DEEPLY COLOURED AND BLACK GLASS IN THE NORTHERN PROVINCES OF THE ROMAN EMPIRE: DIFFERENCES AND SIMILARITIES IN CHEMICAL COMPOSITION BEFORE AND AFTER ad 150*

In this work we attempt to elucidate the chronological and geographical origin of deeply coloured and black glass dating between 100 bc and ad 300 on the basis of their major and trace element compositions. Samples from the western and eastern parts of the Roman Empire were analysed. Analytical data were obtained by means of a scanning electron microscope – energy‐dispersive system (SEM–EDS, 63 samples analysed) and laser ablation – inductively coupled plasma – mass spectrometry (LA–ICP–MS, 41 samples analysed). Among the glass fragments analysed, dark brown, dark purple and dark green hues could be distinguished. Only among the dark green fragments could a clear compositional distinction be observed between fragments dated to the periods before and after ad 150. In the early samples (first century bc to first century ad ), iron, responsible for the green hue, was introduced by using impure sand containing relatively high amounts of Ti. In contrast, a Ti‐poor source of iron was employed, containing Sb, Co and Pb in trace quantities, in order to obtain the dark green colour in the later glass samples. The analytical results obtained by combining SEM–EDS and LA–ICP–MS are therefore consistent with a differentiation of glassmaking recipes, detectable in glass composition, occurring in the period around ad 150.     

ELECTRON SPIN RESONANCE STUDY OF WHITE MARBLES FROM THARROS (SARDINIA): A REAPPRAISAL OF THE TECHNIQUE,POSSIBILITIES AND LIMITATIONS*

The characterization of various samples of white marble from the archaeological site of Tharros (Sardinia) is the starting point for the reexamination of the capabilities of electron spin resonance (ESR) spectroscopy as a tool for identifying the quarries of origin of ancient marble artefacts. Existing methods and data bases are employed for the assignment of our samples, but also reviewed to see if a more extensive use of the technique is feasible. It turns out that ESR spectroscopy, coupled with other available methods, may readily provide valuable information, often yielding the final answer to the problem of marble provenance. However, it is also clear that much work has still to be done to standardize the data collection and analysis procedures and to expand the available data base.     

ACCESSORY MINERALS AS TRACERS IN THE PROVENANCING OF ARCHAEOLOGICAL MARBLES,USED IN COMBINATION WITH ISOTOPIC AND PETROGRAPHIC DATA*

Thirty‐eight archaeological marbles (Roman and medieval) from Modena and Reggio Emilia (northern Italy) were provenanced using the accessory minerals as tracers and the results were compared with those inferred for the same artefacts using isotope composition and MGS (maximum grain size of calcite grains). The number of inferred possible sources is generally lower when using the mineralogical method, which therefore seems to be suited to marble provenancing.     

THE CHARACTERIZATION OF PAINTS AND WATERPROOFING MATERIALS FROM THE SHIPWRECKS FOUND AT THE ARCHAEOLOGICAL SITE OF THE ETRUSCAN AND ROMAN HARBOUR OF PISA (ITALY)*

This work presents the results of a diagnostic survey on the shipwrecks from the archaeological site of the ancient harbour of San Rossore (Pisa, Italy). The original waterproofing, caulking and painting materials were characterized by Fourier transform infrared spectroscopy (FTIR), gas chromatography – mass spectrometry (GC–MS), energy‐dispersive X‐ray microanalysis (EDX) and X‐ray diffraction (XRD). The major constituents of the waterproofing and caulking materials detected on the planks were tricyclic abietanes showing a high degree of aromatization. These compounds are indicative of a pitch obtained from the wood of trees of the Pinaceae family. The analysis of the organic components of the paint samples revealed diterpenoid acids characteristic of Pinaceae resins together with linear long‐chain alcohols and fatty acids, highlighting the presence of beeswax. Noticeably, the characteristic odd carbon number alkanes that are normally present in beeswax were not detected. The EDX and XRD analyses showed that hematite, calcite, cerussite and kaolinite were employed as pigments to paint the ships’ hulls.     

