ac pottery studied in


the present research. (a) Cooking pot. (b) Storage jar. consists of storage jars and jugs. The presence
The pottery was excavated by archaeologists at Tel of a few rounded grains of quartz and some
Hadar (Kochavi 1989). skeletal fragments of Mediterranean fauna
within a calcareous matrix rich in quartz silt
(Fig. 5a) indicates that the raw material was
selected from calcareous sediment of the
rendzina soil raw material was mixed with non- coastal plain.
calcareous basaltic soil. Group 9: manufactured from calcareous sedi-
Group 7: manufactured from calcareous marl. ment from a foreign coastal area. Group 9 con-
This group consists of storage jars and jugs. The sists of a single 'Greek' bowl. The matrix is
composition of the calcareous matrix is almost calcareous, rich in Foraminifera fossils and
lacking in quartz silt, and the presence of Forami- poor in temper particles (Fig. 5b). A large frag-
nifera fossils (Fig. 4b) indicates that the raw ment of coarse crystalline limestone or marble
material was selected from marl. No basalt frag- is observed. The presence of few rounded
ments are found. The matrix contains relicts of grains of quartz and some skeletal fragments
Terra Rossa in the form of mud balls, as well indicates that the raw material was selected
as a few limestone fragments (Fig. 4b), indicat- from calcareous sediment near a coast.
ing that the calcareous marl raw material was The cooking pots were manufactured from
mixed with noncalcareous Terra Rossa. noncalcareous or slightly calcareous soil. The
Group 8: manufactured from calcareous soil was tempered with calcite crystals from an
sediment of the coastal plain. This group additional source. On the other hand, the
106 S. SHOVAL ETAL.
(A) (a)

(b} (bl

Fig. 3. Thin-section photomicrographsof storage jars.


(a) Group 4: manufactured from calcareous alluvium
and characterized by the presence of various types of Fig. 4. Thin-section photomicrographsof tableware
unsorted and rounded grains within crystallized vessels. (a) Group 6: made by the mixing of rendzina
calcareous light matrix (basalt grain is observed in the soil raw material with basaltic soil and characterized by
middle and at the lower right comer, chalk grains are the presence of relicts of noncalcareous soil in the form
dispersed throughout the section). (b) Group 6: of mud balls (a large dark ball is observed in the middle).
manufactured from calcareous rendzina soil and (b) Group 7: made by the mixing of foraminiferousmarl
characterized by the presence of chalk fragments raw material with Terra Rossa soil and characterized by
attached to the soil raw material within partly relicts of noncalcareous soil in the form of mud balls.
crystallized calcareous matrix. (Chalk grains are (Foraminifera fossils are dispersed throughout the
dispersed throughout the section, 40 × magnification, section, and a dark ball appears in the middle left comer;
cross-polarized light.) 40x magnification,cross-polarized light.)

storage jars and most of the tableware vessels respectively. The mixing was performed to
were manufactured from calcareous alluvium or enrich the clay component of the raw material,
calcareous soil. The largest group (Group 4) of and to improve the properties of the raw material
storage jars and tableware vessels was manu- for pottery manufacture.
factured from calcareous alluvium, as identified
by the presence of various types of unsorted
The composition of the ceramic matrix: the
and rounded grains in a light ceramic matrix.
In petrographic Groups 6 and 7, highly calcar- mineral and phase composition
eous rendzina soil or marl was mixed with non- X-ray diffraction. XRD is a useful method for
calcareous Terra Rossa or basaltic soil, estimating the mineral composition of pottery
respectively, as observed from the presence of fired at a high temperature (Maggetti 1981,
relicts of noncalcareous material appearing in 1982; Maggetti et al. 1984; Bertolino &
the form of mud balls. Similar mixing of Fabra 2003; Eramo et al. 2004). However, this
rendzina soil or foraminiferous marl with Terra method is suitable for the determination of
Rossa was previously reported in the region in crystalline materials, but not amorphous phases.
the manufacture of Roman pottery (Wieder & The XRD results of this study demonstrate
Adan-Bayewitz 1999) and Iron Age pithoi from that peaks of Ca-silicates that may relate to
Tel Sasa (Cohen-Weinberger & Goren 1996), the firing process are missing or very weak.
CERAMIC TECHNOLOGY OF IRON AGE POTTERY 107

The rise of the baseline in the diffractograms of of the investigated pottery, the major type of
the examined pottery is related to the presence the clay mineral was also analysed by XRD.
of a pseudo-amorphous phase of fired clay. The results demonstrate that smectite is the
Absence of newly formed Ca-silicates indicates dominant clay mineral in the basaltic soil of
that the pottery was fired below 900 °C. XRD Golan, in the Terra Rossa of Galilee, in the allu-
was also used here as accurate evidence for the vium of Wadi Samakh, in the alluvium soil of the
presence of calcite in the ceramic matrix. The Jordan Valley and in the rendzina soil of Galilee.
strong peaks of calcite in the diffractograms of The raw materials contain some kaolinite mixed
matrix samples of the storage jar and tableware with the smectite. The calcareous sediments in
vessels are in agreement with their calcareous the region are also dominated by smectitic IS
composition observed through petrographic (illite-smectite) accompanied by palygorskite
analysis. Weak or missing peaks of calcite in (Shoval 2004).
the diffractograms of matrix samples of the
cooking pots confirm their slightly calcareous FTIR spectroscopy. F'I'IR spectra of the cera-
or noncalcareous composition. mic matrix of representative cooking pots and
In the alluvium and soil raw materials, which storage jars are shown in Figure 6. The FTIR
are equivalent to those used for the production data are given in Table 2 and arranged according

(a) o.~oi
0.35

0.3O
(a)~l,,3, ,o41 ]
0,25.

0.2O

0.15.

0.3

I=
j ~ 0 .2

(b) < (C) 142o

713

0.7

0otl.I
0..51
• I t 1040

0.3 77 463
"/'/8 713
0,2

Fig. 5. Thin-section photomicrographs of tableware


vessels. (a) Group 8: manufactured from calcareous Wave.umber (era"1)
sediment of the coastal plain and characterized by the
presence of few rounded grains of quartz and some Fig. 6. FTIR spectra of representative pottery.
skeletal fragments of Mediterranean fauna within partly (a) Ceramic matrix of a cooking pot of Group 1 showing
crystallized calcareous light matrix (a skeletal fragment the main S i - O stretching band of fired clay with one
is observed in the middle). (b) Group 9: manufactured maximum at 1041 cm -1. (b) Ceramic matrix of a
from calcareous sediment of a foreign coastal area and cooking pot of Group 1 showing splitting of the main
characterized by a calcareous matrix which is rich in S i - O stretching band into bands at 1053 and
Foraminifera fossils and poor in temper particles. 1079 c m - 1. (c) Bulk pottery material of a cooking pot of
(Foraminifera fossils are dispersed throughout the Group 1 showing the main CO3 band of the calcite
section; a large fragment of coarse crystalline limestone temper at 1426 c m - i. (d) Ceramic matrix of a storage jar
or marble is observed in the lower left corner; of Group 4 showing the main CO3 band of newly formed
40× magnification, cross-polarized light.) calcite at 1438 cm-1.
108 S. SHOVAL ET A L

Table 2. The range of the band maxima in F'FIR spectra and the percentages of calcite in the ceramic
matrix of Iron Age pottery excavated from Tel-Hadar

Group Pottery type Si-O str. (I) Si-O str. (II) Si-O, AI-O def. CO3 % Calcite
(cm - J) (cm- i ) (cm- i) (cm - i)

Group la Cooking pots 1039-1055 - 467-475 1430-1439 7-13


Group lb Cooking pots 1053-1055 1077-1080 463-467 1430-1432 5-12
Group 2a Cooking pots 1050-1056 1074-1083 461-467 1430-1432 3-14
Group 2b Cooking pots 1045-1060 1076-1082 461-468 1430-1441 7-15
Group 3 Cooking pots 1045-1059 1078-1083 461-465 1432-1435 0-10
Group 4 Storage jars 1035-1045 - 461-469 1430-1441 33-57
Pithoi 1037-1045 - 470-475 1430-1431 39-40
Kraters 1031 - 1039 - 459-463 1430-1448 30-55
Bowls 1034-1035 - 463-464 1431 - 1 4 3 2 50-55
Jugs 1033-1034 - 458-459 1434-1436 39
Chalice 1039 - 467 1430 47
Amphora 1041 - 463 1432 30
Lamp 1043 - 466 1431 37
Group 5 Storage jars 1050-1054 1078-1081 462-466 1430-1436 33-50
Krater 1061 1082 467 1435 36
Jug 1061 1082 466 1432 35
Amphora 1050 1080 465 1440 30
Group 6 Storage jar 1041 - 471 1430 55
Bowl 1045 - 467 1430 35
Group 7 Storage jars 1037-1047 - 466-470 1430-1435 50-55
Jugs 1038-1045 - 468-470 1435-1440 45-75
Group 8 Storage jars 1037-1040 - 471-473 1430-1432 40-55
Jugs 1038-1040 - 470-473 1431 - 1 4 3 2 30-55
Group 9 'Greek' bowl 1040 - 470 1432 45
The FFIR data are arranged accordingto the petrographic groups and the potterytype. str., stretching;def., deformation.

to the petrographic groups. FTIR spectroscopy is is distorted by the main band of the fired
a useful method for the phase analysis of smectite).
pottery (Shoval 1994, 2003; De Benedetto In the ceramic matrix of the pottery, the main
et al. 2002), as this technique allows the identi- CO3 band is located above 1430 cm - l (Table 2)
fication of both the amorphous and the crystal- and commonly characterized by a broad shape at
line materials (Shoval et al. 2001, 2002). To the top (Fig. 6d), whereas in the spectra of natural
identify the mineral and phase composition of calcite it appears at 1422cm -~ (Fig. 7d). The
the ceramic matrix of the pottery, the spectra higher frequency of the main CO3 band in the
of the pottery are compared with those of the ceramic matrix can be related to the presence
individual minerals and phases expected; for of newly formed calcite (Shoval et al. 1993).
example, fired kaolinite or fired smectite (both This shift may result from the low degree of crys-
fired at 750 °C), quartz and calcite (Fig. 7). tallinity of the newly formed calcite and the
The spectra of the ceramic matrix of the existence of impurities of magnesium and iron.
cooking pots are indicative of noncalcareous It seems that the microcrystalline calcite of the
ceramic, showing strong S i - O vibrations ceramic matrix was fully decarbonated during
characteristic of fired clay (Fig. 6a and b). firing and calcite was newly formed in the
Those of the storage jars are indicative of cal- ceramic after firing. On the other hand, in the
careous ceramic, showing strong CO3 vibrations spectra of calcite temper of the cooking pots,
characteristic of newly formed calcite, and the main CO3 band appears at about 1425-
weaker S i - O vibrations characteristic of fired 1429 cm -~ and is sharp at the top (Fig. 6c).
clay (Fig. 6d). The main S i - O stretching mode The lower frequency in the calcite crystal is in
appears in the pottery at 1035-1083 cm -1 and accordance with its higher degree of crystallinity
the combined S i - O , A 1 - O bending mode at and lower amount of impurities. It seems that the
4 5 9 - 4 7 5 cm -1 (Table 2). The quartz doublet location of the calcite temper inside the clay
at about 779 and 798 cm -1 (Fig. 7c) appears matrix shield allowed the decomposed calcite
weak in the spectra of the pottery (Fig. 6) and to be recarbonated and reconstructed almost to
demonstrates that some quartz is present its original form (Shoval et al. 1993). However,
(the main S i - O band of quartz at 1085 cm - l in low-temperature firing the calcite in temper
CERAMIC TECHNOLOGY OF IRON AGE POTTERY 109

o ]l.I A" t fired clay (calculated without the CaO com-


ponent of the ceramic matrix) are shown in
0.4 17473 Tables 3 and 4, respectively. The percentages
of calcite in the ceramic matrix, calculated
0,3
according to the CaO portion, are given in the
O,2 tables. The compositions of the examined raw
1A materials are shown in Table 5. The amounts of
12- calcite in the pottery are similar to those in the
1.0": corresponding raw materials. The amounts of
o~ calcite in the ceramic matrix (line a in Tables 3
0.8-" and 4) are similar to those observed by F f I R
~ 0.4. spectroscopy (Table 2) and confirm the quantitat-
ive analysis by the latter method.
< (c) The composition of the fired clay in the
ceramic matrix (without the microcrystalline
calcite component of the ceramic matrix; line b
in Tables 3 and 4) is used here to characterize
0,15 the raw material. In most of the pottery, the
amounts of A1203 in the fired clay are around
(d) 15-20%. These amounts are in accordance
with the smectitic composition of the examined
raw materials (Table 5). It should be mentioned
o.e that, by XRD analysis, smectite was found to
o.6 be the major clay mineral in these raw materials.
oA In most of the pottery the amounts of SiO2,
o2
around 55-60%, are also in accordance with
the smectitic composition of the raw materials.
Wavenumber (cm-!) On the other hand, in kaolinitic raw material
the amounts of A1203 and SiO 2, around 40%
Fig. 7. FTIR spectra of individual phases expected in
pottery composition. (a) Fired smectite (at 750 °C). and 50%, respectively, are significantly different
(b) Fired kaolinite (at 750 °C). (c) Quartz. (d) Calcite. (e.g. kaolin Ramon in Table 5). The amounts of
K20 and MgO are also in agreement with a
smectitic composition of the examined raw
may remain as primary calcite. The relatively
materials. Larger amounts of A1203 in some of
smooth faces of the calcite temper seen in the
the pottery are related to the presence of some
thin sections confirm these observations.
kaolinite in the raw material whereas larger
FFIR spectroscopy was also used for
amounts of SiO2 are related to the presence
quantitative analysis of calcite in the ceramic
of quartz silt. The large amount of FeO is indica-
matrix (Table 2). These amounts were calculated
tive of pottery manufactured from soil raw
according to the intensities of the main CO~
material.
band of calcite at about 1 4 3 0 - 1 4 4 8 c m -
relative to the main S i - O band of the fired
clay at about 1035-1083 cm -~ (Fig. 6d). Cali- The firing temperature of the pottery
bration curves were used for this determination. The firing process of ancient pottery is com-
The results demonstrate that the amounts of monly assessed by investigating the thermal
the calcite component in the ceramic matrix phases that are temperature dependent (Maggetti
(excluding the temper particles) range between 1982; Shoval 1994). In this study, the firing
0 and 15% in the cooking pots and between 30 temperature is estimated using FTIR spec-
and 57% in the storage jars and the tableware troscopy by comparing the spectral properties
vessels. of the pottery with those of the raw materials
fired at various temperatures (Shoval 1994,
2003). The estimation is based on several obser-
The chemical composition of the vations, as follows.
ceramic matrix
The main Si-O stretching band. In the
The content of the major elements in the ceramic spectra of the storage jars of Group 4, the main
matrix was obtained in the selected pottery by S i - O stretching band appears in the range of
point chemical analysis by EDS-SEM. The 1031-1045 cm -1 (Table 2), and this range is
compositions of the ceramic matrix and the close to that observed after firing the raw
110 S. SHOVAL ET AL.

