INVESTIGATION OF ELECTRON PARAMAGNETIC RESONANCE PEAKS IN SOME POWDERED GREEK WHITE MARBLES*

Within the context of white marble provenance research, 42 powdered white Greek marbles have been characterized using electron paramagnetic resonance (EPR) spectroscopy. Phase analysis was first carried out to separate calcitic and dolomitic marbles, then EPR spectra of Mnuc were studied. Investigation of other marble EPR spectra, especially around g — 2.00, led us to characterize five different signals. The intensities of Mn²⁺ lines permit the separatum of eight quarries into two groups, allowing a first discrimination, in the g = 2,00 region, only one signal has been found to be useful for provenance research objectives. The results are cheering and should lead to many other similar experiments.     

NMR as a new tool for cultural heritage application: The provenance of ancient white marbles

Identifying the origin of marble used in antiquity brings back to light details of the economic, social and political organization of classical societies, and characterizing in depth the chemistry of marble is key to discovering its provenance. Beyond X‐ray diffraction, which could reveal the presence of discriminant secondary crystalline phases and the quantification of accessory minerals combined with a multivariate analysis approach, solid‐state nuclear magnetic resonance (NMR) enables one to recognize the local structure arrangement of both crystalline and amorphous materials by looking at one or more selected atoms. In present paper targets the ¹³C nuclide, and thus the major component of marble, calcium carbonate. Whatever their geological origin, marbles ¹³C‐NMR spectra present only one resonance corresponding to the carboxyl function whose intensity and line width vary from one marble to another. If the variation of the NMR signal intensity observed is the result of great T1 variations (from 220 to 5300 s) and is linked to iron content, the line width reflects defects in the calcite crystal in which calcium has been replaced by another element such as magnesium, aluminium or strontium. The specific profile of the NMR signal has been used successfully to help determine the origin of some archaeological items.     

THE PROPERTIES AND IDENTIFICATION OF MARBLE FROM PROCONNESOS (MARMARA ISLAND,TURKEY): A NEW DATABASE INCLUDING ISOTOPIC,EPR AND PETROGRAPHIC DATA*

This paper reports an updated and enlarged archaeometric database of Proconnesos marbles with the aim of attaining more reliable inter‐ and intra‐site identification. Quarry and artefact samples (n = 397) from 23 different quarrying areas were characterized using petrographic, isotopic and EPR results. The most distinct property of Proconnesos marbles is their extremely weak EPR intensity, associated with the low concentration of Mn²⁺impurities. This feature, supported by the contribution of other important isotopic and petrographic variables, forms the basis for the correct identification of Proconnesos marbles. Within the site the distribution of properties is relatively homogeneous; only limited intra‐site discrimination is possible. All the experimental results, as well as the quarry samples are made available to other researchers willing to measure additional experimental properties, thus increasing the rate of within the site discrimination. Extensive survey has proved that, although about 10% of the samples exhibit maximum grain size below 1.0 mm, no locations exist where fine grained marbles could be intentionally quarried. The historical aspects of Proconnesos marble quarrying and usage are also discussed.     

Response of cathodoluminescence of alkali feldspar to He+ ion implantation and electron irradiation

Cathodoluminescence (CL) of minerals such as quartz and zircon has been extensively studied to be used as an indicator for geodosimetry and geochronometry. There are, however, very few investigations on CL of other rock-forming minerals such as feldspars, regardless of their great scientific interest. This study has sought to clarify the effect of He+ ion implantation and electron irradiation on luminescent emissions by acquiring CL spectra from various types of feldspars including anorthoclase, amazonite and adularia. CL intensities of UV and blue emissions, assigned to Pb²⁺ and Ti⁴⁺ impurity centers respectively, decrease with an increase in radiation dose of He⁺ ion implantation and electron irradiation time. This may be due to decrease in the luminescence efficiencies by a change of the activation energy or a conversion of the emission center to a non-luminescent center due to an alteration of the energy state. Also, CL spectroscopy of the alkali feldspar revealed an in-crease in the blue and yellow emission intensity assigned to Al-O^?-Al/Ti defect and radiation-induced defect centers with the radiation dose and the electron irradiation time. Taken together these results indicate that CL signal should be used for estimation of the α and β radiation doses from natural radionuclides that alkali feldspars have experienced.     