A QUANTITATIVE FABRIC ANALYSIS APPROACH TO THE DISCRIMINATION OF WHITE MARBLES*

Quantitative fabric analysis was applied in order to discriminate better among white marbles from various quarries of archaeological interest. This method provides an effective complementary tool to a characterization based upon petrography, cathodoluminescence microscopy and stable isotopes. Very good discrimination of marbles is achieved with the help of simple variables such as major axis and the shape-specific PARlS-factor. Using quantitative fabric analysis, marbles with similar cathodomicrofacies, as, for example, the Naxian quarries of Apiranthos, Koronos, Flerio and Kinidaros and the quarry of St. Beat (French Pyrenees), can be distinguished from each other. Marbles collected within one quarry may display dissimilar cathodomicrofacies. The common origin of such specimens can be determined with the aid of quantitative fabric analysis, as shown for the quarries of Kinidaros as well as St. Béat.     

MINERO‐PETROGRAPHIC AND GEOCHEMICAL CHARACTERIZATION OF ‘GRECO SCRITTO’ MARBLE FROM CAP DE GARDE,NEAR HIPPO REGIUS (ANNABA,ALGERIA)*

This work presents the results of the first mineralogical, petrographical and geochemical characterization of the marble quarried from the Cap de Garde headland, not far from Annaba (Algeria). This site is traditionally held by archaeologists to be the main source of supply of the so‐called ‘greco scritto’ marble, which was much used by the Romans for architectural and decorative–ornamental purposes, locally from the first century bc , and in Rome and central and southern Italy from the late Flavian period until the fourth century ad . The databank relating to the quarried material, created here for the first time, is used to establish the origin of ‘greco scritto’ found in six important Roman cities of North Africa: Hippo Regius and Cuicul (Djemila), in Algeria; Volubilis, in Morocco; Cyrene, in Libya; and Carthage and Utica in Tunisia. The results of this archaeometric study support the hypothesis (already put forward by authors) that the ‘greco scritto’used in the Roman Mediterranean originated from different sites, and suggest the existence of a number of North African quarries, also in the vicinity of Annaba.     

ANALYTICAL CHARACTERIZATION OF ROMAN PLASTERS OF THE ‘DOMUS FARINI’ IN MODENA*

The paper refers to the analytical characterization of Roman painted plasters dating back to the second century ad . The following techniques were used: optical microscopy (OM), scanning electron microscopy (SEM–EDS), micro‐Raman and Fourier transform infrared spectroscopies (µ‐Raman and FT–IR), X‐ray diffraction (XRPD), colorimetry and thermal analyses (TG/DTA). The investigation analysed the chemical composition and structure of the plasters, the chemical composition of the pigment layers, the use of binders and any chemical alteration of pigments as well as deterioration of the samples. Stratigraphic analysis of plasters allowed identification of their individual components, which proved helpful in finding out more about the mural painting technique employed.     

NON-DESTRUCTIVE ANALYSIS OF JINGDEZHEN BLUE AND WHITE PORCELAINS

The energy dispersive X-ray fluorescence method is used for the non-destructive qualitative analysis of Jingdezhen blue and white porcelains, which include the imperial wares of the Yongle, Xuande, Chenghua, Jiajing and Wanli periods of the Ming dynasty, the imperial wares of the Kangxi, Yongzheng, Qianlong, Jiaqing, Daoguang and Guangxu periods of the Qing dynasty, and those of the Republic and the contemporary period. The distribution pattern of the X-ray fluorescence intensities of the six characteristic elements for porcelain manufactured at different times has been investigated.     