Table 3. The major element composition (normalized to 100%) obtained by point analysis in selected
Iron Age cooking pots from Tel-Hadar
Sample number Ceramic matrix and fired clay composition % Calcite

SiO2 A1203 MgO FeO Ti02 K20 CaO

Group 1
1574/1 (TH-7) a 56.13 17.84 2.56 11.38 2.00 2.37 7.72 14
b 62.92 20.19 2.33 10.65 1.22 2.69 -
1778/1 (TH-37) a 58.95 12.35 4.77 15.03 1.22 1.43 6.25 11
b 62.96 13.05 5.00 15.84 1.28 1.88 -
1783/3 (TH-31) a 58.96 19.45 2.00 11.15 1.69 3.36 3.39 6
b 61.04 19.96 2.04 11.47 1.74 3.75 -
1834/2 (TH-8) a 58.46 21.25 2.68 10.37 1.19 2.18 3.87 7
b 60.90 21.88 2.73 10.71 i.22 2.55 -
1844/3 (TH-42) a 56.38 20.12 2.42 12.32 2.15 2.09 4.52 8
b 59.18 20.84 2.49 ! 2.78 2.22 2.49 -
Group 2
1734/1 (TH-2) a 61.13 17.78 1.52 8.55 1.31 1.47 8.24 15
b 66.77 18.97 1.61 9.21 1.39 2.06 - -
1756/1 (TH-6) a 62.78 17.76 1.41 10.58 2.96 1.79 2.72 5
b 64.57 18.12 1.44 10.83 3.01 2.04 -
2021/1 (TH-5) a 64.88 17.24 1.39 10.03 2.54 1.91 2.01 4
b 66.24 17.50 1.40 10.20 2.58 2.09 -
2264/1 (TH-259) a 60.49 19.57 1.38 10.88 2.09 1.50 4.09 7
b 63.17 20.18 1.43 11.26 2.14 1.83 -
Group 3
11/106 (TH-115) a 60.28 17.82 1.83 10.22 1.55 3.08 5.22 9
b 63.51 18.85 1.93 10.83 1.64 3.24
171/185 (TH-119) a 58.39 19.94 2.51 9.73 1.12 2.05 6.26 11
b 61.96 21.29 2.66 10.42 1.19 2.48 -

a, The compositionof the ceramicmatrix;b, the compositionof the firedclay (normalizedwithoutthe amountof CaO). The percentages
of calcite in the ceramicmatrix,calculatedaccordingto the CaO portion,are given.

materials between 700 and 800 °C (Shoval decarbonization occurs at about 600 °C (Shoval
2003). In the spectra of some of the cooking et al. 1993), indicating that the storage jars
pots of Groups 2 and 3, this band splits in the were fired above this temperature. Similar
ranges of 1045-1060 and 1 0 7 6 - 1 0 8 3 c m -1 results were observed in slightly calcareous
(Table 2), and these ranges are close to those matrix of cooking pots.
observed after firing the raw materials between
800 and 900 °C (Shoval 2003). The OH stretching band of rehydroxylated
The S i - O and A l - O deformation bands. The clay. After removing the water bands, a weak
combined S i - O , A 1 - O bending mode appears OH band is observed in the spectra of cooking
with one peak in the range of 4 5 9 - 4 7 5 c m - l pots at 3 6 2 0 - 3 6 3 2 cm -1 (Shoval et al. 1991).
(Table 2), which is typical of dehydroxylated Because smectite was found to be the main
fired clay. Thus, the firing was performed above clay mineral in the raw material, the 3 6 2 0 -
the dehydroxylation temperature of smectite. 3632 cm -1 band is related to the presence of
some rehydroxylated smectite in the ceramic.
The main C03 band. The appearance of the The weak intensity of this band indicates that
main CO3 band above 1430 c m - l in the spectra small amounts of rehydroxylated smectite are
of the matrices of most storage jars can present in the ceramic matrix. Thus, the firing
be related to the presence of newly formed was performed below the temperature for non-
calcite. In the calcareous ceramics the calcite is reversible dehydroxylation of the smectite
newly formed after the firing (Shoval et al. (Shoval et al. 1991). In smectite, rehydration
1993). Thus, the firing was performed above and rehydroxylation occur at room temperature,
the decarbonation temperature of the micro- after dehydration and dehydroxylation by
crystalline calcite in the ceramic matrix. In heating to temperatures as high as 800°C
mixtures of clay and microcrystalline calcite, (Heller et al. 1962).
CERAMIC T E C H N O L O G Y OF IRON AGE P O T T E R Y 111

Table 4. The major element composition (normalized to 100%) obtained by point analysis in selected
Iron Age storage jars and tableware vessels from Tel-Hadar
Sample number Ceramic matrix and fired clay composition % Calcite

SiOz A1203 MgO FeO TiO2 K20 CaO

Group 4
1562/1 (TH-24) a 49.91 11.39 2.50 8.86 0.95 1.07 25.33 45
b 67.00 14.82 3.20 11.62 1.22 2.14 -
1783/2 (TH-28) a 41.01 14.27 2.30 6.40 1.55 2.58 31.89 57
b 60.48 20.05 3.17 9.12 2.14 5.04 - -
1828/2 (TH-32) a 41.20 13.54 4.75 7.01 1.05 2.33 30.12 54
b 59.28 18.71 6.41 9.74 1.41 4.46 -
1746 (TH-98) a 42.16 14.78 2.76 7.44 1.49 2.11 29.26 52
b 59.94 20.13 3.69 10.22 1.99 4.02 -
1844/2 (TH-40) a 37.84 13.56 2.43 8.64 2.47 2.76 32.29 58
b 55.63 19.54 3.44 12.52 3.46 5.41 -
Glvup 5
1783/1 (TH-30) a 49.71 11.38 2.23 7.13 1.52 1.81 26.22 47
b 67.42 14.94 2.88 9.48 1.97 3.31 - -
2039/1 (TH-313) a 42.37 12.81 3.29 5,47 1.12 2.90 32.03 57
b 62.81 17.91 4.86 8.40 1.69 4.33 - -
2044/1 (TH-324) a 42.51 11.82 2.80 6.30 1.56 2.73 32.26 58
b 64.59 14.28 4.01 9.33 2.24 5,55 - -
Group 6
2060/1 (TH-302) a 43.21 11.98 1.85 6.57 1.45 2.64 32.30 58
b 63.88 16.94 2.56 9.45 2.02 5.15 -
1803/1 (TH-303) a 51.89 13.81 3.10 8.84 1.50 2.06 18.81 34
b 64.00 16.64 3.69 10.70 1.77 3.20 -
2152/1 (TH-310) a 58.82 11.55 2.22 7.54 1.35 1.32 20.20 36
b 68.25 15.85 0.91 5.28 1.47 8.23 - -
Group 7
2 1 0 5 / 2 (TH-326) a 42.49 14.93 1.06 6.77 1.17 2.09 31.50 56
b 62.27 20.83 1.46 9.63 1.62 4.19 -
2217/1 (TH-263) a 48.78 11.62 2.90 5.79 0.90 2.14 27.87 50
b 67.60 15.54 3.81 7.86 1.19 3.99 - -
1565/1 (TH-206) a 46.15 16.03 1.77 6.74 1.66 2.18 25.48 45
b 62,14 20.75 2.27 8.84 2.13 3.88 - -
2207/1 (TH-317) a 34.48 11.70 1.46 3.90 0.62 1.71 46.13 82
b 64.27 20.24 2.46 6.94 1.07 5.01 - -
2374/1 (TH-99) a 34.48 15.51 1.70 6.03 0.67 2.83 38.79 69
b 59.86 22.22 2.90 7.38 1.49 6.14 -
Group 8
2225/1 (TH-301) a 43.01 15.62 1.22 7.59 1.67 1.98 28.91 52
b 60.85 21.10 1.62 10,41 2.23 3.79 -
2220/1 (TH-270) a 49.74 17.45 2.39 6.41 0.85 4.72 18.44 33
b 60.99 20.81 2.81 7.73 1.01 6.66 - -
1702/1 (TH-316) a 40.28 15.66 2.19 5.48 0.51 4.21 31.67 57
b 59.05 21.81 2.98 7.78 0.72 7.67 -
2348/1 (TH-260) a 51.18 22.36 1.06 7.66 2.20 1.53 14.01 25
b 59.83 25.45 1.19 8.80 2.49 2.23 - -
Group 9
1842/1 (TH-325) a 43.42 17.46 1.76 5.83 0.52 3.45 27.56 49
b 60.14 23.10 2.30 7.85 0.69 5.91 -

a, The composition of the ceramic matrix; b, the composition of the fired clay (without the amount of CaO). The percentages of calcite in
the ceramic matrix, calculated according to the CaO portion, are given.

F r o m t h e s e o b s e r v a t i o n s , it s e e m s that the
Tempering of the cooking pots
c o o k i n g p o t s w e r e fired at a b o u t 7 5 0 - 8 5 0 °C The cooking pots were tempered with broken
a n d the s t o r a g e j a r s a n d the t a b l e w a r e v e s s e l s at p i e c e s o f c a l c i t e c r y s t a l s that w e r e a d d e d to the
a b o u t 6 5 0 - 7 5 0 °C. c l a y e y r a w m a t e r i a l f r o m an a d d i t i o n a l s o u r c e
112 S. SHOVAL ET AL.

Table 5. The major element composition (normalized to 100%) of local alluvia and soils

Sample Ceramic matrix and fired clay composition % Calcite

SiO2 A1203 MgO FeO TiO2 K20 CaO

Basaltic soil of a 54.69 16.42 4.87 12.48 1.98 2.11 7.44 13


Golan b 59.90 17.77 5.23 12.33 2.12 2.65 - -
Terra Rossa of a 61.88 18.72 1.88 10.34 1.63 1.63 3.93 7
Galilee b 64.42 19.89 1.89 10.45 1.64 1.72 - -
Alluvium of a 38.29 14.98 3.27 9.64 1.71 0.99 31.11 56
Wadi Samakh b 59.35 18.97 4.50 12.53 2.32 2.32 -
Alluvium soil of a 42.78 11.86 2.83 6.51 1.43 2.62 31.98 57
Jordan Valley b 63.90 16.68 3.54 9.30 2.53 4.06
Rendzina soil of a 31.36 9.03 2.56 8.38 1.46 1.38 45.84 82
Galilee b 58.35 15.94 4.42 14.72 2.44 4.13 -
Bentonite Ramon 62.28 22.10 2.75 6.74 1.04 5.09 - -
Kaolin Ramon 51.14 38.40 0.13 1.77 8.56 0 - -

a, The compositionof the bulk material; b, the compositionof the clay component(normalizedwithout the amount of CaO). The
percentages of calcite in the ceramic matrix, calculated according to the CaO portion, are given. Analysesof two referenceclays,
kaolin (kaolinite)Ramonand bentonite(smectite)Ramon.are addedfor comparison.

