Appl. Phys. A 79, 221227 (2004) DOI: 10.

1007/s00339-004-2523-3

Applied Physics A
Materials Science & Processing

r. alaimo1 g. bultrini2 ` 2, u i. fragala r. giarrusso1 i. iliopoulos3 g. montana4

Archaeometry of sicilian glazed pottery

1 CEPA s.r.l.,

Palermo, Italy of Chemical Science, University of Catania, Italy 3 Department of Geology, University of Patras, Greece 4 Department of Chemistry and Physics of the Earth, University of Palermo, Italy
2 Department

Received: 1 October 2003/Accepted: 15 December 2003 Published online: 19 May 2004 Springer-Verlag 2004
ABSTRACT Petrographic and chemical analyses of the ceramic

body of 114 majolica artefacts manufactured in Sicily over a wide time range (16th-19th century) are presented. All the analysed samples, which belong to museums and private collections, were previously attributed to Sicilian workshops based on stylistic features evaluated by expert historians of art. Unambiguous identication of the production sites of majolica handicrafts in Sicily remains, however, open to question when this relies only on purely stylistic considerations. To this end compositional and/or textural markers have been searched for in the ceramic body of the majolica artefacts in order to differentiate between the centres of manufacture which were active in Sicily in previous centuries. The study of thin sections has allowed the characterization of the raw materials as well as the microscopic fabric of manufacture from four of the more relevant Sicilian production sites, namely: Caltagirone, Sciacca, Palermo and Santo Stefano di Camastra. Chemical data, including minor and trace elements, have been submitted to computer assisted multivariate statistical techniques. Principal component analysis (PCA) and linear discriminant analysis (LDA) have dened compositional ceramic reference groups and, consequently, have enabled a more realistic discrimination of provenance. These data have documented several imports of majolica from Naples, while the same artefacts were previously attributed to Sicilian workshops, based on stylistic considerations.
PACS 81.05.Je;

82.80.-d; 91.60.Mk

Introduction

Production of ceramic artefacts began in Sicily during prehistoric times. It continued without signicant pause in the pre-roman, roman and medieval periods and still remains active today. Motivations for this extensive ceramic production in the Sicilian territory are associated with the presence of extensive exploitable clay deposits and, at the same time, to the high level of skilfulness of local craftsmen which has developed over the centuries. The rst example of the Sicilian majolica was the so called proto-majolica, the distinctive features of which were the
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high quality of both the glazed coating and the clay body. Sicilian majolica drives its roots into the rich cultural background created by the arabian-norman (9th-12th AD) and swabian (13th AD) dominations. The most relevant manufacturing centres, located in the central-eastern part of the island (Gela, Siracusa and Caltagirone), were strongly inuenced by decorative motifs of arabian inspiration [1]. Starting from the 16th century, the production of Sicilian majolica was expanded with the manufactories of Palermo, Sciacca, Burgio, Collesano and Naso where the synergistic coexistence of arabian, renaissance and baroque stylistic inuences gave rise to the production of superb works of art. At the end of the 18th century, the majolica production of western Sicily, especially of tiles, gradually diminished both in quality and quantity because of the large importation from Naples (central Italy). Nevertheless, in the same period, a new production of majolica took place at Santo Stefano di Camastra, on the Tyrrhenian coast of eastern Sicily [1]. Surprisingly, even though the sicilian ceramic production in the medieval and post-medieval age played an important role in the whole Mediterranean basin, information on the chemical and mineralogical characteristics of these manufactures is at present inadequate. In fact, in the great majority of the studied cases, the precise chronological/spatial positioning of a given majolica artefact (that is to say place and period of production) is, at the moment, generally dened by an expert art historian, whose evaluation is based on the style of decoration (association of pigments and ornamental design). Only in recent times, has a systematic scientic study (archaeometry) of sicilian pottery been carried out, aiming at a rational classication of local productions, namely understanding of manufacturing techniques and characterizing the composition of the raw materials [24]. In several casestudies, however, the distinction between autochthonous and imported artefacts still remains an open question. Stylistic considerations simply based on macroscopic observations either of decorations or of forms are often not adequate to establish unambiguously both the site and the production techniques of the ceramic artefact. In the present work a petrographic and chemical study has been carried out on 114 majolica artefacts (oor tiles and vases) dating from the 16th to the 19th centuries. These artefacts, belonging to both museums and private collections, had