WHITE,VEINED MARBLE FROM ROMAN AMMAIA (PORTUGAL): PROVENANCE AND USE

A multimethod approach using petrography and strontium (Sr) isotopic analysis was applied to determine the geological source of 17 marble artefacts from the Roman town of Ammaia (Portugal). All samples are calcitic, with dolomite, quartz and muscovite as accessory minerals. The marbles are characteristically medium‐grained with a maximum grain size (MGS) between 0.98 mm and 1.82 mm, have a heteroblastic texture, and have curved to embayed calcite grain boundaries. ⁸⁷Sr/⁸⁶Sr values of marble leachates range from 0.708488 to 0.708639. Comparison with Hispanic and Mediterranean marbles suggests the Estremoz Anticline as the most likely source for the Ammaia marble, especially for architectural marble. This hypothesis is supported by the geographical proximity of the Estremoz marble district and the long and expensive overland transport required for other marbles to reach Ammaia.     

ON THE WHITE AND COLOURED MARBLES OF THE ROMAN TOWN OF CUICUL (DJEMILA,ALGERIA)

This paper reports the results of an archaeometric study of the local and imported marbles found in the Roman town of Cuicul (now Djemila, Algeria), a research project funded by the Sixth Framework Programme of the European Union. Of the few imported coloured lithotypes that have been found, four are of Greek origin and one was imported from Asia Minor. In addition, two other classical Roman coloured stones found on the site are probably of local North African origin (most likely one from Numidia and one from Algeria). With regard to the grey and white marbles employed in the statuary and architecture, petrographic study in thin section and the δ¹³C and δ¹⁸O isotopic data emphasize the frequent use of the local fine‐grained lithotype from Filfila (Skikda) together with imported Greek lithotypes (i.e., Pentelic marble, the dolomitic variety of Thasian marble, and Parian marble from Lakkoi) as well as different varieties of the so‐called ‘greco scritto’, whose provenance in some cases still remains uncertain. In fact, the petrographic and geochemical features of the marbles do not always match those known for the classical ‘greco scritto’ from the quarry of Cap de Garde, near Annaba (Algeria).     

A Petrographic Study of the Anthropomorphic Stelae from the Megalithic Area of Saint‐Martin‐De‐Corléans (Aosta,Northern Italy)

The Megalithic Area of Saint‐Martin‐de‐Corléans (Aosta, northern Italy) consists of anthropomorphic stelae dated to the Copper Age and the beginning of the Early Bronze Age. They were carved in different lithologies of varying provenance according to two successive artistic styles, ‘ancient’ and ‘evolved’. A minero‐chemical and a petrographic investigation were carried out on 47 stelae and on reference samples collected from eight different outcrops, aiming to define the provenance of the stone materials. The variety of rocks used for the manufacture of the stelae reflects the geological complexity of the Aosta Valley. Most of the stelae examined were classified as foliated impure marbles, grey banded marbles (‘Bardiglio’), calcschists and metabasites belonging to the Combin Zone (Piedmont Nappe), which outcrops in close proximity to the Megalithic Area. Some stelae of the evolved group consisted of massive marbles with silicate‐bearing layers, attributed to the Sion–Courmayeur Zone. Similar stone materials were reported for the stelae of the same age found at the archaeological area of Petit Chasseur (Sion, Switzerland). This is archaeometric confirmation of the archaeological affinity between the stelae occurring at the two prehistoric sites, supporting the hypothesis of cultural exchanges over the Grand St Bernard Pass since the Early Copper Age.     