(Shoval et al. 1993). The cooking pots have high calcite crystals prevents cracking and fracturing
concentrations of calcite temper. The amounts of owing to thermal shock during rapid heating or
the calcite temper, calculated by subtracting the cooling of the vessels. This was explained by
percentages of calcite in the bulk pottery from the similarity between the thermal expansion
the percentages of the microcrystalline calcite
in the ceramic matrix, are up to 32%. According
to Tite et al. (2001), the production of pottery (a)
with high toughness and thermal shock resistance
requires low firing temperatures and high temper
concentrations. The high temper content used in
the production of cooking pots suggests that the
requirement for high thermal shock resistance
was a factor that at least influenced the techno-
logical choice in this case (Tite et al. 2001). In
the investigated cooking pots, the high temper
concentration may be related to the use of smec-
titic clay raw material for their production. Swel-
ling smectitic clay is less suitable for ceramic
production than kaolinitic clay. The temper par-
ticles were necessary during the manufacture of
(c)
the pottery to reduce high plasticity and the col-
lapse of the smectitic clay during the shaping of
the vessels, as well as to prevent shrinking and
cracking during the drying of the pots.
Most of the cooking pots were tempered with
broken pieces of large calcite crystals that were
added to the clayey raw material from an
additional source. Three types of calcite crystals
were found in the pottery (Fig. 8). The rhombo-
hedral calcite and the coarse crystalline calcite
were probably collected from veins, druses and
speleothems. The large calcite crystals were Fig. 8. Thin-section photomicrographsof calcite
temper types in cooking pots. (a) Temper of
crushed and mixed for tempering during pro-
rhombohedral calcite (in the middle left corner).
duction (Porat 1989). Large calcite crystals are (b) Temper of coarse crystalline calcite (drusy calcite,
not readily available and therefore the potters in the middle right corner). (c) A large fragment of
must have made great efforts to collect them. speleothem (in the middle, 40x magnification,
According to Arnold (1985), tempering with cross-polarized light).
CERAMIC TECHNOLOGY OF IRON AGE POTTERY 113

coefficient of the calcite crystals and the sur- smectitic clay allowed the low-temperature sin-
rounding fired clay during firing. However, this tering. The clay from soil is relatively poorly
is true only at low firing temperatures, at which crystallized and rich in natural iron oxide, both
calcite crystals do not decompose. If the firing of which induce earlier sintering. In very fine-
temperature is high enough for decomposition textured raw material (such as soil), the sintering
of the calcite crystals to quicklime, the thermal begins earlier than in coarse raw material
expansion coefficient would no longer be (Rice 1987). Moreover, very fine ferrous oxide
similar to that of the clay (Broekmans et al. (FeO) in a reduced state may act as a flux
2004). at temperatures between 800 and 900°C
Limestone particles composed of polycry- (Grimshaw 1971). It seems that the high iron
stalline calcite should have similar thermal oxide content in the basaltic soil or in the Terra
expansion coefficients to those of large calcite Rossa acts as an efficient flux material, which
crystals (Shoval et al. 1993). Although limestone reduces the sintering temperature during firing.
is much more readily available than large calcite The potters used noncalcareous raw material
crystals, potters usually rejected it for the prep- for the preparation of cooking pots to produce
aration of cooking pots (Arnold 1985). Alterna- dense ceramic, impermeable and stable on
tive tempering with coarse limestone particles cooking directly over fire, and able to withstand
is inappropriate as it brings about earlier and repeated heating and cooling.
intense decarbonation during firing, which
causes defects in the pots (Shoval et al. 1993). Consolidation o f the calcareous ceramic. The
Limestone has small calcite crystals with large lower firing temperature of the storage jars
specific surface area, more crystalline defects and tableware vessels, at about 650-750 °C,
and impurities, which lead to earlier intensive was obtained by using calcareous raw material.
thermal decarbonation compared with large Lime is used as a flux, and vessels prepared
calcite crystals. The rapid release of carbon from this clay are sintered at lower tempera-
dioxide gas (CO2) is accompanied by blowing tures. However, in storage jars and tableware
and fracturing, which induces mechanical vessels containing a large amount of calcite in
damage in the pots. Furthermore, after firing, the ceramic matrix (Tables 2 and 4) it seems
the hygroscopic quicklime (CaO) picks up moist- that, instead of sintering the clay, the potters
ure from the air, forming calcium hydroxide used lime technology to achieve consolidation
(Ca(OH)z). The formation of calcium hydroxide of the vessels (Shoval 2003). It should be
is accompanied by volume expansion, which noted that Tables 2 - 4 represent the amounts
induces stresses in the surrounding clay body, of microcrystalline calcite mixed with the clay
causing defects in the vessels (Arnold 1985). in the ceramic matrix, but not that in the
Tempering with broken pieces of large calcite calcite temper or other carbonate particles.
crystals prevents cracking and fracturing during Firing the calcareous raw material above
the firing as it provides higher resistance to 600 °C was sufficient for decomposition of the
thermal decomposition and this seems to be the microcrystalline calcite to quicklime (Shoval
reason for their use in cooking pot production et al. 1993). The consolidation of the storage
(Shoval et al. 1993). jars was achieved by recrystallization of micro-
crystalline calcite during the recarbonation
process. Consolidation by cementation with
Processes that allow consolidation calcite required lower firing temperatures than
o f the ceramic those necessary to complete the sintering of
the clay. Indeed, in these storage jars, a micro-
Although the cementation of the ceramic body by graphic texture of microcrystalline calcite
sintering of the clay usually occurs upon firing (micrite) is observed in the ceramic matrix
above 900-1000 °C (Rice 1987; Traore et al. and such a texture, with a low degree of crystal-
2000), lower firing temperatures were found linity, is typical of newly formed calcite
here for the cooking pots and for the storage (Maciejewski & Relier 1989). The use of lime
jars and tableware vessels. technology for cementation of lime-based plas-
ters and mortars (Kingery 1988; Moropoulou
Consolidation o f the noncalcareous ceramic. The et al. 2005) and for production of Vaiselle
relative low firing temperature of the cooking Blanche ('Whiteware', Goren 1991) was
pots, at about 750-850 °C, suggests that the already known from the Neolithic period. It
cementation to ceramic was obtained by low- seems that after firing, the storage jars were
temperature sintering of the clay. It seems that carefully stored for a period of time to complete
the use of soil raw material composed of the solidification by recrystallization of the
114 S. SHOVAL ET AL.

newly formed calcite. It should be noted that large fragment of coarse crystalline calcite or
some pozzolanic activity was found in mixtures marble may suggest an origin on a Mediterranean
of quicklime and meta-clay, and such a process island, where marble is exposed. Indeed, the
was used for the cementation of ancient plasters pottery is fine and thinner than in the other
and mortars (Moropoulou et al. 2004, 2005). groups. It is reasonable to assume that this
particular pottery was imported, rather than
to suppose a sudden change in the local
The origin of the pottery technique.
The place of production of each petrographic
group of the pottery is related to the area in
which the raw material is common. Local
Summary
ceramic is recognized by temper particles The manufacturing technology
collected near the site, whereas imported
ceramic is identified by temper particles not The results demonstrate that the potters in bibli-
found in the vicinity. cal times had knowledge of raw materials and
temper particles, thus allowing them to select
suitable ones, according to the advantages of
The cooking pots. The cooking pots of each, for the manufacture of cooking pots,
Groups 1 and 3 were manufactured from basaltic storage jars and tableware vessels.
soil, which is common on the Golan basalt ( 1) The cooking pots were manufactured from
plateau, east of the excavated area. Group 2 noncalcareous or slightly calcareous raw
was produced from Terra Rossa, which is material, whereas the storage jars and most of
common on Upper Cretaceous limestone and the tableware vessels were manufactured from
dolostone of the Galilee Mountains, west of the calcareous raw material.
excavated area. (2) This tradition of pottery making was
applied during the Iron Age by using noncalcar-
The storage jars and the tableware vessels. eous and calcareous raw materials available near
Group 4, the largest petrographic group, was each production site; this is the reason for the
manufactured from calcareous clay- variability in raw materials.
alluvium. Such alluvium, containing both basalt (3) The potters preferred to use clayey soils
and carbonate grains, is present in the vicinity and alluvium as raw materials, rather than
of the Tel Hadar site only in the drainage clayey sediment for this purpose. The clay from
system of the Golan slopes, toward the shore of soil is relatively poorly crystallized and rich in
the Sea of Galilee (in the river beds of Wadi natural iron oxide, both of which induce earlier
Samakh and the Yarmouk river). Group 5 was sintering. Alluvium and soil are available in the
produced from calcareous alluvium soil. Such vicinity of the site and there was no need to
soil, containing small amounts of highly weath- bring the raw material from a distance.
ered basalt grains, is common in the Jordan (4) Basaltic soil and Terra Rossa were used as
Valley south of the Sea of Galilee. Group 6 noncalcareous or slightly calcareous raw
was manufactured from calcareous rendzina materials for the preparation of the cooking
soil mixed with noncalcareous basaltic soil. pots. It should be noted that the common noncal-
Rendzina soil is common on Eocene chalk, and careous geo-material in the region is clayey
basaltic soil is common on Neogene basalt soil, whereas sediments are usually calcareous,
flows, both of which appear nearby in the particularly appearing as marls.
Galilee Mountains. The presence of Foraminifera (5) Alluvium, rendzina soil and clayey sedi-
fossils of Eocene age within the chalk fragments ment were used as calcareous raw materials for
supports this observation. Group 7 was produced the preparation of the storage jars and tableware
from calcareous marl mixed with noncalcareous vessels.
Terra Rossa. Marls are common in Maastrichtian (6) To reduce the high calcareous properties of
and Paleocene formations, and Terra Rossa is the rendzina soil or marl, the raw materials were
common on Upper Cretaceous limestone and mixed with noncalcareous Terra Rossa or basal-
dolostone, both of which appear nearby in tic soil, as observed from the presence of relicts
Western Galilee-Lebanon. Group 8 was manu- of noncalcareous material appearing in the
factured from calcareous sediment of the form of mud balls.
coastal plain. Such sediment is common in the (7) The potters kept the attached coarse par-
northern Mediterranean shore. Group 9 was pro- ticles of the alluvium and soil raw materials as
duced from calcareous sediment from a foreign natural temper. Tempering by adding large
coastal area and seems to be imported. The calcite crystals from an additional source was
CERAMIC TECHNOLOGY OF IRON AGE POTTERY 115

used only for the production of cooking pots (4) The large storage jars of Group 4 are of
from soil-derived raw material. The raw local production. It seems that for production of
materials are rich in smectite and the temper par- large vessels designed for storage of dry foods,
ticles were necessary during the manufacture of a coarse local calcareous raw material produced
the pottery to reduce the high plasticity and by using lime technology was sufficient. These
prevent collapse of this clay. vessels were probably used as containers for
(8) Alternative tempering of the cooking pots storing the food intended for marketing in the
with coarse limestone particles composed of columned hall. It is reasonable to assume that
polycrystalline calcite is inappropriate as it large jars of local production were not trans-
brings about earlier and intense decarbonation ported over large distances.
during firing, which causes defects in the pots. (5) Tableware vessels of Group 4 are also of
(9) The cooking pots were fired at about local production. These vessels, which were
750-850 °C and the cementation to ceramic designed for everyday use, are coarse and thick
was obtained by low-temperature sintering of and usually not burnished or decorated. They
the clay. The use of soil raw material composed served as tools for preparing foods and for eating.
of smectitic clay allowed low-temperature (6) The cooking pots of Groups 1-3 were
sintering. imported to Tel Hadar from Golan and from
(10) The storage jars and most of the tableware Galilee. For their preparation, a higher quality
vessels were fired at about 650-750 °C. The raw material was needed. They served as
large amount of calcite in the ceramic of Group 4 implements for heating foods. However, Group
indicates that instead of sintering the clay, 2 includes some large cooking pots that had
the potters used lime technology to achieve been not used, and these pots were probably
consolidation of the vessels. Consolidation by intended for marketing in the columned hall.
cementation with calcite required lower firing (7) The pottery of Groups 6 - 8 was imported
temperatures than those necessary to complete to Tel Hadar from far away. These vessels are
the sintering of the clay. burnished or colour-slipped and part of them
(11) A higher quality of noncalcareous or was decorated with brown-red bands. They
slightly calcareous raw material was necessary were imported for marketing because of the
for the manufacture of cooking pots to produce quality of the ware and probably subsequently
dense ceramic that was impermeable and stable used for storing oils or other expensive products.
in cooking directly over fire and able to with- (8) The imported storage jars of Groups 6 - 8
stand repeated heating and cooling. were probably brought as containers for the
traded goods.
(9) The 'Greek' bowl of Group 9 was possibly
The archaeological context imported from a Mediterranean island. This
The results are placed in an archeological pottery is fine and thinner than that of the other
context, as follows. groups and decorated inside with a red cross.
(1) The various petrographic groups of pottery (10) The variability in the raw materials indi-
excavated in the pillared building of Tel Hadar cates that during the Iron Age the pottery
reflect the trade connections of this site with needed at each site was prepared by the local
the surrounding region. These groups demon- potters. There was no pottery-making centre for
strate that the pottery was manufactured in regional production.
different locations and imported to Tel Hadar. (11) The major technological evolution in the
(2) The petrographic groups demonstrate that Iron Age, relative to that in previous periods, is
the pottery was manufactured in the vicinity of the specification in the use of raw materials and
the site, as well as in the Golan, the Jordan manufacturing technologies for the production of
Valley, Galilee, Western Galilee-Lebanon and different functional vessels. The transformation
the northern shore. Thus, Tel Hadar had connec- from hand-made to wheel-made pottery becomes
tions with these regions. widespread during the Bronze Age 2a and pro-
(3) The many storage and tableware vessels duction in workshops began in this period.
found in the storage rooms of the pillared build- (12) The technology used by the potters of
ing and their various origins indicate that the the ninth century is similar to that in the 1 lth
site was used as a trading post. It seems that century, indicating a similar tradition of pottery
columned hall of the pillared building was used production.
for marketing. The large granary rooms of the (13) The major technological evolution in later
ground floor were also used for this purpose. periods relative to that of the Iron Age is the
The movement of goods seems to have covered establishment of pottery-making centres for
a large area. regional production. These centres specialized
116 S. SHOVAL ETAL.