THE CHEMICAL COMPOSITION OF BLUE PIGMENT ON CHINESE BLUE‐AND‐WHITE PORCELAIN OF THE YUAN AND MING DYNASTIES (ad 1271–1644)*

The chemical compositions of the glazes and pigments of 39 blue‐and‐white porcelains of Ming Dynasty date and three of Yuan date were examined by SR‐XRF. Both the analysis of the Fe/Mn ratio in the light blue areas of the glaze and a comparison of the Fe/Mn values between light blue, dark blue and clear glaze areas reveals that the samples can be divided into three groups. The results indicate that there are two significant changes of provenance of blue pigment during the Ming Dynasty and that some kinds of pigment were most probably imported from the Middle East. Considering literature records and other scholars’ studies, an outline picture of the pigment used on Chinese blue‐and‐white porcelain produced in Jingdezhen in the Yuan and Ming Dynasties is presented.     

MULTIVARIATE ANALYSIS OF THE ENERGY DISPERSIVE X-RAY FLUORESCENCE RESULTS FROM BLUE AND WHITE CHINESE PORCELAINS*

The energy dispersive X-ray fluorescence technique was employed to study non-destructively the surface of 66 samples of Chinese porcelain, of different periods and origins, and determine the contents of 13 chemical elements, namely, Ti, Mn, Fe, Co, Ni, Cu, Zn, Ga, Pb, Rb, Sr, Y and Zr. Principal components analysis was performed on these 13 variables, and scatter plots, incorporating the first, second and third principal components, used to study the clustering behaviour of the data. Based on these results, discriminant analysis was then performed on the data, and discriminant functions established for attributing the period and origin of the porcelains.     

THE PETROGRAPHY AND CHEMISTRY OF THIN‐WALLED WARE FROM AN HELLENISTIC– ROMAN SITE AT SEGESTA (SICILY)*

Samples of Roman thin‐walled ware from Segesta (northwestern Sicily), dating back to the early Imperial period, were studied by optical microscopy (OM) and Neutron Activation Analysis (NAA). Up to now, this class of Roman fine tableware has only occasionally been evaluated archaeometrically. Nevertheless, numerous production centres are believed to have been simultaneously active in the western Mediterranean area. Petrographic and chemical data seem to be in agreement with the archaeological hypothesis of local manufacture in Segesta for most of the analysed samples, through a comparison with kiln wasters and local raw materials. The effectiveness of thin‐section petrography for determining the provenance of such a tiny tempered class of pottery and the integrated use of two different grouping procedures (petrography and chemistry) were also tested.     

THE USE OF TRACE ELEMENT ANALYSIS OF ENTRAPPED SLAG INCLUSIONS TO ESTABLISH ORE – BAR IRON LINKS: EXAMPLES FROM TWO GALLO‐ROMAN IRON‐MAKING SITES IN FRANCE (LES MARTYS,MONTAGNE NOIRE,AND LES FERRYS,LOIRET)*

Knowledge of the iron trade in ancient times rests on determining the source of the objects recovered during archaeological excavations. Unfortunately, attributing the origin is not always possible using archaeological tools alone. Trace element data of the ore and the archaeological material (reduction and reheating slags, entrapped slag inclusions from the bloom, bar iron and iron blades) from two Gallo‐Roman iron‐making centres, Les Martys (Montagne Noire) and Les Ferrys (Loiret), were determined using ICP–AES/MS and LA–ICP–MS. The results highlight a continuity of composition that makes it possible to establish a link between the initial ore and the semi‐finished iron products.     

A MULTIDISCIPLINARY APPROACH TO THE CHARACTERIZATION OF ROMAN GRAVESTONES FROM AQUILEIA (UDINE,ITALY)*

The results of an archaeometric study on gravestone production in Aquileia (northeastern Italy) during Roman Republican times are reported here. The artefacts are made of limestone, quarried from the sedimentary sequence of the Trieste Karst (Carnican Alps, northeastern Italy), as testified by historical sources which refer to the ‘Roman Quarry’ at Aurisina. The rock types used for the gravestones are petrographically, geochemically and geochronologically homogeneous, and display similar faunal assemblages. In addition, their age is restricted to the Santonian – Lower Campanian. Comparisons between archaeological finds and rock specimens from various active and inactive quarries in this area suggest that quarrying during Roman Republican times was limited to a specific stratigraphic horizon of the sedimentary sequence, corresponding to the higher part of the ‘Roman Quarry’.     