The Architectural Reuse of Roman Marble and Stone Spolia in the Early Medieval Monte Sorbo Church (Sarsina,Central Italy)

We present the results of a multi‐method archaeometric study concerning the architectural elements reused in Monte Sorbo church (Sarsina, central Italy) between the eighth and ninth centuries AD . The provenance study has focused on classical marbles and stones, which clearly do not originate from the local Apennine geological formations and are thought to come from extra‐regional sources. A large fraction of the tested marbles is from Asia Minor, coming from both the Proconnesian district on Marmara Island and, probably, the Hasançavuslar site near Ephesus (Greco scritto). Of the four remaining marbles investigated, one is from the Carrara district and three are from different Greek quarrying areas, such as Mount Pentelikon (Athens) and the Thasos and Paros islands. The data also highlight the reuse of decorated gravestones made of Pietra di Aurisina as architectonic elements. This limestone is a fossiliferous carbonate stone outcropping in the Trieste Karst region (north‐eastern Italy), which was exploited by both the Romans and the Byzantines. The assignment of all of the columns of the central nave to the same source area provides an argument in favour of their provenance from a single monument, which was probably located in Sarsina or Ravenna, with the ‘colourful taste’ that is typical of the late Antonine and Severian periods.     

A NEW METHOD FOR THE DETERMINATION OF THE PROVENANCE OF WHITE MARBLES BY CHEMICAL ANALYSIS OF INCLUSION FLUIDS: THE MARBLES OF THE MAUSOLEUM OF BELEVI/TURKEY*

A new method is presented in this paper to pinpoint the origin of white marbles using the chemical analysis of fluids occurring as micro-inclusions in calcitic or dolomitic marbles. Beside the conventional methods usually applied for this purpose, the analyses of significant anions and cations in fluids extracted from white marbles were used to characterize different types of marbles. Using this new approach it is possible to distinguish different groups of marbles which cannot be separated isotopically. A case study was performed on the mausoleum of Belevi, close to Ephesus in Turkey, and the quarries in the area of the mausoleum. The marbles used for the architecture of the mausoleum cannot be distinguished isotopically but were split into two groups when using fluid inclusion analysis. The corresponding quarry for the high-quality marble (cella walls, columns etc.) turned out to be the Kentli Çiftliği quarry, which also supplied the marbles for the classical Artemision. According to the chemical and fluid data it can be shown, however, that neither the adjacent famous antique quarry of Belevi nor the underground mine of Kusini, some 5 km away from the mausoleum, are the sources for the marbles used for the construction or decoration of the mausoleum.     

Source and character of syntaxial hydrothermal calcite veins in Paleoproterozoic crystalline rocks revealed by fine‐scale investigations

Calcite veins in Paleoproterozoic granitoids on the Baltic Shield are the focus of this study. These veins are distinguished by their monomineralic character, unusual thickness and closeness to Neoproterozoic dolerite dykes and therefore have drawn attention. The aim of this study was to define the source of these veins and to unravel their isotopic and chemical nature by carrying out fine‐scale studies. Seven calcite veins covering a depth interval of 50–420 m below the ground surface and composed of breccias or crack‐sealed fillings typically expressing syntaxial growth were sampled and analysed for a variety of physicochemical variables: homogenization temperature (T_h) and salinity of fluid inclusions, and stable isotopes (⁸⁷Sr/⁸⁶Sr, ¹³C/¹²C, ¹⁸O/¹⁶O), trace‐element concentrations (Fe, Mn, Mg, Sr, rare earth elements) and cathodoluminescence (CL) of the solid phase. The fluid‐inclusion data show that the calcites were precipitated mainly from relatively low‐temperature (T_h = 73–106°C) brines (13.4–24.5 wt.% CaCl₂), and the ⁸⁷Sr/⁸⁶Sr is more radiogenic than expected for Rb‐poor minerals precipitated from Neoproterozoic fluids. These features, together with the distribution of δ¹³C and δ¹⁸O values, provide evidence that the calcite veins are not genetic with the nearby Neoproterozoic dolerite dykes, but are of Paleozoic age and were precipitated from warm brines expressing a rather large variability in salinity. Whereas the isotopic and chemical variables express rather constant average values among the individual veins, they vary considerably on fine‐scale across individual veins. This has implications for understanding processes causing calcite‐rich veins to form and capture trace metals in crystalline bedrock settings.     