in the manufacture of particular types of vessels. The Infrared Spectra of Minerals, Mineralogical
For example, the bulk of the c o m m o n cooking Society, London, Monograph, 4, 465-482.
ware of Roman Sepphoris was supplied by the GOREN, Y. 1991. The beginnings of ceramic pro-
Kefar Hananya site located in the Galilee duction in Israel, technology and typology of
region (Adan-Bayewitz & Perlman 1990). proto-historic ceramic assemblages in Eretz
Israel (6th-4th millennia B.E.C.). PhD thesis,
The Hebrew University of Jerusalem.
The excavations at Tel Hadar were carried out in the fra- GRIMSHAW, R. W. 1971. The Chemistry and Physics
mework of the Land of Geshur Archaeological Project, of Clays and other Ceramic Materials. Wiley,
of The Institute of Archaeology, Tel Aviv University, by Chichester.
M. Kochavi (director) and E. Yadin (field director at Tel GUALTmRI, A. & BELLOTO, M. 1998. Modelling the
Hadar). The supply of pottery and fruitful discussions structure of the metastable phases in the reaction
are gratefully acknowledged. This research was supported sequence kaolinite-mullite by X-ray scattering
by the Israel Science Foundation administered by the experiments. Physics and Chemistry. of Minerals,
Israel Academy of Sciences and Humanities and 25, 442-452.
completed through the support of the Open University HEIN, A., DAY, P. M., CAU ONTIVEROS, M. A. &
of Israel Research Authority. Both are gratefully KIL1KOGLOU, V. 2004. Red clays from central and
acknowledged. eastern Crete: geochemical and mineralogical
properties in view of provenance studies on ancient
ceramics. Applied Clay Science, 24, 245-255.
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Fibre-tempered pottery of the Stallings Island Culture from
the Crescent site, Beaufort County, South Carolina:
a mineralogical and petrographical study
M I C H A E L S. SMITH 1 & M I C H A E L B. T R I N K L E Y 2
1Department of Earth Sciences, University of North Carolina, Wilmington,
NC 28403-5944, USA (e-mail: smithms @uncw.edu)
2Chicora Foundation, Inc., PO Box 8664, Columbia, SC 29202, USA

Abstract: Late Archaic to Early Woodland (4500-3000 years BP) Stallings Island Culture
fibre-tempered plainware pottery is found from northern North Carolina to NW Florida and
is often separated into two temper groups (Stalling and Orange series) based upon fibre type.
Thirty-four sherds were studied to determine textural or mineralogical characteristics to
assist in form and type separation. This study finds that only a few of the sherds were domi-
nated by fibre. The fibre is visible as secondary porosity (voids) with some carbonized
remains and exhibits specific shape and orientation at different locations within the sherd.
Only two sherds had carbonized stem fragments that allowed identification of the Spanish
moss (Tillandsia usnedoides). The remainder of the Crescent site plainware pottery has
such low (to no) fibre contents as to be indistinguishable from similar age sand-tempered
Thorn' s Creek waxes. The identity and textural features of the fine-grained aplastic minerals
(quartz, feldspar, biotite and opaque minerals) in the paste are similar in both fibre- and
non-fibre-tempered sherds, and this suggests that the materials used are consistent with sedi-
ment extraction from a fluvial coastal plain or estuarine setting. These observations indicate
that the degree of fibre incorporation in these sherds may be related to the specific clay
source (or manufacturing location) or represent examples of an evolving pottery manufac-
turing process within the Stallings Island Culture.

Archaeological ceramics can provide important clarify the identity and amount of the fibre
insights into the culture, technology, and devel- temper.
opment of a civilization. By examining the
forms and the methods of decoration, clues to
cultural evolution or trade among cultures are Archaeological context
suggested. However, many prehistoric ceramics Around 4500 years BP, the Stallings Island
do not allow easy or definitive separation by Culture established a Late Archaic seasonally
these methods. When this situation arises, occupied shellfish-collecting society along the
analytical investigation via a variety of tech- southeastern Atlantic coastal environments with
niques (Rice 1987; Sinopoli 1991) such as a material cultural assemblage equivalent to
petrographic investigation is used to identify that found on Archaic sites (Sassaman 1993,
the plastic (paste) and the aplastic (temper) pp. 16-19). Their occupation sites are rep-
components of the pottery. resented by large shell middens that range from
This study examines 34 sherds of late Archaic the Tar River drainage in North Carolina, south-
to Early Woodland pottery recovered from ward to NW Florida. Stallings Island fibre-
the Crescent site (Stallings Island Culture) in tempered ceramics (4500-3000 years SP) were
Beaufort County, South Carolina. Trinkley & named after a major shell midden site on an
Hacker (1986, p. 166) and Trinkley (1998) island in the Savannah River near Augusta,
have previously discussed the form and type of Georgia (Fig. 1) and represent the oldest
this pottery, its 14C and supplied information documented ceramics in the southeastern USA
concerning the macroscopic investigation of (Stoltman 1966; Calmes 1968). The ceramics
similar sherds. This study was undertaken to were generally simple shallow bowls and large,
determine if any textural or mineralogical wide-mouthed bowls, with some deeper jar
characteristics would allow further form forms. Although most of these ceramics were
and type separation of this pottery as well as plain, some with punctuated (drag and jab)

From: MAGGETTI,M. & MESSIGA,B. (eds) 2006. Geomaterialsin CulturalHeritage.


Geological Society, London, Special Publications, 257, 119-125.
0305-8719/06/$15.00 © The Geological Society of London 2006.
120 M.S. SMITH & M. B. TRINKLEY

Orange period ceramics are shallow, fiat-based


and straight-sided circular bowls and rectangular
trays that are often undecorated (Sassaman
1993). The later Orange ware is more decorated,
with less rectangular trays, some mixture of sand
and fibre-tempering as well as the appearance of
coiling manufacture in the final Orange period
(c. 3250-3000 years BP; Sassaman 1993, p. 20).
By 3000 years BP (Early Woodland period),
fibre-tempered ceramic technology appears to
have spread throughout much of the Deep
South from the southeastern Atlantic coast to
the Okeechobee Basin area of South Florida
(Sassaman 1993). During the early Gulf
Formational period (c. 4500-3000 years BP;
Jenkins 1982) of Alabama, middle Tennessee,
and eastern Mississippi, fibre-tempered ceramic
technology (Wheeler Culture) was acquired as
a by-product of trade between the Stallings
Island and Orange Cultures of the southeastern
Atlantic coast and the Poverty Point Culture of
the lower Mississippi River Valley (Sears &
Griffin 1950; Jenkins et al. 1986). However, fibre-
tempered ceramics were eventually replaced by
plain, fabric-impressed, and cord-marked sand-
Fig. 1. Map of the southeastern US Atlantic coastal tempered Alexander ceramics during the later
region with locations of major Late Archaic pottery Gulf Formational period.
styles. Adapted from Sassaman(1993). Location of
Crescent site in Beaufort County, South Carolina is
designated by filledpentagon. It shouldbe noted that the Petrographic techniques
Stallings and Thom's Creek ceramic styles overlap
along the Coastal Plain of South Carolinabetween the Petrographic analysis is the principal method of
Santee and SavannahRivers. identifying minerals (and other substances) in
archaeological pottery (Rice 1987). Standard
(27 mm × 46 ram) petrographic thin sections
surface decoration were found (Griffin 1943; were prepared. All of the thin sections were
Trinkley & Hacker 1986, pp. 160-162). epoxy impregnated because of the friable nature
Temporally overlapping the Stallings Island of the sherds. Grain-size values are very fine
series are the sand-tempered Thom's Creek (<0.0625 ram), fine (0.0625-0.25 mm), medium
pottery (4000-2900 years BP; Calmes 1968). (0.25-0.49mm), coarse (0.50-1.0ram) and
This series is found with the Stallings wares very coarse ( > 1.0 ram). Colour identification
along the coastal areas of South Carolina was based upon the Munsell colour chips
between the Savannah and Santee Rivers and (Geological Society of America (GSA) 1991),
into the interior Coastal Plain (Sassaman 1993, and colours were observed under fluorescent
p. 20; Fig. 1). Trinkley (1980, 1983) indicated lamps and described from a dry surface.
that the fibre-tempered Stallings ware preceded The thin sections were point-counted using the
the sand-tempered Thom's Creek ware by a techniques of Stoltman (1989a,b) and Stoltman
few centuries, even though they share many et al. (1992). The point step was 0.1 mm so as
design attributes and co-occur at many sites to allow statistically significant counts (>300
north of the Savannah River (Sassaman 1993). points per thin section) and also to overlap with
Contemporary with Stallings Island fibre- the macroscopic evaluation of the size distri-
tempered pottery along the southeastern Atlantic bution of paste and aplastic materials (Trinkley
coast are fibre-tempered Orange ware from sites & Hacker 1986; Trinkley 1998). In any point-
in NE Florida and SE coastal Georgia (4000- counting technique the assumption is that the
3000 years BP; Sassaman 1993, pp. 20-21). component has a nearly spherical grain shape.
Orange period sites have been located at With this pottery, the evidence for the presence
Canaveral National Seashore, Fort Matanzas and abundance of fibre temper is provided by
National Monument, and Timucuan Ecological secondary porosity (voids) that contains some
and Historic Preserve (Fig. 1). The earliest carbonized remnants. As the fibre voids are of
CRESCENT SITE FIBRE-TEMPERED CERAMICS 121

two different shapes and orientations, the influ- A p l a s t i c (temper) c o m p o n e n t s


ence of this orientation may account for some The dominant aplastic mineral is quartz with a
of the percentage differences (and ranges) that very coarse to very fine grain size. The very
were observed. coarse to coarse crystals are angular to subangu-
The point count categories used were paste lar quartz rock fragments with sutured grain
(clay minerals and amorphous phases), quartz boundaries, undulatory extinction, and little
(separated by grain size), fibre, feldspar (noted rounding of the corners or edges.
as feldspar unless optical characteristics The medium grain size quartz is monocrystal-
allowed specific designation as either plagioclase line (single crystals) with a blocky (rectangular)
or alkali feldspar), opaque minerals, other to elongate slivers grain shape (Fig. 2). The
(includes epidote/clinozoisite, biotite and shape and texture suggest that the mineral
amphibole) and ACF (argillaceous clots or frag- grains were broken away from the parent rock
ments of air-dried clay; see Whitbread 1986). fragment. The fine to very fine quartz is also
Several features are observed in both hand monocrystalline and subangular to blocky in
specimen and thin section that may represent shape. There was very little rounding of the
compositional or mineralogical changes caused edges of these crystals and no well-rounded
by the firing conditions as well as by use or crystals were observed.
burial. Oxidation features (commonly a red to Feldspar is found in very small modal abun-
red-orange colour) were observed on both dance (<5 vol%) with only sherd JBM-6
the inner and outer sherd surfaces, extending having more feldspar (<15 vol%). The grain
inward for several millimetres. The region size ranges from medium to fine and the grain
between these oxidized zones (called the core) shape is blocky and rectangular to subrounded,
is generally reduced and is either black or primarily controlled by the two cleavage
smoky grey. Lastly, some of the sherds show directions (Fig. 2). Most feldspar is untwinned,
secondary carbonate infilling in the fibre void yet some sherds have potassium feldspar (micro-
spaces. This mineralization may have resulted cline; tartan albite-pericline twinning) in
from burial and interaction with ground water addition to plagioclase feldspar (polysynthetic
or may be a result of use. twins; JBM-30). The feldspars all exhibit some
form of alteration (e.g. sericite and argillite)
reflecting the deep weathering that is common
Petrographic results in the Coastal Plain sediments (Nystrom et al.
Table 1 summarizes the petrographic results and 1991; Ward et al. 1991).
textural characteristics of the samples. The rivers In the fine to very fine grain size fraction
of the study area (Fig. 1; e.g. Savannah, Santee, opaque minerals (probably iron oxides) along
and Altamaha Rivers) drain the igneous and with mica (biotite), epidote, and an amphibole
metamorphic basement rocks of the Piedmont (hornblende) were found (i.e. JBM-20, JBM-
region to the west and downcut through the 29). These minerals were probably part of the
Late Cretaceous to Pleistocene aged sediments sediment (clay component) used as paste
of the Coastal Plain (Horton & Zullo 1991; (similar in grain size) and are found in very
Nystrom et al. 1991; Ward et al. 1991). These low abundance (< 1 to 3 vol%) similar to that
Piedmont-draining rivers have a larger capacity described by Nystrom et al. (1991) and Ward
and carry relatively large amounts of sediment et al. (1991) for the sedimentary rocks deposited
that is less mature than the reworked (and in this region.
heavily weathered) sediment carried by Coastal A few argillaceous inclusions (ACF) were
Plain draining rivers (Soller & Mills 1991, found (Whitbread 1986). They are fine- to
p. 299). The Crescent site is located in Pliocene medium-grained (0.1-0.5mm) clots, which
to Pleistocene sediments (and terrace deposits) have a red (brick red to red black) colour and
that were deposited through either the reworking are ellipsoidal to spherical in shape, with irregu-
of Piedmont-derived quartz- and feldspar-rich lar surfaces that feather into the surrounding
sediments or during transgressive-regressive paste. The ACF are either composed totally of
cycles caused by eustatic sea-level fluctuations clay minerals or dotted with inclusions of
(Nystrom et al. 1991; Soller & Mills 1991). quartz and feldspar (similar in size to the aplastic
In addition, although these sherds are from the grains in the paste), and may represent air-dried
southeastern Atlantic coastal region, there clay fragments. Although they are not found in
was no petrographic or textural evidence for all of the sherds, they are distinctive at both the
any type of shell material or carbonate rock macroscale and the microscale and were prob-
fragments. ably formed (or incorporated) during vessel
122 M.S. SMITH & M. B. TRINKLEY