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Supposed provenance Palermo Caltagirone Sciacca S. Stefano di C. Trapani
TABLE 1

been attributed by specialist art historians to certain manufacture centres in Sicily: Caltagirone, Palermo, Sciacca, Trapani and Santo Stefano di Camastra. The analytical approach in the present study was rst aimed at the denition of compositional and/or textural markers for each relevant sicilian majolica workshop. Then, analytical results were used to create an apposite data-base of the composition of ceramic-bodies made of sicilian clayey raw materials. In addition, chemical data were processed with multivariate statistical procedures to assess the possibility of grouping or discrimination for the different ceramic pastes in terms of site-related compositional features. Finally stylistic-based provenances were compared and contrasted with analytical-derived provenances to assess the reliability of attributions made by art historians.
2 Experimental

Sample frequency 18 42 19 17 18

Tipology

Age

Floor tiles Floor tiles (6), plates and vessels (36) Floor tiles Floor tiles Floor tiles

17th-19th cent. 16th-19th cent. 16th-17th cent. 19th-20th cent. 18th-20th cent.

Sicilian majolica: types, age and historical-artistic provenance

Most of the present majolica artefacts were supplied by the Museo Regionale della Ceramica of Caltagirone, the rest by private collectors. Prototypical examples are displayed in Fig. 1. These have been selected considering both typologies, stylistic relevance and historical periods (Table 1). Fairly representative portions (4 6 g) of the ceramic bodies were sampled using an appropriate water-cooled circular saw to obtain cross sections. All the collected samples were analysed by optical microscopy (OM) and X-ray uorescence (XRF) to obtain mineralogical, petrographic and chemical information. Microscopic examination by transmitted polarized light was carried out on thin-sections using a Jenapol 30G-0060 microscope. The main goal was to discriminate among groups of majolicas having similar ceramic bodies. This discrimination was in terms of typology and relative frequency of crystalline aplastic constituents as well as in terms of textural properties including the grain packing and size distribution. In addition, attention was paid to the optical properties of the groundmass as well as to relics of limestone fragments and/or calcareous microfossils formed because of the incomplete thermal dissociation during the ring process [5, 6]. Chemical analyses (XRF) were carried out on the ceramic body with a Philips PW1400 WDS spectrometer. As reference materials for matrix effect correction and calibration lines USGS, IAEA and NBS sets of international stan-

dards (silicate rocks, soils, brick clays, lacustrine sediments) were used. Nine major elements (Si, Al, Ca, Mg, Fe, Na, K, Ti, and Mn) and some minor and trace elements (Rb, Sr, Y, Zr, Cr, Ni, V, Ba, La, and Ce) were determined following inter-laboratories calibrated procedures carefully described elsewhere [7]. Chemical data were submitted to a computer assisted multivariate statistical treatment by cluster analysis (PCA) and linear discriminant analysis (LDA).
3 3.1 Results and discussion Petrography

The analysis of thin sections under the polarising microscope allowed grouping of the 114 samples of majolica into ve distinct petrographic classes (hereafter labelled groups 1, 2, 3, 4, and 5). The parameters used to establish petrographic groups referred to the mineralogical composition of aplastic constituents (temper) and to the groundmass as well as to various textural aspects (grain size distribution, packing, sorting and temper morphology). Samples included in each petrographic group 1 5 show strong analogies in terms of the above mentioned features of the ceramic body. A petrographic group can be considered as representative of the ceramic paste of a specic production centre. This represents a suitable criterion only in a given geographical/geological context, for a narrow chronological interval and for a particular typology/use of artefacts. Compositional and textural characteristics of the 5 recognized petrographic groups are summarized in Table 2 and can be described as follows: Group 1 (21 samples) is characterised by a packing of aplastic constituents (temper) ranging from 5 to 15%