New data of 87Sr/86Sr ratio in classical marble: an initial database for marble provenance determination

⁸⁷Sr/⁸⁶Sr ratios are presented for white marbles collected from some of the most famous classical quarry areas of the Mediterranean: Carrara, Paros, Naxos, Pentelikon, Dokimeion, Hymettus, Thasos, and Proconnesus. These ratios range from 0.7071 to 0.7092. The ranges of the different quarry areas are notably superimposed; this prevents a common adoption of this parameter in distinguishing the quarry locations for the classification of the provenance of marbles used during classical times for architectural and sculptural artefacts. However some quarry areas show peculiar distributions of their isotopic values, which could help to assign the provenance to an unknown marble artefact.Adding these new data to the scarce number of strontium isotopic compositions measured on white marbles and available in the relevant literature, permits the creation of an initial database of 11 classical quarry locations. This database confirms that the strontium isotope ratio could be used in marble provenance determination, together with petrographic and geochemical methods, as an ancillary technique.     

AN UPDATED,MULTI‐METHOD DATABASE OF EPHESOS MARBLES,INCLUDING WHITE,GRECO SCRITTO AND BIGIO VARIETIES*

An updated database of Ephesos marbles including 244 samples from 16 quarrying districts is reported. The unknown Greco Scritto quarries near Hasançavuslar and the Bigio marbles from the quarries of Belevi and of Mt Panayir are also presented. The paper, however, is mostly devoted to the identification of the Ephesos white marbles, whereas the problems posed by the Bigio and Greco Scritto varieties are deferred to future work. The samples have been characterized by isotopic analysis, EPR spectroscopy and additional petrographic and optical properties. Owing to the complex geology of the region, the white marbles of Ephesos exhibit rather inhomogeneous properties and are conveniently classified into four marble groups, which can be almost completely discriminated. The problem of distinguishing the Ephesos white marbles from other similar varieties has been dealt with by statistically comparing the Ephesos samples with all the similar, medium‐grained varieties present in the marble database. Although some of the four Ephesos groups can be reliably identified, general solution of the discriminant problem is difficult. Historical archaeological information is needed to reduce the complexity of the problem by eliminating unlikely provenances. In this way relevant problems, such as the discrimination between Ephesos and Proconnesos marbles, can be solved.     

Cultural Heritage Documentation and Conservation: Three-Dimensional (3D) Laser Scanning and Geographical Information System (GIS) Techniques for Thematic Mapping of Facade Stonework of St. Nicholas Church (Pisa,Italy)

This article reports the mapping of the stones, including marbles and brick masonry, used for building the facade of the medieval Church of St. Nicholas (XI century ad), one of the most interesting churches in Pisa, due also to the nearby famous octagonal bell tower. Mapping of stone materials was performed using a computer-aided design (CAD)/geographical information system (GIS) software package for storing and processing spatial information of the ashlars, obtained using three-dimensional (3D) laser-scanning data, combined with high-resolution images, and stone-to-stone observations. Based on collected data, the facade of the Church of St. Nicholas appeared mostly composed of rocks belonging to the metamorphic Tuscan sequence, quartzites, and marbles from Mt. Pisano area. Other types of rocks were also observed, as black limestones quarried at some kilometers northwest from Pisa in the Monti d’Oltre Serchio area, white Apuan marbles and Macigno sandstones. Conversely, intarsia appeared mainly made up of serpentinite and, subordinately, red limestones laid in white Apuan and Mt. Pisano marbles.     