Table 1. Petrographic summa~ for Crescent site sherds

Sample Quartz Feldspar Fibre Mica (biotite) Other

JBM- I med-coarse* Voids only Opaque minerals


JBM-2 med-coarse 5-10% Hornblende
JBM-3 v. coarse-fine 5-10% Hornblende
JBM-4 v. coarse-fine 2-3% (plag) 5-10%
JBM-5 med-fine <2% 5-10% ACF
JBM-6 v. coarse-fine <15% 5-10%
JBM-7 med-fine 10-20% (core)
JBM-8 v. coarse-fine <2% 5-10% <<1%
JBM-9 med-fine < 1% Void only 2%
JBM- 10 med-fine ,-~ 1% Voids only 2%
JBM- 11 coarse-fine < i% 1-2% Hornblende
JBM-12 v. coarse-v, fine <1% 5-10% <1% Opaque minerals
JBM-13 <1% 5-10%
JBM-14 fine-v, fine '~ >30% Voids infilled with
carbonate
JBM-15 fine-v, fine >30% ACF
JBM-16 fine-v, fine <1% 5-10% 3%
JBM-17 v. coarse-fine None Opaque minerals
JBM-18 v. coarse-fine None Quartz -opaque
rock fragment
JBM-19 coarse-v, fine <1% <5%
JBM-20 med-fine <1% <5% Hornblende
JBM-21 fine !% <5% Hornblende, zircon,
opaque minerals
JBM-22 med-fine <1-2%
JBM-24 v. coarse-v, fine 5-10%
JBM-25 v. coarse-v, fine <1% 5-10%
JBM-26 v. coarse-fine 1 grain 10-20% (core)
JBM-27 fine-v, fine > 30% 1-3% Epidote
JBM-28 fine-v, fine >30% 3-5%
JBM-29 med-v, fine 5-10% 2-3% Hornblende
JBM-30 v. coarse-v, fine 5% (K-spar/plag) 5-10% Epidote
JBM-31 fine-v, fine 5% (plag) None 2 grains
JBM-32 coarse-v, fine 2-3% (plag) 5-10% <1% Voids infilled
with carbonate
JBM-33 reed-fine 1-2% (plag) 5-10%
JBM-34 med-v, fine 1% (plag) 5-10% ACF
JBM-35 v. coarse-med 3-5% (plag) None 1% Quartz rock
fragment
*Grain-size values are very fine (<0.0625 mm), fine (0.0625-0.25 mm), medium (0.25-0.49 mm), coarse (0.50-1.0 mm) and very
coarse (> 1.0 mm). ACF, argillaceousclay fragment; K-spar. alkali feldspar.

formation and are not considered to be tempering JBM-3 l, JBM-35; see Fig. 3) have mineralogical
material introduced by the potter. Further evi- and textural characteristics more similar to Early
dence for this interpretation is that the argillac- W o o d l a n d s (c. 3000 years BP) sand-tempered
eous clots do not contain inclusions that differ Thorn's Creek style pottery (Trinkley 1980,
from those found in the paste. 1983; Smith 1997), if not for the provenance of
the archaeological site.
The fibre component, based upon carbonized
Fibre (temper) component secondary porosity, makes up (at least) 3 5 - 4 0
The fibre (temper), which is often only visible as vol% in the fibre-dominated sherds (Table 1).
secondary porosity containing some carbonized Based upon the m o r p h o l o g y and textures of the
remains, is found as either elongate or oval to stem fragments in thin section, the likely identity
round voids. Only a few sherds were dominated of the fibre is Tillandsia usnedoides (Spanish
by fibre (i.e. JBM-14, JBM-27, JBM-28; moss) and not pounded palmetto frond as found
Table 1). A n u m b e r of the sherds without visible in the northern Florida and southern Georgia
evidence for fibre (i.e. JBM-17, JBM-18, Orange series ceramics (Simpkins & Allard
CRESCENT SITE FIBRE-TEMPERED CERAMICS 123

Fig. 2. JBM-30 (crossed-polarized light). Very coarse


to fine-grained aplastic components with 5-10 vol% Fig. 4. Sherd JBM-8 (plane-polarized light). Cross-
fibre (as voids and carbonized remnants). The large grain section of carbonized fibre stem fragment showing
near the centre of the sherd is polygranular quartz with vascular traces and stem wall texture. Photomicrograph
sutured grain boundaries. These rock fragments are from core region of sherd. Scale bar represents 0.4 mm.
subangular to subrounded and many of the
monocrystalline quartz grains (the blocky to sliver-like
medium-sized grains) probably have a similar origin. stem fragments (round voids) are concentrated
Also visible are blocky feldspars, polysynthetic twinned in the reduced core whereas the stem fragments
plagioclase (upper left) and mica laths (centre). It should
be noted how the outer surface appears to have had a (elongate voids) are found in the regions near
floated surface treatment, possibly a self-slip. Scale bar both the interior and exterior surfaces. The regu-
represents 0,4 mm. larity of this orientation suggests this was the
result of the manufacturing process. The outer
surfaces of the sherds (those that contain fibre)
1986; Fig. 4). The cross-sections of the stem are devoid of fibre. This absence might be the
(oval voids) are generally more abundant than result of floating or smoothing practices that
the stem fragments (elongate voids) and are were applied by the potter to the ceramic to
found to exhibit specific orientation within the bring up fine clays to cover the fibre, although
sherds (Fig. 4). In general, the cross-sections of one sample was found to have what appears
to be a self-slip (Fig. 2). These observations
generally concur with the fibre analysis study
by Simpkins & Allard (1986) on 60 Stallings
sherds from Florida, Georgia and South Carolina.
Lastly, several sherds (JBM-14, JBM-32) were
observed to have infilling (or rimming) of the
secondary porosity by calcite mineralization.
This is probably a result of post-depositional
groundwater interaction rather than a response
to cooking procedures (Sassaman 1993, pp.
186-188).

Paste components
The petrographic investigation of the paste
reveals a nearly isotropic (at 6 0 x objective
magnification) matrix with a reddish to reddish-
Fig. 3. Sherd JBM-35 (plane-polarized light). Very black hue. This material is probably a mixture
coarse to medium-grained aplastic material and lack of of extremely fine-grained clay minerals and
fibre temper (or voids; black circles are epoxy bubbles). amorphous phases. Resolvable within this
The blocky grain (upper left) is feldspar and subrounded
grain (lower right) is quartz. Polygranular quartz rock matrix are fine to very fine aplastic grains.
fragments with sutured grain boundaries and undulatory These grains (mainly quartz, some feldspar, and
extinction, as well as smaller blocky feldspar, rare opaque minerals) are monocrystalline, subangu-
biotite, and monocrystalline quartz grains (the blocky to lar to blocky in shape, and with very little round-
sliver-like medium-sized grains) from the remainder of ing of the edges. These results are consistent with
the temper. Scale bar represents 0.4 mm. the macroscale examination by Trinkley (1998).
124 M.S. SMITH & M. B. TRINKLEY

Oxidation features (red to red-orange colour) palaeobotantical techniques that required com-
were observed extending inward (to several plete destruction of the sherds to separate out
millimetres) on both the inner and outer sherd the fibre components. In that study they found
surfaces, whereas the core region was generally very little of the diagnostic-scale botanical com-
reduced and was black to smoky grey. ponent that would allow specific identification of
the Spanish moss species. The presence of the
fibre is an important temper component in
Conclusions the majority of the samples and suggests that it
Although the Stallings Island Culture pottery is was either actively incorporated into the pottery
identified macroscopically as fibre tempered, materials or was commonplace to the clay
the results of this study indicate that both fibre source materials. The orientation of the fibre
and non-fibre-tempered wares coexisted at the reveals that its presence was part of the manufac-
Crescent site. Regardless of whether they were turing process and not a casually incorporated
fibre- or non-fibre-tempered wares, the mineralo- substance. Why fibre was an important com-
gical and textural characteristics of the aplastic ponent may be related to its potential to
(temper) components are consistent with the cushion thermal shock. Thermal shock resistance
macroscale typological analysis (Trinkley & is affected by the paste composition, as well as
Hacker 1986; Trinkley 1998). The dominant the distribution and uniformity of aplastic com-
aplastic (temper) components are quartz ponents and vessel shape (Rye 1981). The use
(mineral and rock fragment) with minor alkali of an organic temper would result in a secondary
feldspar, plagioclase and carbonized fibre. porosity left behind after firing that would help
Quartz is either angular to subangular monocrys- arrest crack development (Rye 1981; Bronitsky
talline mineral crystals or polycrystalline rock & Hamer 1986; Skibo et al. 1989). A mixture
fragments. The identity and textural features of of fibre and quartz aplastic temper could rep-
the fine-grained aplastic minerals found in the resent possible attempts to improve the thermal
paste are also consistent in both the fibre- and properties of the pottery (Rye 1981; Bronitsky
non-fibre-tempered sherds. Quartz, possibly feld- & Hamer 1986; Skibo et al. 1989). Furthermore,
spar, very fine opaque minerals, mica (biotite), Sassaman (1993, pp. 161-163) reported that
epidote, and an amphibole (hornblende) are Stallings fibre-tempered pottery may have
found in the paste. A few brick-red argillaceous evolved from cooking vessels heated by indirect
inclusions (ACF; 0.1-0.5 mm) were found in methods (stone boiling using soapstone) to later,
some sherds. These observations indicate that more directly heated vessels (over a fire) where
the materials used in the pottery formation are better thermal shock resistance would be an
not inconsistent with sediment (and clay) extrac- important property. Skibo et al. (1989, p. 140)
tion from a fluvial Coastal Plain or estuarine suggested that although an organic-tempered
setting in the southeastern USA (Nystrom et al. pot may be more easily abraded and have slightly
1991; Ward et al. 1991). In addition, there were less thermal shock resistance, its lightness would
no indicator minerals or substances (e.g. shell allow its easy transportation in a mobile, food-
material or carbonate clasts) that would point to gathering society, as well as allowing the
a marine source for the clay minerals. The very manufacture of this pottery in one sitting,
coarse to coarse-grained aplastic components in without the need for intermediate drying stages.
these sherds are often quartz rock fragments However, some of the pottery at this site lacks
with sutured grain boundaries and undulatory fibre and more closely resembles the sand-
extinction. The texture and optical characteristics tempered Thom' s Creek wares (Fig. 1). Although
of this material, as well as the small amount of all of the material factors proposed for the pro-
feldspar, biotite, and lack of carbonate or shell duction of fibre-tempered pottery (Rye 1981;
material, is consistent with sediments derived Bronitsky & Hamer 1986; Skibo et al. 1989)
from the metamorphic terranes of the eastern may have been important considerations, the
Piedmont and western Coastal Plain (Fig. 1) by incorporation of fibre may have been simply
the Piedmont-draining rivers (Nystrom et al. related to the specific clay source (or manufactur-
1991; Soller & Mills 1991). ing location) or it may represent examples of a
The rare instances of carbonized fibre temper continually evolving pottery manufacturing
that have extant textural features (Fig. 4) process in the Late Archaic to Early Woodland
suggest that the identity may be Spanish moss Period in this area.
(Tillandsia usnedoides) rather than the pounded
palmetto frond found in similar fibre-tempered The authors would like to thank M. Maggetti and
Orange wares of northern Florida (Simpkins & B. Messiga for the opportunity to report on the Late
Allard 1986). Simpkins & Allard (1986) used Archaic to Early Woodland Stallings Island Culture
CRESCENT SITE FIBRE-TEMPERED CERAMICS 125

ceramics; we also acknowledge the insightful and helpful SINOPOLI, C. M. 1991. Approaches to Archaeological
comments and suggestions by our reviewer that improved Ceramics. Plenum, New York.
the manuscript. SKIBO, J. M., SCHIFFER, M. B. • REID, K. C. 1989.
Organic-tempered pottery: an experimental study.
American Antiquity, 54, 122-146.
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Chemical-mineralogical characterization of historical bricks from
Ferrara: an integrated bulk and micro-analytical approach
G I A N L U C A BIANCHINI, E L E N A M A R R O C C H I N O ,
ALESSANDRO MORETTI & CARMELA VACCARO
Dipartimento di Scienze della Terra, Universitgl degli Studi di Ferrara,
Via Saragat 1, 1-44100 Ferrara, Italy (e-mail: bncglc@unife.it)

Abstract: In this paper we present bulk X-ray fluorescence-X-ray diffraction (XRF/XRD)


and microanalytical scanning electron microscope-electron microprobe analysis (SEM-
EMPA) data on historical bricks from Medieval or Renaissance buildings of Ferrara (NE
Italy) to provide insights into the nature and provenance of the raw material as well as
clues on the sintering techniques. Chemical data indicate that the starting materials were
obtained by mixing high Cr-Ni clay and subordinate sand (both quarried from the Po
river alluvial deposits) with the possible introduction of a Na-rich flux component. Thin-
section observation, XRD and micro-analytical data indicate the presence of key accessory
phases such as pyroxene, amphibole, epidote and rare olivine in the pre-fired mineral assem-
blage, confirming the utilization of the Po river sediments. Recognition of neo-formation
firing phases (e.g. melilite, wollastonite), together with composition of micas, amphiboles
and interstitial glasses, indicate kiln temperatures between c. 800 and 1000 °C. This pro-
vides guidelines for making new compatible and durable bricks to be utilized for restoration,
and contributes to the preservation of historical masonry.