Samples Distribution Packing Group 1 Group 2 Group 3 Group 4 Group 5 21 37 18 15 23 5%15% 10%15% 5%10% 3%10% 5%10% Size vfs vfs cs-ms vfs vfs

Distinguishing features Aplastic inclusions Mineralogy quartz, micrite clots, chert, quartzarenite fragments quartz, K-feldspar, plagioclase rounded quartz grains quartz, K-feldspar, mica, metamorphite fragments quartz, orthoclase, sanidine, plagioclase, clinopyroxene, volcanic fragments

Groundmass

isotropic with red colour, frequent decomposition casts isotropic with green colour, common decomposition cast heterogeneous texture

Legend: vfs = very ne sand (0.060.125 mm); ms = medium sand (0.250.5 mm); cs = coarse sand (0.51.0 mm)
TABLE 2

Results of petrographic analysis through the optical microscope

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FIGURE 1 Prototypical majolica oor tiles: a Palermo 18th century b Caltagirone 16th century c Sciacca 17th century d Santo Stefano di Camastra 18th century e Trapani 18th century

(area), with a moderate degree of sorting. Grain size is mainly variable from coarse silt (< 0.06 mm) to very ne sand (0.06 0.125 mm). Mineralogical composition is given by quartz (predominant) and minor amounts of feldspars, chert and quartzarenite grains. A distinctive characteristic of the samples belonging to this group is represented by the substantial presence of micrite clots (1520% area) and/or macropores both deriving from the thermal decomposition of calcareous lithoclasts (bioclasts, microfossils and limestone fragments). Pores are characterized by evident reaction borders (Fig. 2a). Group 2 (37 samples) is characterized by homogeneously distributed temper with a 1015% aplastic packing. The grain size distribution is quite uniform, thus mainly falling in the class of very ne sand (0.06 0.125 mm), with a maximum grain diameter of 0.15 0.2 mm. Aplastic inclusions are pre-

dominantly composed of quartz. Subordinate constituents are K-feldspar (orthoclase, microcline), plagioclase, chert and micas (mainly biotite). Amphibole was only sporadically detected (Fig. 2b). Group 3 (18 samples) is characterized by the presence of a distinctly bimodal grain size distribution, with modes corresponding with coarse silt (< 0.06 mm) and medium sand (0.25 0.5 mm). The total content of aplastic inclusions ranges from 5 to 10%. Their mineralogical composition is almost exclusively represented by quartz with occasional K-feldspar grains (Fig. 2c). The roundness of quartz grains varies from angular to subangular for the ne sand class (0.125 0.25 mm) and from subrounded to rounded in the coarse sand class. The groundmass is optically inactive with frequent cast pores probably caused by thermal decomposition of calcareous fossils (foraminifera and bivalves).

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FIGURE 2 Polarizing microscope microphotographs (crossed nicol; scale bar = 0.2 mm) showing fabrics corresponding to the recognized ve petrographic groups a Group 1 b Group 2 c Group 3 d Group 4 e Group 5

Group 4 (15 samples) presents scarce aplastic grain packing (about 35%) mainly falling into the very ne sand size category (0.06 0.125 mm). Quartz is the prevalent mineralogical phase while K-feldspar (orthoclase and microcline), plagioclase, micas and fragments of metamorphic rocks are subordinate components (Fig. 2d). The groundmass shows an evident heterogeneous structure probably due to coarse mixing of two different kind of clays. Group 5 (23 samples) is characterized by a moderate packing of aplastic constituents (510%) with very ne size (0.06 0.125 mm) and a relatively low sorting (area distribution). These inclusions consist of prevalent quartz and of a relatively minor quantity of K-feldspar (sanidine, orthoclase, and microcline), plagioclase, micas, chert, diopsidic pyroxene and volcanic lithics (Fig. 2e). It is worth noting that such volcanic aplastic components, with the presence of bulky and heuedral crystals of sanidine, might represent a distinctive character for provenance hypothesis.
3.2 Assessment of provenance hypothesis