COMPOSITION PROFILES AND TIME EVOLUTION OF BURIED MARBLE PATINAS BY LA–ICP–MS AND LASER‐INDUCED MICRO‐PHOTO‐LUMINESCENCE

The present work aims to study surface composition profiles on buried marbles as well as their time evolution. Fifty samples from gravestones, buried for up to 80 years, were analysed by laser‐induced photoluminescence and LA–ICP–MS. The results include profiles of ²⁵Mg, ²⁷Al, ⁵⁵Mn, ⁵⁷Fe, ⁸⁸Sr and organic complexes of calcium, existing in the marble patina. The depth at which ⁸⁸Sr reaches its bulk value proved to be the best parameter to measure patina thickness. A diffusion model adopted from dissolution studies made on gravestones exposed to the atmosphere was successfully applied to the patina thickness data. The model fails to predict patina thicknesses for ancient excavated objects. However, it seems that ‘Sr alteration depth’ values alone can be used for discriminating ancient from recently buried surfaces.     

The Asiatic marbles of the Hadrian's Villa at Tivoli

Multi-method provenance studies, including petrographic, isotopic, electron paramagnetic resonance and trace chemical analyses, have been carried out on 20 white, 9 black and 1 red artifacts purposely selected to investigate the use and distribution of sculptural marbles at the Hadrian's Villa. A large fraction of the marbles tested (21 samples, 70%) are shown to be from Asia Minor, mostly originating from the recently discovered site of Göktepe near Aphrodisias (15 or 71%). All the 9 black samples investigated and 6 out of 11 white Asiatic marbles are from Göktepe, the remaining being Docimium marble from Iscehisar (4 samples) and Aphrodisias marble from the city quarries (1 sample). The single red sculpture tested proved to be Carian red marble from the Iasos quarries, whereas non-Asiatic marbles include 3 Carrara and 6 Pentelicon samples. The selection of marbles tested is preliminary and incomplete, but, despite this, the results are noteworthy, especially since the marble of other sculptures from the Villa has already been identified as Göktepe. Together with other published results, the marble distribution at the Hadrian's Villa seems to suggest that the use of sculptural marbles in the Roman world underwent considerable changes around the turn of the 1st and the 2nd century AD. The evidence supporting this hypothesis is briefly summarized in the conclusions.     

CARBON AND OXYGEN ISOTOPE RATIOS OF MARBLES FROM SOME ANCIENT QUARRIES OF WESTERN ANATOLIA AND THEIR ARCHAEOLOGICAL SIGNIFICANCE

¹³C/¹²C and ¹⁸O/¹⁶O ratios have been measured for 42 marbles from the main quarry localities of archaeological interest of Western Anatolia (Marmara, Ephesos, Aphrodisias, Denizli and Afyon) in order to test the possibility of isotopically characterizing ancient marbles from this region. The various groups of samples are not clearly distinguishable on a δ¹³C-δ¹⁸O diagram. However, if only white or slightly coloured samples are considered, the isotopic method appears to be much more selective.     

PETROGRAPHIC AND ISOTOPIC CHARACTERIZATION OF THE MARBLE OF THE ISLAND OF TINOS (GREECE)*

Most outcrops of good‐quality crystalline marble in Mediterranean countries were exploited in Greek and Roman times. Hence, a wide variety of marble is now found in archaeological excavations. The precise determination of the provenance of a marble object is of great archaeological importance, and is now mostly obtained by coupling the petrographic study of a thin section with the analysis of the C and O stable isotopes, or by stereomicroscopy and EPR. The existing databases are considerable but still insufficient, because our knowledge about and study of ancient Mediterranean quarries remain incomplete. The contribution of this research is to add new petrographic and isotopic data on small quarries on the Greek island of Tinos that were exploited in antiquity. This marble belongs to the same geological horizon; it is quite pure, sometimes dolomitic and characterized by a low‐T, high‐P metamorphism that produced a limited recrystallization (MGS varying from 0.64 to 2.50 mm) on marine limestone protoliths. The petrographic features are quite distinctive: the fabric is strongly lineated and often stressed; and the accessory minerals are ubiquitary quartz, ore minerals, graphite and muscovite. As far as the isotopic data are concerned, δ¹³C_PDB varies from 1.1 to 2.7, and δ¹⁸O_PDB from ?1.7 to ?11.4. Both the features and the data have been compared with those of similar marbles used in antiquity, showing that their combination mirrors the fingerprint of the Tinos marble.     