Ancient bricks from Medieval and Renaissance style with numerous sumptuous palaces. This
buildings of Ferrara (NE Italy) have been building boom utilized bricks (cotto ferrarese)
studied using bulk techniques that analyse a and mortars as the dominant building materials.
few grams of homogenized (powdered) sample, The use of these construction materials is
and microanalytical techniques that allow com- related to the geographical position and the
position analysis of single phases of materials geomorphological framework of the Ferrara
that are heterogeneous at a micrometre scale. area, which is characterized by the widespread
This characterization provides useful clues to presence of silico-clastic sediments (and the
constrain the provenance of the original raw lack of rock outcrops; Amorosi et al. 2002).
materials and the historical firing techniques. Bricks and a few cotto decorative elements
These data provide information useful to were collected from some important historical
understand the physico-chemical behaviour of monuments of the city. These included the
the studied bricks that will be helpful in future Monastery of Sant'Antonio in Polesine (built in
preservation and restoration strategies. several phases during the 12th-16th centuries),
the Church of Santa Mafia in Vado (founded
in the 10th century and extensively modified in
Historical background the 15th-16th centuries), the Church of Santo
The Medieval city of Ferrara (NE Italy, Fig. 1), is Stefano (founded in the 10th century, but rebuilt
located in the eastern part of the Po alluvial plain, in the 15th-16th centuries), the Cathedral of
where at that time the Primaro river branched off Ferrara (apse, 15th- 16th centuries), the Schifanoia
from the main course of Po river (Bondesan et al. Palace ('Hall of Stuccoes', 15th- 16th centuries),
1995; Ferri & Giovannini 2000). This geo- and the surrounding city walls (15th century).
graphical position, situated on a major waterway
at a natural crossroads between the Adriatic
Sea and the Po alluvial plain, contributed to the Bulk chemical composition of historical
flourishing of the city, which peaked during the
Renaissance. In this period, the Este family bricks from Ferrara
promoted a further fortification of the wall ring Chemical composition (major and trace
and embellished the city centre in a grandiose elements) of terracottas sampled from the

From: MAGGETTI, M. & MESSIGA, B. (eds) 2006. Geomaterials in Cultural Heritage.


Geological Society, London, Special Publications, 257, 127-140.
0305-87191061515.00 © The Geological Society of London 2006.
128 G. BIANCHINI E T A L .

(a) (b)

Ferrara

Ci~' Walls

Fig. 1. Sketch map showing (a) the geographical position of Ferrara; (b) the locations of the studied historical
buildings. S. Stef, Church of Santo Stefano; Schifa, Schifanoia Palace; SMV, Church of Santa Maria in Vado; StAPol,
Monastery of Sant'Antonio in Polesine.

historical buildings of Ferrara and its city walls that CaO-rich clays ultimately led to bricks
was determined by X-ray fluorescence (XRF) characterized by better physico-mechanical
using a Philips PWI400 spectrometer. The properties (e.g. higher compressive strength,
method was calibrated with a wide range of higher durability) because carbonates have a
natural standards, and the precision and accuracy positive influence on brick textures by promoting
were better than 5%. Representative analyses a higher degree of vitrification (Elert et al. 2003).
of bricks and cotto decorative elements from his- The A1203 content of the studied bricks is
torical buildings and the city walls are presented generally lower (and the SiO2 content slightly
in Table 1. Major element analyses have been higher) than that of the local clays, showing a
recalculated and summed to 100% including rough trend towards the composition of the
LOI (loss of ignition at 1100 °C), and trace local sands. The occurrence of coherent trends
element data are expressed in parts per millions in other plots (see the K20 v. SiO2 diagram)
(ppm). indicates that such sands were used to temper
To investigate the nature of the raw material, the original clay body. This is confirmed by
these results were compared with data that thin-section analysis, in which we observed that
included natural sediments from the Po alluvial several samples are not homogeneous and are
plain around Ferrara (Bianchini et al. 2002a, characterized by distinct textural domains
plus our unpublished data; Table 2) and plotted (e.g. portions characterized by different grain
using bivariate diagrams with SiO2 wt% as a sizes; presence of detrital grains). This suggests
variation index (Fig. 2). The relatively restricted that the original raw materials were often
CaO range typical of the studied terracotta mixed to obtain a suitable composition.
(in contrast to the high CaO variability recorded in On the other hand, the excess of Na20
the local clays) suggests that the most carbonate- recorded in the studied materials (compared
rich pelitic sediments were preferentially quar- with the local clay composition) cannot be
ried as raw materials for brick production. This ascribed to the introduction of sand in the starting
means that the Ferrara brick-makers noticed body clay. This feature could be induced by
FERRARA HISTORICAL BRICKS 129

Table 1. Major (wt%) and trace element (ppm) composition of bricks and terracotta samples from the historic
buildings and city walls of Ferrara.

Sant' Antonio in Polesine Church (StAPol)

EMT 19MT 32MTint 104MT 105MT 107MT 122MT 154MT


SiO2 54.80 52.71 54.04 52.03 54.11 53.11 55.27 52.55
TiO2 0.71 0.74 0.64 0.75 0.68 0.71 0.67 0.73
A1203 14.91 15.21 13.34 14.52 15.14 15.35 14.77 15.11
Fe203 5.78 6.48 5.32 6.16 5.79 6.22 5.76 6.56
MnO 0.12 0.12 0.15 0.14 0.11 0.12 0.11 0.13
MgO 4.79 5.17 3.51 4.20 5.06 5.26 4.90 4.86
CaO 10.28 10.97 13.66 13.80 9.94 10.21 9.42 13.14
NaeO 1.91 1.57 1.48 0.97 1.95 1.65 1.90 1.20
K20 2.04 2.29 2.09 2.35 2.08 2.73 2.24 2.27
P205 0.20 0.19 0.23 0.18 0.20 0.23 0.18 0.18
LOI 4.46 4.55 6 4.90 4.95 4.43 4.80 3.27
Total 100 100 100 100 100 100 100 100
Ni 152 167 156 127 153 165 150 166
Co 21 20 21 18 21 21 19 21
Cr 239 252 202 169 231 222 221 241
V 89 127 114 116 110 118 98 121
Cathedral

C1 C8 C9 MT2 MT3 MT6 MT14 MT15


SiO2 57.76 54.91 53.90 55.90 53.89 54.59 52.20 54.48
TiO2 0.65 0.64 0.63 0.68 0.62 0.64 0.62 0.65
A1203 13.64 13.96 14.28 13.86 12.60 13.82 12.55 13.64
Fe203 5.44 5.50 5.53 5.76 5.20 5.40 5.15 5.50
MnO 0.11 0.12 0.11 0.12 0.10 0.10 0.11 0.11
MgO 4.14 4.18 4.22 4.69 4.42 4.05 4.25 4.07
CaO 9.22 9.13 9.02 11.49 11.67 8.48 11.33 10.22
Na20 1.47 1.28 1.12 1.51 1.48 1.08 1.52 1.40
K20 2.13 2.39 2.54 2.20 2.42 2.30 2.66 2.35
P205 0.25 0.27 0.21 0.25 0.26 0.21 0.28 0.25
LOI 5.2 7.63 8.45 3.54 7.34 9.32 9.32 7.33
Total 100 100 100 ! 00 100 100 100 100
Ni 143 148 148 161 143 145 133 142
Co 17 14 19 21 14 17 17 17
Cr 201 187 194 216 229 188 199 201
V 92 104 102 100 133 112 98 102
Santo Stefano Church (S.Stef)

SL36 SL37 SL39 SL40 SL41 SL46


SiO2 55.69 56.30 56.50 49.03 56.61 51.07
TiO2 0.72 0.67 0.72 0.68 0.71 0.67
A1203 14.32 13.37 15.07 14.51 15.47 15.57
Fe203 6.42 5.90 6.33 6.27 6.07 5.85
MnO 0.13 0.12 0.12 0.11 0.12 0.08
MgO 4.14 4.65 4.54 3.84 5.56 5.00
CaO 10.96 12.36 8.47 10.81 10.29 9.40
Na20 0.87 0.99 0.72 0.68 1.21 0.62
K20 2.31 2.05 2.46 2.30 2.08 2.48
P205 0.43 0.48 0.34 0.47 0.35 0.28
LOI 4.02 3.11 4.73 11.31 1.52 8.97
Total 100 100 100 100 100 100
Ni 144 140 151 152 155 159
Co 19 20 22 19 22 21
Cr 252 239 233 218 242 304
V 100 95 98 100 93 124

(Continued)
130 G. BIANCHINI ETAL.

Table 1. Continued

City Walls
* • . :, , * * *

1EG 7EG 9EG 17EG 19EG 22EG 33EG 35EG 37EG 40EG
SiO2 54.70 53.37 52.06 53.03 54.87 53.36 51.73 47.80 51.11 53.54
TiO2 0.74 0.70 0.76 0.73 0.79 0.69 0.64 0.69 0.73 0.70
A1203 16.16 14.47 16.80 15.94 16.78 14.92 13.95 14.96 15.80 15.26
Fe203 6.62 5.96 7.18 6.70 7.10 6.03 5.46 6.34 6.46 5.99
MnO 0.11 0.11 0.12 0.13 0.12 0.12 0.12 0.12 0.13 0.12
MgO 4.68 4.32 4.93 5.13 5.14 4.40 4.72 4.74 5.61 4.82
CaO 9.76 13.26 10.67 11.89 9.51 12.94 11.92 11.43 8.87 11.16
Na20 1.24 1.23 1.04 1.16 1.23 1.27 0.84 1.26 1.39 1.33
K20 2.48 2.09 2.66 2.38 2.55 2.24 2.59 2.52 2.50 2.22
P205 0.29 0.28 0.40 0.28 0.25 0.30 0.33 0.29 0.21 0.33
LOI 3.23 4.20 3.38 2.62 1.66 3.74 7.70 9.85 7.18 4.52
Total 100 100 100 100 100 100 100 100 100 100
Ni 179 159 199 197 195 157 144 166 185 165
Co 19 18 19 22 25 22 16 25 22 20
Cr 264 200 288 246 248 204 188 238 253 231
V 104 97 118 102 116 80 91 87 131 82
Santa Maria in Vado Church (SMV)
* * , * * *

SL25 SL26 SL27 SL28 SL29 N4 N 13 N20


SiO2 56.50 53.54 53.10 50.78 54.58 54.46 50.58 49.28
TiO2 0.70 0.74 0.68 0.65 0.70 0.72 0.67 0.60
A1203 16.08 16.95 14.30 14.92 15.46 16.34 14.66 12.78
Fe203 6.08 6.78 5.90 5.69 6.24 6.20 5.91 5.04
MnO 0.11 0.09 0.12 0.11 0.13 0.08 0.12 0.10
MgO 4.75 5.15 5.54 4.64 4.77 4.98 4.92 3.57
CaO 8.12 8.79 11.86 11.15 10.34 7.72 10.86 12.00
Na20 0.89 0.88 1.07 0.73 1.10 0.93 0.88 1.12
K20 2.47 2.72 2.02 2.63 2.14 2.76 2.48 2.06
P205 0.28 0.28 0.38 0.35 0.36 0.17 0.22 0.23
LOI 4.01 4.08 5.03 8.35 4.19 5.63 8.72 13.22
Total 100 100 100 100 100 100 100 100
Ni 148 187 156 150 160 164 159 112
Co 22 25 21 22 22 23 19 15
Cr 210 262 243 207 259 233 240 170
V 114 135 117 114 110 120 117 81
Schifanoia Palace (Schifa)
* * . , * * * *

SE 15P SE9P SE 19P SN6P SE20P SS5P SS4P SEIOP


SiO2 51.66 53.11 53.46 54.05 54.34 54.61 54.89 58.23
TiO2 0.70 0.76 0.73 0.68 0.71 0.75 0.76 0.80
A1203 14.77 15.49 15.30 14.35 14.83 15.26 15.40 14.78
Fe203 6.08 6.69 6.37 6.04 6.06 6.50 6.61 6.89
MnO 0.13 0.13 0.12 0.13 0.12 0.13 0.13 0.14
MgO 4.87 4.71 5.17 5.00 4.88 5.28 5.31 3.56
CaO 11.80 11.46 11.87 10.94 i 1.01 10.19 11.24 10.88
Na20 1.16 1.34 1.33 1.53 1.56 1.61 1.36 1.47
K20 2.34 2.42 2.19 2.31 2.10 2.36 2.43 2.59
P205 0.17 0.21 0.20 0.20 0.19 0.19 0.19 0.28
LOI 6.31 3.68 3.28 4.77 4.20 3.12 1.7 0.38
Total 100 100 100 100 100 100 100 100
Ni 155 162 172 154 153 169 181 152
Co 22 23 21 20 19 22 24 20
Cr 227 243 250 224 229 251 262 221
V 112 123 92 103 112 120 107 111

Symbols: *, bricks; = , cotto decorative elements.