ROMAN AND MEDIEVAL GLASS FROM THE ITALIAN AREA: BULK CHARACTERIZATION AND RELATIONSHIPS WITH PRODUCTION TECHNOLOGIES*

Compositional investigations were performed on 81 Roman and medieval glass fragments (first to 14th centuries ad ) from four Italian archaeological sites. The samples were soda–lime–silica in composition, with natron as flux for the Roman and early medieval glass samples, and with plant ash as flux for the late medieval ones. The varying colours are due to the differing FeO, Fe ₂ O ₃ , MnO and Sb ₂ O ₃ contents. Hierarchical cluster analysis identified six compositional groups related to age, which were compared with those found in the literature. In this way, technological continuity from the Roman to the early medieval period and the appearance of plant ash technology in the ninth century, 200 years in advance of the period previously believed, are demonstrated.     

PRODUCTION TECHNOLOGY OF ROMAN LEAD‐GLAZED POTTERY AND ITS CONTINUANCE INTO LATE ANTIQUITY

A broad selection of Roman lead‐glazed pottery dating from the first century ad through the fifth century ad was studied to establish locations of workshops and to address their technology of production. The ceramic bodies were analysed by ICP–AES. In addition, lead isotope analysis was undertaken on a selection of glazes. These findings suggested that there were several regions responsible for the production of lead‐glazed ceramics in the western Roman world, including central Gaul, Italy and, probably, Serbia and Romania. Using the body compositions as a starting point, the glazing techniques employed by each of the potential workshops were examined using electron probe microanalysis. It was determined that there were two primary methods of glazing. The first method used lead oxide by itself applied to non‐calcareous clay bodies, and the second method used a lead oxide‐plus‐quartz mixture applied to calcareous clay bodies. Based on these data for clay composition and glazing method, transfer of technology from the Hellenistic east to the western Roman world was proposed. Likewise, the inheritance of lead‐glazing technology into late antiquity was established by making comparisons to lead‐glazed ceramics dating to the seventh to ninth centuries from Italy, the Byzantine world and Tang Dynasty China.     

TRACE ELEMENT GEOCHEMISTRY OF NATIVE COPPER FROM THE WHITE PINE MINE,MICHIGAN (USA): IMPLICATIONS FOR SOURCING ARTEFACTS*

Eighty-five samples of native copper from the White Pine mine in upper Michigan were analysed by neutron activation to document geochemical variability within a single locality. Silver, sodium, antimony and scandium contents vary by two orders of magnitude, whereas arsenic values vary by three orders of magnitude. This variability reinforces the need for provenance studies of artefacts to examine sufficient samples to test for heterogeneity within the source area. The White Pine suite contains some of the most impure native copper that has been analysed to date. Arsenic and silver values of these impure samples overlap with those of European coppers, but consideration of several elements can still distinguish native copper from European copper.     

COOKING AND PAINTED WARE FROM SAN GIUSTO (LUCERA,FOGGIA): THE PRODUCTION CYCLE,FROM THE SUPPLY OF RAW MATERIALS TO THE COMMERCIALIZATION OF PRODUCTS*

Archaeological excavation at the San Giusto site (Lucera, Italy) has unearthed a Late Antique kiln that was most certainly dedicated to the production of cooking ware. An archaeometric study of numerous specimens of cooking and painted ware found at this site was carried out using optical microscopy, scanning electron microscopy, micro‐Raman spectroscopy, X‐ray diffraction, X‐ray fluorescence, inductively coupled plasma mass and optical emission spectrometry and instrumental neutron activation analysis. The integration of historical–archaeological data with archaeometric data has revealed that these specimens can be attributed to the San Giusto site. Furthermore, the production cycle of this ware can thus be reconstructed: from the diversified supply of raw materials (fluvial and marine sediments), to the relatively complex preparation of the paste, to firing at variable temperatures (600–750°C for cooking ware; 850–1050°C for painted ware).     