Petrographic Characterization and Provenance Determination of the Crystalline Marbles Used in the Roman City of Banasa (Morocco): New Data on the Import of Iberian Marble in Roman North Africa

This paper reports the results of an archaeometric study of the crystalline marbles used in the Roman city of Banasa (Morocco). On‐site surveys allowed a detailed inspection of the monuments of the ancient city and sampling of the different marble lithotypes used for architectural purposes and sculptures. The inventory was completed by the study of both the grey‐and‐white streaked or spotted marble items stored in the warehouse of the archaeological site and of those currently exhibited at the National Archaeological Museum of Rabat. Provenance determination of 28 samples was carried out by means of a multi‐method approach combining mineralogical–petrographic data and C–O stable isotope analyses as the first step, and cathodoluminescence microscopy as a complementary technique to verify possible unusual alternative origins of some marbles. The analytical results obtained were compared with both the most reliable international databases and the few available studies dealing with the use of marble in other Roman towns in Morocco (e.g., Volubilis, Thamusida and Sala‐Chellah). They point to a variety of classical marble sources such as Carrara, Mount Penteli, Paros, Marmara and probably Mount Filfila (Algeria), and prove a significant import of Iberian lithotypes.     

Origin of palaeo‐waters in the Ordovician carbonates in Tahe oilfield,Tarim Basin: constraints from fluid inclusions and Sr,C and O isotopes

Petrographic features, isotopes, and trace elements were determined, and fluid inclusions were analyzed on fracture‐filling, karst‐filling and interparticle calcite cement from the Ordovician carbonates in Tahe oilfield, Tarim basin, NW China. The aim was to assess the origin and evolution of palaeo‐waters in the carbonates. The initial water was seawater diluted by meteoric water, as indicated by bright cathodoluminescence (CL) in low‐temperature calcite. The palaeoseawater was further buried to temperatures from 57 to 110°C, nonluminescent calcite precipitated during the Silurian to middle Devonian. Infiltration of meteoric water of late Devonian age into the carbonate rocks was recorded in the first generation of fracture‐ and karst‐filling dull red CL calcite with temperatures from <50°C to 83°C, low salinities (<9.0 wt%), high Mn contents and high ⁸⁶Sr/⁸⁷Sr ratios from 0.7090 to 0.7099. During the early Permian, ⁸⁷Sr‐rich hydrothermal water may have entered the carbonate rocks, from which precipitated a second generation of fracture‐filling and interparticle calcite and barite cements with salinities greater than 22.4 wt%, and temperatures from 120°C to 180°C. The hydrothermal water may have collected isotopically light CO₂ (possibly of TSR‐origin) during upward migration, resulting in hydrothermal calcite and the present‐day oilfield water having δ¹³C values from ?4.3 to ?13.8‰ and showing negative relationships of ⁸⁷Sr/⁸⁶Sr ratios to δ¹³C and δ¹⁸O values. However, higher temperatures (up to 187°C) and much lower salinities (down to 0.5 wt%) measured from some karst‐filling, giant, nonluminescent calcite crystals may suggest that hydrothermal water was deeply recycled, reduced (Fe‐bearing) meteoric water heated in deeper strata, or water generated from TSR during hydrothermal water activity. Mixing of hydrothermal and local basinal water (or diagenetically altered connate water) with meteoric waters of late Permian age and/or later may have resulted in large variations in salinity of the present oilfield waters with the lowest salinity formation waters in the palaeohighs.