Labels: StAPol, bricks and terracotta elements from the Monastery of Sant'Antonio in Polesine; SMV, bricks and terracotta elements from
the Church of Santa Maria in Vado; S.Stef, bricks and terracotta elements from the Church of Santo Stefano; Schifa, bricks and terracotta
elements from Schifanoia Palace; Cathedral, bricks and terracotta elements from the Cathedral of Ferrara.
FERRARA HISTORICAL BRICKS 131

Table 2. Major (wt%) and trace element (ppm) composition of natural sediments from the Ferrara surrounding
Low-Cr clay* High-Cr clay* Po river sands

SL8 SL9 SL10 SL14 SL4 SL16 SLI7 SL18 ME1 F5C2 F6C4 F8C4
SiO2 49.63 49.00 47.88 47.20 53.49 45.57 5 1 . 1 1 51.27 69.83 58.14 60.85 62.05
TiO2 0.75 0.75 0.72 0.68 0.72 0.67 0.70 0.74 0.36 0.39 0.41 0.41
A1203 1 9 . 0 5 1 8 . 4 6 1 7 . 6 3 15.90 20.96 1 4 . 9 4 1 7 . 0 7 17.94 9.51 1 0 . 7 2 10.37 9.96
Fe203 6.95 7.09 6.49 6.76 6.06 6.09 6.14 6.51 2.66 3.52 3.64 3.34
MnO 0.10 0.12 0.10 0.14 0.04 0.12 0.07 0.07 0.07 0.06 0.08 0.08
MgO 3.15 3.03 3.01 2.99 3.20 4.32 4.69 4.23 3.85 4.23 3.47 3.31
CaO 6.47 7.65 7.93 9.72 1.32 11.04 6.37 4.82 6.10 10.31 8.79 9.03
Na20 0.35 0.36 0.39 0.48 0.71 0.53 0.67 0.48 1.98 1.53 1.79 1.79
K20 3.38 3.37 2.99 2.58 3.38 2.22 2.51 2.67 1.98 2.07 2.03 1.91
P205 0.18 0.24 0.24 0.28 0.00 0.33 0.17 0.15 0.08 0.11 0.12 0.12
LOI 9.98 9.95 1 2 . 6 2 13.27 1 0 . 1 4 1 4 . 1 6 10.5 11.12 3.58 8.91 8.46 8.00
Total 100 100 100 100 100 100 100 100 100 100 100 100
Ni 82 82 80 89 112 145 155 162 83 96 87 81
Co 20 20 18 18 17 21 29 32 13 14 12 10
Cr 136 143 134 122 268 210 288 281 138 132 138 124
V 163 155 148 144 174 124 146 158 40 59 56 55
*Analysesfrom Bianchiniet al. (2002a).

soluble salts precipitated from Na-bearing more abundant than chlorite. The High-Cr sedi-
aqueous solutions. However, the common occur- ments have a coarser grain size and a lower abun-
rence of such Na20 excess appears to be unre- dance of clay minerals, with chlorite (Mg-rich
lated to the spatial distribution of the sampled chlorite in this group of samples) predominating
bricks, some of which were located indoors and over s m e c t i t e + m i x e d layers. Most of the
far from the floor (i.e. in a position not accessible studied Medieval or Renaissance bricks and ter-
to rain and/or ground water). Therefore, we racotta elements seem to have been prepared
suspect the addition of an 'exotic' Na-rich com- starting from High-Cr sediments, as these clays
ponent as a fluxing agent incorporated during the show a chemical affinity with the present-day
firing phase. In this regard, excluding feldspar- Po river sediments. The Low-Cr compositions
rich lithologies (no enrichment in A1203 is (recorded in only a few samples) are analogous
observed) and salts such as Na2CO3 (not avail- to the sediments of rivers flowing from the
able in the area and too expensive in Medieval Bolognese Apennines. This probably means
times), we speculate that either vegetable ash that Low-Cr clays were not available in the
(obtained by burning seaweed?; see Chapman Ferrara area at that time. It is plausible to
& Chapman 1980; Stiaffini 1999) or common assume that Low-Cr clays were introduced in
marine salt (NaCI) were used. Introduction of the area only after important hydraulic works in
the latter component would cause acceleration the 14th-16th centuries (Bondesan et al. 1995)
of mineral decomposition and subsequent crys- resulted in the diversion of some Apenninic
tallization of newly formed Ca-silicates. This torrent-rivers (e.g. the Reno river) into the
would lower the prograde chemical reactions southern branches of the Po river (which was
by c. 100-200 °C compared with those in flowing south of Ferrara at that time).
NaCl-free ceramic systems (Maggetti & Von The only two brick samples characterized
Der Crone 2004). by a Low-Cr affinity have to be considered as
To address the provenance of the materials outliers, possibly representing 'allochthonous'
used, trace elements such as Ni and Cr (Fig. 3) bricks probably made in neighbouring areas
indicate that the clay sediments around Ferrara where Reno river sediments were available.
can be separated into two groups characterized
by high (Cr > 1 8 0 p p m and Ni > 1 0 0 p p m ; Mineralogical composition of historical
High-Cr) and low (Cr <180ppm and
Ni < 1 0 0 p p m ; Low-Cr) contents. Bianchini bricks from Ferrara
et al. (2002a) showed that the Low-Cr sediments The mineralogical composition of the terracottas
are characterized by a higher proportion of clay was investigated by X-ray powder diffraction
minerals in which smectite + mixed layers are (XRD) carried out using a Philips P W I 8 6 0 / 0 0
132 G. BIANCHINI E T A L

200. • StAPol
++ +
raSMV
180.
+ ~.~<x+x ++ °SSmf
+ + x .~-w
~ + 160 0 Schifa

140
0 Cathedral ..
120
° City Warts +," + •
X Po Sands
100 × Low-Cr clay
10 x X + l"figh-Cr clay
80
X
60

40 Low-Cr clay
50 55 60 65 70 75
quadrant
Ig 20

16 0
14
0 4o 8o 120 160 2o0 240 280 320
12
Cr (m~)
• .-

o $ Fig. 3. Binarydiagram for Ni v. Cr. Symbols and labels


~ 6 +
xx as in Figure 2. Quadrants delimited by dotted lines are
4
+++
useful to identify the nature of the clay raw materials
2 ., (High-Cr v. Low-Cr),
0 . . . . ; . . . . ; . . . . ; . . . . ; " " , , I
50 55 60 65 70 75

(1) Carbonate-beating mineral assemblages


+
~x + (calcite _+ dolomite) with ubiquitous quartz,
35 illite/muscovite, biotite, iron oxides, alkaline
o feldspar and plagioclase. Amphibole has been
o~ xx detected, but it is not ubiquitous. M e l i l i t e _
wollastonite may also be present. These
x
J3 .... : .... : .... [ .... I''''I mineral associations have been recognized in
55 ~ 65 ~ 75 samples from the Monastery of Sant'Antonio in
Polesine, the Church of Santa Maria in Vado,
and the city walls.
(2) Clinopyroxene-bearing (carbonate-free)
mineral assemblages, with quartz, alkaline feld-
spar, plagioclase, iron oxides, melilite and wol-
~" 1.0 lastonite. Biotite and illite/muscovite are not
ubiquitous and amphibole is rare. These
mineral associations are typical for samples
0.0 .... '. . . . . I .... : .... I .... I
50 55 60 65 70 75 from the Church of Santo Stefano.
Si02 Ovt%)
Both mineral parageneses can be observed in
• SU~Pol }
the samples from the Ferrara Cathedral, and
0 SMV +H~Cf~ } mineral analyses are not yet available for
eSS~f Bricks and x Low-Or
d~ Natural
decorative elements sediments Schifanoia samples.
0 Still ~Po~
These mineral parageneses do not appear to be
• Cry Wds
consistent with the (CaO + MgO)-A1203-SiO2
phase diagram (Fig. 4) in which the stability
Fig. 2. Major element oxide bivariate diagrams. fields of firing phases are reported (Duminuco
Analyses recalculated to 100% on an H20-CO2 (LOI) et al. 1998; Riccardi et al. 1999; Artioli et al.
free basis. Low-Cr clay, clays characterized by 2000). In Figure 4 the historical terracottas
'Apennine' affinity; High-Cr clays, clays closely and the local clay composition plot mainly in
comparable with the present-day fine sediments of the the subtriangle Q z - W o ( D i ) - A n that corre-
Po river; other abbreviations as in Figure 1. sponds to the quartz-wollastonite (diopside)-
plagioclase equilibrium paragenesis. However,
the common presence of carbonates and/or meli-
lite (recorded by XRD in several samples)
diffractometer with graphite-filtered Cu-Ka radi- suggests that equilibrium conditions were not
ation (.A = 1.54 A). The diffraction patterns were attained. This can be ascribed to the inhomogen-
collected in the 20 angular range from 5 to 50=, eity of the original starting material, which
with 5 seconds per step (0.02: 20). Most consists of several micro-domains of different
samples can be attributed to two distinct composition, and indicates a limited mobility of
mineral parageneses (Bianchini et al. 2002b), the chemical species during the firing processes
as follows. (Duminuco et al. 1998; Riccardi et al. 1999).
FERRARA HISTORICAL BRICKS 133

SiO 2 (wt%)
Bricksand 'cotto' decorative //~
e l e m e n t s o f F e r r a r a historical / t\
buildings ~ ,

, " ii~

Wo" Di ..... ~l~errara lays


~

CaO+MgO(wt%) A120 3 (wt%)


Fig. 4. (CaO + MgO)-AI203-SiO2 phase diagram with compositions of historical bricks and terracotta elements
from Ferrara. Compositions of firing phases, such as wollastonite, diopside, melilite (gehlenite) and plagioclase
(anorthite), as well as relative tie-lines, are reported.

For the same reason, XRD bulk analyses ignored common felsic minerals (i.e. quartz and
cannot be considered completely reliable for feldspars) and focused investigation on acces-
the estimation of firing temperatures (Duminuco sory minerals, which provide more reliable
et al. 1998; Riccardi et al. 1999). This is evident insights into the raw material provenance as
when we consider some samples apparently well as clues to the firing temperatures.
characterized by 'misleading parageneses' con- In particular, micas (biotite and muscovite;
taining carbonate minerals (an indicator of Table 3) and amphiboles (Table 4) were
low firing temperature, i.e. < 850 °C) and clino- examined and compared with data on their
pyroxene and/or plagioclase (usually considered firing behaviour (i.e. temperature stability
high-temperature products, i.e. > 950 °C). fields; Maggetti et al. 1984; Capel et al. 1985;
Brindley & Lemaitre 1987; Dumunico et al.
1998; Riccardi et al. 1999; Cultrone et al.
Microanalysis of constituent phases 2000; Bianchini et al. 2002b).
The apparent incongruence in the recorded The K-poor composition of biotites (Table 3)
mineral parageneses can be examined using does not reflect a mineral destabilization
petrographic thin-section observation and in that occurs during the firing process. Similar
situ analytical techniques capable of investi- compositions are commonly observed in a wide
gating the reactions occurring in the various variety of sedimentary environments where
micro-domains. Microanalytical data have been pristine biotite crystals progressively release
obtained by: (1) scanning electron microscope potassium, ultimately leading to the formation
(SEM) at the University of Ferrara using a of hydrobiotite (Blum & Erel 1997; Murphy
Cambridge Stereoscan S-360 that provided et al. 1998).
semiquantitative analyses and sample images at In sample MT3 muscovite is colourless,
a scale of a few tens of micrometres; (2) electron whereas hydrobiotite is nearly opaque but still
microprobe analysis (EMPA) using a CAMECA homogeneous in composition, and amphibole is
SX-50 at the CNR-IGG Institute of Padova with characterized by a wide compositional range,
natural silicates and oxides as standards to which includes coarse and homogeneous crystals
provide quantitative analyses of the constituent of orange hornblende and edenite and brown par-
phases. gasite. Actinolite microcrystals have been found
Microprobe analyses were focused on coarse within the finer matrix.
detritic grains possibly representing traces of The orange colour of hornblende suggests oxi-
the sand fraction introduced as temper. Among dizing conditions and firing temperatures around
the mineral phases that constitute the sand we 800 °C, and the absence of destabilization
Table 3. Representative compositions of mica (muscovite and hydrobiotite) in historical bricks from Ferrara

Sample: MT3 MT 15

Mineral: Destabilization
Muscovite Hydrobiotite Muscovite Hydrobiotite products on
hydrobiotite

MT3p3c MT3p3d MT3p4c MT3p4d MT3p4f MT3pld MTI5 2a MTI5 2b MTI5 3a MTI5 3a* MTI5 lb MTI5 2 h MT15 21 MTI5 4a MTI5 4c

SiO2 53.23 48.51 29.36 28.70 27.62 26.30 46.58 47.71 50.23 47.75 32.10 28.66 27.95 59.52 84.99
TiO2 0.08 0.10 0.04 0.03 0.04 0.02 0.1 I 0.08 0.06 0.39 0.01 0.96 0.52 0.43 0.05
A1203 27.53 32.09 19.48 19.00 22.87 21.36 38.05 38.86 30.21 36.88 21.60 22.41 22.13 15.21 7.12
Cr203 0.00 0.04 0.05 0.05 0.02 0.03 0.00 0.00 0.00 0.04 0.00 0.01 0.05 0.06 0.00
FeO 3.48 1.93 28. I 1 28.33 27.62 30.3 i 0.33 0.34 1.25 0.86 22.71 24.12 24.56 9.98 1.04
MnO 0.01 0.00 0.05 0.08 0.14 0.28 0.07 0.02 0.09 0.00 0.29 0.02 0.04 0. I 0 0.07 >
7:
MgO 3.22 1.95 15.40 16.40 15.96 10.53 0.26 0.20 2.71 0.53 12.22 13.52 12.75 3.66 0.67 ¢3
CaO 0.10 0.11 0.22 0.38 0.03 0.97 0.32 0.18 0.8 i 0.03 0.37 0.32 0.42 0.06 0.03
Na20 1.41 0.85 0.97 0.87 0.66 1.05 1.90 1.18 2.91 0.98 !.96 1.93 2.18 !.59 1.05
K20 8.68 8.57 1.81 i.80 1.18 2.27 10.46 10.55 6.27 10.06 4.02 3.41 3.47 5.95 4.31 t~
Total 97.73 94.14 95.48 95.64 96.14 93.13 98.09 99.13 94.54 97.53 95.27 95.37 94.08 96.55 99.32
.r-,
Cations/I 1 oxygens
Si 3.44 3.23 2.27 2.23 2.11 2.14 3.01 3.04 3.31 3,09 2.43 2.20 2.19 Non-stoichiometric
Ti 0.00 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.02 0.00 0.06 0.03
AI 2. i 0 2.52 1.78 ! .74 2.06 2.05 2.90 2.91 2.35 2.81 1.93 2.03 2.05
Cr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Fe 0.19 0.10 1.82 1.84 1.76 2.06 0.02 0.02 0.07 0.05 i .44 1.55 1.61
Mn 0.00 0.00 0.00 0.01 0.01 0.02 0.00 0.00 0.01 0.00 0.02 0.00 0.00
Mg 0.3 ! 0.19 ! .78 ! .90 1.81 1.28 0.03 0.02 0.27 0.05 1.38 ! .55 1.49
Ca 0.01 0.01 0.02 0.03 0.00 0.09 0.02 0.01 0.06 0.00 0.03 0.03 0.04
Na 0.18 0.1 i 0.15 0.13 0.I0 0.17 0.24 0.15 0.37 0.12 0,29 0.29 0.33
K 0.72 0.73 0.18 0.18 0.12 0.24 0.86 0.86 0.53 0.83 0.48 0.33 0.35
Total 6.95 6.88 8.00 8.05 7.97 8.04 7.08 7.01 6.96 6.97 7,99 8.04 8.09
Atomic formula units (a.f.u.) on the basis of 11 oxygens,
FERRARA HISTORICAL BRICKS 135