The analysis of the results of optical microscopy observation for the ceramic bodies following historical-artistic classication previously mentioned, in the large majority of the majolica samples, gives identical conclusions. Namely each petrographic group can be safely related to a specic manufacturing site. In other words a satisfactory matching between stylistic and petrographic attribution has been found as shown in Table 3. Therefore, samples stylistically accepted as manufactured in Palermo show the compositional and textural characteristics described for petrographic Group 1. The large majority of majolica attributed to Caltagirone manufacture fall in Group 2 and almost all the samples of Group 3 had been previously assigned to Sciacca. Similarly, a large majority of samples with the petrographic characteristics of Group 4 had been proposed as being from S. Stefano di Camastra. Finally, all the samples belonging

Manufacture centre Palermo Caltagirone Sciacca S. Stefano di C. Trapani Naples

Stylistic attribution (individuals) 18 42 19 17 18 0

Petrographic attribution (individuals) 21 37 18 15 0 23

It has been already mentioned (vide supra) that all the majolica samples submitted for petrographic analysis were previously attributed to ve well known sicilian manufacturing centres (Palermo, Caltagirone, Sciacca, Santo Stefano di Camastra and Trapani) by means of stylistic criteria mostly based on the glaze decoration (motifs, design and association of pigments).

TABLE 3 Number of majolica samples (individuals) assigned to each stylistic and petrographic category

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to Group 5 had been stylistically attributed to the Trapani manufacture. The observed correlation found between petrographic groups and stylistic classications cannot be considered accidental. Therefore the peculiarities of each petrographic group were compared with mineralogical and textural characteristics of clayey raw materials occurring in the territory of the considered production centres [810] to x all the possible connections with the characteristics of raw materials occurring in the same locations. As a matter of fact, the petrography of the ceramic pastes of Groups 1 4 has been found in close agreement with that of related raw materials historically exploited for majolica production, respectively, in the manufactures of Palermo, Caltagirone, Sciacca and Santo Stefano di Camastra. The only exception is represented by petrographic Group 5. In fact, the corresponding ceramic paste is characterized by the presence of volcanic minerals (sanidine and clinopiroxene) and lava fragments which are denitely not compatible with clayey raw materials found in the territory of Trapani and, in general, with the lithology of the area. Aplastic inclusions of Group 5 have closer resemblance to those known for manufacture from Naples which, starting from the 15th century, represented a ourishing majolica production centre [11, 12].
3.3 Establishing production sites by chemical data processing

per while CaO (with negative loading) the calcareous content of the clayey raw material. The rst principal component appears to be the most important factor in distinguishing between chemical groups. Variables with positive loadings separate Naples (Group 5) and Santo Stefano di Camastra (Group 4) productions, while variables with negative loadings separate Caltagirone manufacture (Group 2). Based on PC1 inuences, both the Palermo (Group 1) and the Sciacca (Group 3) have similar scores. The second principal component (PC2) allows the separation between these latter groups to a minor extent. The third component (PC3) allows a sharp separation between Group 1 and Group 3. The unambiguous identication of production sites by chemical data processing has required application of linear discriminant analysis (Fig. 5). In this case, compositional groups and corresponding production sites become clearly differentiated into well dened cluster. There is, therefore, evidence that reference petrographic groups also represent reliably homogeneous chemical groups. These results can be considered the starting point for future research aiming towards the increase in knowledge about this intriguing matter by providing new data either about the presently considered sicilian manufactures or about other as yet unstudied majolica production centres.
4 Conclusions