MULTI‐METHOD MARBLE PROVENANCE DETERMINATIONS: THE CARRARA MARBLES AS A CASE STUDY FOR THE COMBINED USE OF ISOTOPIC,ELECTRON SPIN RESONANCE AND PETROGRAPHIC DATA*

A multi‐method approach, based on petrography, stable isotope data and electron spin resonance spectroscopy for assigning the provenance of white marbles, is presented. A total of 11 experimental variables has been used, including the quantitative measurement of the sample colour and its homogeneity. On this basis we attempt to distinguish the three main quarrying basins of the Carrara district, that is, Torano, Miseglia and Colonnata. Such discrimination, extremely uncertain on the basis of the single techniques, may be performed with acceptable confidence’ using a properly selected subset of six petrographic, isotopic and spectroscopic variables. The final resubstitution and jackknifed re‐assignment rates are, respectively, 85% and 81%. Inclusion of the remaining five variables into the classification rule does not improve the results, but simply increases data overinterpretation. The practical possibility of using such an approach for more general provenancing problems is considered.     

PROVENANCE DETERMINATION OF LAVA FLAGSTONES FROM THE ROMAN ‘VIA CONSOLARE FLAMINIA’PAVEMENT (CENTRAL ITALY) USING PETROLOGICAL INVESTIGATIONS*

Trachyte lava flagstones from the northernmost stretch of the Roman ‘Via Consolare Flaminia’pavement and trachyte lavas from the most exploited quarries in Roman times were compared from a petrological point of view. ‘Via Consolare Flaminia’was the most important route used by the Romans to reach northern Italy and all the northern provinces of the Empire. A provenance for the flagstones as coming from the trachyte quarries of the Euganean Hills (Veneto region, northern Italy) is suggested by the similarity of both the fundamental mineral assemblage and the major trace element geochemistry. The location of the quarries of the Euganean Hills next to the harbours of the northern Adriatic Sea strongly supports the hypothesis that the Romans carried the flagstones by ship towards the coasts of the central Adriatic Sea.     

AN ASSESSMENT OF COMPOSITIONAL AND MORPHOLOGICAL CHANGES IN MODEL ARCHAEOLOGICAL GLASSES IN AN ACID BURIAL MATRIX

The degradation mechanisms of glass in a buried context result in surfaces that have been depleted in various elements. The stability of the glass is primarily affected by the burial environment and the glass composition. However, in all archaeological glasses, the corroded layer that is formed on the surface tends to be low in alkalis, high in silica and lacking in cohesion. The extent to which the material has degraded, along with the physical nature of the corrosion, has a profound effect upon a wide range of factors affecting the stability of artefacts, as well as the choice of conservation techniques to be employed. This study has a number of objectives: determination of the morphology of the surface of the leached layer in glasses of two different compositions with different surface finishes; examination of the transition between the corroded material and the unaffected substrate; and investigation of concentration profile of different elements within the surface layers, as a function of depth. The study uses two glasses, fabricated under laboratory conditions, to replicate two common glass types found in the historical environment; a soda–lime–silica glass typical of those found in the Roman period throughout the Mediterranean and northwestern Europe, and high‐lime–potash glasses typical of those of Western Europe in the late medieval period. Three different surfaces have been prepared to mimic alternative manufacturing techniques such as blown, cast and ground surfaces for each composition. The glasses have been corroded under controlled laboratory conditions to replicate the buried environment. Imaging and chemical information is obtained using SEM–EDX and morphological information using IFM to produce 3‐D mapping from topographical surfaces.