Table 4. Representative compositions of amphibole in historical bricks from Ferrara

Sample: MT3 Experimental C1


trial
Mineral: Actinolite Hornblende Pargasite Edenite Actinolite actinolite
(fired at
MT3ple MT3plf MT3p3a MT3p3b MT3p2c MT3p2d MT3plb MT3plc clc 800 °C)

SiO2 58.56 5 7 . 0 1 48.52 47.73 43.02 43.20 48.72 47.79 57.90 56.03
TiO2 0.00 0.03 0.23 0.20 1.36 1.33 0.10 0.15 0.01 0.00
A1203 0.08 0.14 9.70 9.59 11.84 11.79 8.22 10.08 1.12 2.75
Cr203 0.00 0.06 0.09 0.20 0.07 0.04 0.00 0.00 0.11 0.29
FeO 3.78 3.46 11.85 11.83 15.06 15.27 13.81 14.81 5.85 5.94
MnO 0.10 0.10 0.19 0.30 0.18 0.20 0.34 0.39 0.22 0.15
MgO 22.20 21.58 1 3 . 8 6 1 3 . 7 5 10.35 9.94 12.74 11.95 20.83 19.69
CaO 13.33 1 3 . 5 7 1 2 . 7 9 1 2 . 5 5 1 1 . 8 2 11.50 9.92 9.49 12.01 12.27
Na20 0.21 0.11 0.98 1.03 1.30 1.42 2.45 2.53 0.65 0.95
K20 0.03 0.04 0.30 0.31 1.57 1.57 0.28 0.29 0.52 0.03
Total 98.30 9 6 . 1 1 98.50 9 7 . 5 1 96.58 96.26 96.57 97.47 99.20 98.11
Cations/24 oxygens
Si 7.59 7.99 6.97 6.95 6.50 6.56 7.18 7.00 7.45 7.79
Ti 0.00 0.00 0.03 0.02 0.16 0.15 0.01 0.02 0.01 0.00
A1 0.01 0.02 1.64 1.65 2.11 2.11 1.43 1.74 1.09 0.45
Fe 0.41 0.41 1.42 1.44 1.90 1.91 1.70 1.82 0.69 0.69
Mn 0.01 0.01 0.02 0.04 0.02 0.03 0.04 0.05 0.02 0.02
Mg 4.28 4.51 2.97 2.98 2.33 2.25 2.80 2.61 3.60 4.08
Ca 3.08 2.04 1.97 1.96 1.92 1.87 1.57 1.49 1.97 1.83
Na 0.05 0.03 0.27 0.29 0.38 0.42 0.70 0.72 0.27 0.26
K 0.01 0.01 0.06 0.06 0.30 0.30 0.05 0.05 0.13 0.01
Total 15.44 1 5 . 0 2 1 5 . 3 5 1 5 . 3 8 1 5 . 6 3 15.60 15.48 15.50 15.21 15.12
Atomicformulaunits on the basis of 24 oxygens.Amphibolenomenclatureaccordingto Leakeet al. (1997).

evidence indicates a temperature lower than clays, but not recorded at 900 °C; Fig. 5) would
900 °C (Maggetti et al. 1984). Moreover, the per- confirm that sample MT3 has been fired at a
sistence of actinolite (well equilibrated up to temperature between 800 and 900 °C.
800 °C in our firing experiments of the local The interpretation of the observed anhedral
crystals of epidote (approaching the ideal
Ca2(Fe,A1)3(SiOa)3(OH) composition; Table 5)
is not straightforward. This mineral is not
reported as a common firing phase in ceramics.
Its stability field appears to be confined at temp-
eratures lower than 550 °C, as suggested by
natural analogues in contact metamorphic para-
geneses (albite + epidote hornfels facies; Lentz
et al. 1995; Moor & Gunderson 1995; Singoyi
& Zaw 2001 ; Martfnez-Serrano 2002). Therefore
the observed epidote microcrystals may represent
relicts of coarser crystals present in pre-fired
mineral assemblages. This agrees with the pre-
sence of epidote in the sand fraction of sediments
from the Po river (Marchesini et al. 2000).
In sample MTI5 amphibole and epidote are
not detected, muscovite is still colourless and
hydrobiotite is totally destabilized. Microprobe
Fig. 5. Scanning electron micrograph of an actinolite investigation of hydrobiotite crystals indicates
amphibole in an experimental trial obtained by firing a that they are not homogeneous and stoichiometric
local clay at 800 °C. Chemical analysis of the same balanced compositions of hydrobiotite coexist
crystal by EMPA is also reported. with non-stoichiometric SiO2-A1203-K20-rich
136 G. BIANCHINI ETAL.

Table 5. Representative compositions of epidote in The observation of crystal habits (euhedral v.


historical bricks from Ferrara anhedral) is useful to discriminate between
phases originally present in the pre-fired mineral
Sample: C1 C1 C1 MT3
epidote epidote assemblage and neoformed phases (Fig. 6).
Within the fine matrix of sample MT15,
Mineral: Cla cld clg MT3p4e SEM analysis recorded extremely variable
compositions (in terms of Si, Ca, A1 and Mg;
SiO2 38.06 38.94 39.31 37.40 Figs 7 and 8). These analyses do not fit stoichio-
TiO2 0.06 0.14 0.08 0.01 metrically with potential firing phases (e.g. wol-
A1203 22.41 28.08 28.28 21.04 lastonite, melilite, clinopyroxene) and could be
FeO 13.00 5.25 5.60 13.55
MnO 0.09 0.06 0.15 0.19 interpreted as the compositions of glassy blebs.
MgO 0.07 0.06 0.07 0.00 The different glass compositions within the
CaO 23.93 2 4 . 5 8 24.58 22.68 same sample may be related to lack of equili-
Na20 0.05 0.04 0.03 0.00 brium melting, and result in the coexistence of
K20 0.01 0.05 0.04 0.00 different micro-domains that were not homogen-
Total 97.68 97.20 98.13 94.87 ized during the firing processes. This implies that
Cations/25 during the incipient partial melting, the compo-
oxygens sition of the neoformed melt phase (glass) is
Si 6.24 6.14 6.14 6.33 strongly influenced by the particular paragenesis
Ti 0.01 0.02 0.01 0.00 of each micro-domain.
AI 4.33 5.22 5.21 4.20 Microanalysis also revealed, in sample MT 15,
Cr 0.00 0.00 0.00 0.00 the presence of euhedral crystals of olivine
Fe 1.78 0.69 0.73 1.92
Mn 0.01 0.01 0.02 0.03 (Fig. 9). This may represent evidence for the
Mg 0.02 0.01 0.02 0.130 origin of the raw materials. The persistence of
Ca 4.20 4.15 4.12 4.11 olivine (a mineral very susceptible to weathering
Total 16.59 1 6 . 2 4 16.24 16.58 processes) in the mineral assemblage of the
starting sediments, together with the high
Atomic formulaunits on the basis of 25 oxygens. N i - C r clay content, suggests that sediments
from the Po (a river hydrological basin that con-
tains mafic and ultramafic rocks) may be the
compositions (Table 3). This sample is also source. This hypothesis is strengthened by the
characterized by the widespread presence of presence of olivine (Fig. 10) in experimental
glassy films within the fine matrix that brick trials manufactured in our laboratories
suggest a higher firing temperature compared using alluvial clays of the Po river.
with sample MT3 (probably approaching
1000 °C).
The persistence of carbonate cannot be used as C o n c l u s i o n s
an indicator of low firing temperature because In this paper, chemical and mineralogical
the reactivity of large crystals of carbonate (poss- characterization of bricks and terracotta elements
ibly introduced as temper) is often limited to from historical buildings and city walls of
surfaces and would allow carbonate preservation Ferrara has allowed us to evaluate the nature of
as a metastable phase at a higher temperature the original raw material (i.e. clay-rich sediment
than expected. Moreover, experiments show of local provenance) and to define technological
that not all CaO could combine with other information regarding the manufacture (i.e. firing
oxides to form new calc-silicate phases during temperatures between c. 800 and 1000°C).
firing. This would lead to rehydration of the This information provides guidelines for the
free CaO and the formation of secondary production and use of new bricks, tiles and terra-
calcite (Maggetti et al. 1984). Furthermore, cotta elements that are durable and compatible
carbonate could also be related to weathering with the historical materials. The proper pre-
processes that form 'secondary' calcite in servation of ancient architectural heritage is
microcracks and pores (Lopez-Arce & Garcia- extremely important and should be taken into
Guinea 2005). account during the restoration of damaged his-
Clinopyroxene and plagioclase cannot be con- torical masonries. This study shows that to
sidered as indicators of high firing temperature characterize the old materials and to establish
because they occur as accessory minerals in the causes of the decay, as well as to plan for
natural sediments of the Ferrara surroundings suitable protective or restoration treatment, it is
(Marchesini et al. 2000) and could have been necessary to identify and characterize the
present in the pre-fired mineral assemblage. materials that were used to make these
Ill I~I
Anhedral clinopyroxene

Spectrum 4

/
' ~ 'O~c~mtuge t 10~ "m~mmm~

) 2 4 8 8 t0 12
~1$c~e 2324 (:Is Ox$~: 9~198key (6 cts)

~'ig. 6. Scanning electron micrographs (and EDS spectra) of pyroxene crystals recorded in sample MT15; (a) euhedral orthopyroxene plausibly present in the pre-firing mineral
lssemblage; (b) anhedral clinopyroxene microcrystal in the matrix (plausible neoformation).
"• "%4. ""

°'* :>I-: :.,: t


..w ,m

*.',,,,;,. • QZ "

%'- N

/
4CIn 'l~c:lNnlm~ 1 ~i~ "llllln ~ I ,lleci~ I,inlo !

i ~ec~
2 3 6 s
Curs~. O.c40~,v~)ds)
6 ; 0
. . . . . . . .
gl
~'1
! Z 3 4 $
'd'8o~lOOec~ Curoct $~Jrl I~,,'~ms)
6 T O 9I t 3 •
tl OJeo¢,W~V
$
cb

~'ig. 7. Scanning electron micrographs (and EDS spectra) of silica-rich glassy patches within the matrix of sample MTI5.
FERRARA HISTORICAL BRICKS 139

~ 'a~m twpt • lq~ 'ea:mn~ t

Fig. 8. Scanning electron micrographs (and EDS spectra) of calcium-rich glassy patches within the matrix of sample MT15.

Fig. 10. Scanning electron micrographs of an olivine


crystal in an experimental trial obtained by firing a local
clay at 800 °C. Chemical analyses of the same crystal by
EMPA are also reported.

architectural elements. This gives the restorer


adequate information for choosing suitable new
materials when replacement is necessary and to
avoid incorrect restoration materials, such as
1 2 3 4 5 6 7 8 9 10
~e ~g61 ¢tS Cursor~ ;'o314 ~ V ( g d , ) were used in the Piazza Municipale of Ferrara,
where new floor tiles were totally damaged and
Fig. 9. Scanning electron micrographs (and EDS broken by f r e e z e - t h a w cycles during the first
spectrum) of a euhedral olivine crystal in sample MTI5. winter.
140 G. BIANCHINI ETAL.

L. Beccaluva and F. Siena are kindly acknowledged for composition and microstructure. Journal of Cul-
their preliminary review of the manuscript. The authors tural Heritage, 4(2) 91-99.
are also grateful to R. Tassinari (Universit/a di Ferrara) FERRI, R. & GIOVANNINI, A. 2000. Analisi dello
and R. Carampin (CNR-IGG, Padova) for their analytical sviluppo urbanistico della citth di Ferrara nel
assistance, and to the reviewers for their constructive quadro dell'evoluzione geomorfologica del
comments. territorio circostante. In: GALLINA, M. (ed.) Dal
Suburbium al Faubourg: evoluzione di una realt~
urbana. ET, Milan, 9-24.
References LEAKE, B. E., WOOLLEY, A. R., ARPS, C. E. S., et al.
AMOROSI, A., CENTINEO, M. C., DINELLI, E.