Computer assisted multivariate statistical analysis was performed on chemical compositional data of ceramic bodies. The raw chemical data for the samples are available upon request from the authors. The purpose of multivariate processing was the appraisal of compositional groups (PCA) as well as the determination of distinctive features in terms of statistical canonical variables (LDA) for each of the above manufacturing centres. The latter discriminant functions, once established, certainly may represent a reference parameter for provenance studies of the main production sites of majolica in Sicily, beside petrographic analysis [13, 14]. The results of the principal component analysis (PCA) are shown in Figs. 3 and 4. In the space dened by the rst two components PC1 and PC2, which account for the 43% of the total variance (Fig. 3), the samples of majolica previously attributed to Naples production (petrographic Group 5) can be easily distinguished from those made either in Caltagirone (Group 2) or in S. Stefano di Camastra (Group 4). Clusters representing majolica manufactured in Palermo (Group 1) and Sciacca (Group 3) show superimposed elds. Nevertheless, extraction of the third component (PC3), which account for 13% of total variance, produces separation between these two groups of samples (Fig. 4). It is useful to consider loading variables, reported in Table 4, for each considered principal component in order to identify chemical elements which are more efcient in determining the separation between groups. For example, in the rst component (PC1), Al2 O3 , K2 O and Rb (with higher positive loadings) might represent feldspatic-micaceous tem-

In this study a total of 114 ceramic bodies of majolica artefacts, manufactured in Sicily in different times from the 16th to the 19th AD, were investigated by optical microscopy (OM) and X-ray uorescence (XRF) in order to identify their compositional and textural markers. The petrographical, mineralogical and textural analyses have allowed the grouping of these ceramic materials into ve distinct categories whose petrographic features are strictly related to those of the sicilian clayey formations found in well dened, separate locations. In four cases (Caltagirone, Sciacca, Palermo and S. Stefano di Camastra) a perfect cor-

Variable SiO2 Al2 O3 CaO MgO Fe2 O3 Na2 O K2 O TiO2 MnO Rb Sr Y Zr Cr Ni Ba La Ce V

TABLE 4

PC1 -0.26 0.94 0.63 0.10 0.34 0.15 0.72 0.34 0.21 0.78 0.34 0.21 0.23 0.21 0.70 0.56 0.58 0.55 0.55

PC2 0.49 0.67 0.23 0.24 0.63 0.23 0.45 0.77 0.44 0.42 0.01 0.45 0.58 0.32 0.23 0.15 0.38 0.31 0.47

PC3 0.01 0.05 0.22 0.57 0.43 0.46 0.14 0.67 0.19 0.04 0.68 0.30 0.05 0.67 0.19 0.41 0.35 0.36 0.39

Factor loadings for the majolica samples data set

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FIGURE 3 Principal component analysis performed on XRF compositional data from sicilian majolica samples. Projection on the plane formed by the PC1 versus PC2 factor scores

FIGURE 4 Principal component analysis performed on XRF compositional data from sicilian majolica samples. Projection on the plane formed by the PC1 versus PC3 factor scores

FIGURE 5 Linear discriminant analysis (LDA) of the studied majolica samples

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REFERENCES

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respondence has been found with provenance studies proposed by historians. Only the group of ceramic artefacts, previously assigned to the production centre of Trapani based on stylistic criteria, has been found to have microstructural characteristics entirely different to the mineralogical features of the clay raw materials available in that area. By contrast, the results of the present petrographical study suggest provenance from Neapolitan production, thus demonstrating a remarkable trade of Neapolitan tiles toward western Sicily. Furthermore, chemical compositional data for ceramic bodies, submitted to computer assisted multivariate statistical analyses (PCA and LDA), have conrmed the same grouping obtained by petrographic examinations and have allowed the denition of compositional ceramic reference groups useful to locate the provenance of the sicilian majolicas. Finally, from an archaeometric point of view the results indicate that the present experimental approach that combines the modern multivariate statistical analysis techniques and minero-petrographical investigation, can be a powerful analytical tool in the archaeological provenance studies of potteries.
ACKNOWLEDGEMENTS The Science and Technology Park of the Sicilian Regional Government (PSTS, Italy) and MIUR (Ministry of Italian University Research) are gratefully acknowledged for their nancial support for Progetto Terrecotte .

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