SHAFT‐HOLE AXES FROM SLOVENIA AND NORTH‐WESTERN CROATIA: A FIRST ARCHAEOMETRIC STUDY ON ARTEFACTS MANUFACTURED FROM META‐DOLERITES*

A group of Copper Age shaft‐hole axes from Caput Adriae (northeastern Italy, western Slovenia and northwestern Croatia) manufactured using meta‐dolerite have been analysed for major and trace elements. All the samples show magmatic textures and well recognizable relicts of primary mineralogical phases. Petrographic observations suggest an ophiolitic provenance of the protolithic source(s) while geochemical data indicate that the original magmas originated in a fore arc or pre arc tectonic setting. Strong similarity has been found with several lithotypes from the Banija Ophiolite Complex (Croatia), here indicated as the most probable source area. Considering the available archaeometric data about shaft‐hole axes found in northern Italy and Caput Adriae in comparison to those of axe blades discovered in the same area, it emerges that there is a utilization of different rock types, the source of which appears to be quite close to the discovery sites. In the investigated area the shaft‐hole axes are largely made from ophiolitic‐related rocks which are associated with copper deposits. Consequently there may have been a relation between the localization of the geological sources of shaft‐hole axes and the development of metallurgical activities.     

SHAFT‐HOLE AXES FROM CAPUT ADRIAE: MINERALOGICAL AND CHEMICAL CONSTRAINTS ABOUT THE PROVENANCE OF SERPENTINITIC ARTEFACTS*

The change of raw materials used to produce stone axes during the Neolithic to Copper Age transition in northeastern Italy, central and western Slovenia and northwestern Croatia (Caput Adriae) has been recently linked to the development of early European metallurgy. Serpentinite shaft‐hole axes occur commonly in the archaeological context of this region and their rounded irregular shape suggests that the raw material was mainly sourced from secondary deposits. The aim of the present study is to characterize with multiple analytical methods, including synchrotron radiation, the axes and locate the primary outcrop(s) of raw materials and related secondary exploitation areas. All the analysed artefacts are manufactured from peridotites and probably pyroxenites completely metamorphosed in greenschist facies and characterized by antigorite, diopside and magnetite, sometimes rimmed by penninite. Mineralogical and petrographic data exclude most Eastern Alps outcrops as possible raw material sources, thus limiting the research to the Hohe Tauern. Chemical data reveal a close homogeneity for the peridotite‐derived axes and therefore demonstrate a selection of the most suitable raw material for axe production. Provenance from Hohe Tauern and related secondary deposits of the Drava River hydrographical system agrees with previous studies, as this region is rich in copper ore deposits, which have been exploited since prehistory.     

A STUDY OF GLASS BEADS FROM THE HALLSTATT C–D FROM SOUTHWESTERN POLAND: IMPLICATIONS FOR GLASS TECHNOLOGY AND PROVENANCE*

Eighty‐one samples taken from 68 glass beads found in southwestern Poland on sites of the Lusatian culture from the Hallstatt C and Hallstatt D subphases were analysed by EPMA. A subsample of 18 of these were additionally subjected to analysis by means of LA–ICP–MS in order to validate the results obtained by EPMA. Some glass was made using mineral soda and some using plant ash rich in sodium. Both high‐magnesium soda–lime glass (HMG) and low‐magnesium soda–lime glass (LMG) were identified. A large number of samples are characterized by low MgO content and medium K₂O content (LMMK glass), combined with low concentrations of CaO and high Fe₂O₃ and Al₂O₃. All the LMMK glass contains numerous silica crystals and inclusions composed of a number of elements (most frequently Cu, Co, Sb, As, Ag, Ni and Fe). The LMMK glass was presumably made in Europe during the Hallstatt C.     

First large‐scale provenance study of pigments reveals new complex behavioural patterns during the Upper Palaeolithic of south‐western Germany

The use of red iron‐based earth pigments, or ochre, is a key component of early symbolic behaviours for anatomically modern humans and possibly Neanderthals. We present the first ochre provenance study in Central Europe showing long‐term selection strategies by inhabitants of cave sites in south‐western Germany during the Upper Palaeolithic (43–14.5 ka). Ochre artefacts from Hohle Fels, Geißenklösterle and Vogelherd, and local and extra‐local sources, were investigated using neutron activation analysis (NAA), X‐ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that local ochre sources were continuously and systematically accessed for c.29 500 years, with periodic events of long‐distance (about > 300 km) ochre acquisition during the Aurignacian (c.35–43 ka), suggesting higher mobility than previously suspected. The results reveal previously unknown long‐term, complex spatio‐temporal behavioural patterns during the earliest presence of Homo sapiens in Europe.     

ARCHAEOMETRIC INVESTIGATIONS OF SGRAFFITO CERAMIC TILES (FIFTEENTH‐SIXTEENTH CENTURIES) RECOVERED FROM EXCAVATIONS IN UDINE (NORTH‐EAST ITALY)*

Most of the Renaissance sgraffito tiles excavated in Udine (Italy) constitute a homogeous group, the tile body having a CaO/MgO molar ratio ?= 3:2. They were produced using a dolomite‐ and calcite‐containing clay fired at 900–950°C. A small group of samples, with a lower firing temperature and a CaO/MgO ratio ?= 2:3, was probably produced in a different factory. Slip and transparent glaze, characterized by optical microscopy and inductively coupled plasma atomic emission spectrometry, are an illite‐rich clay and a lead silicate, respectively.     

THE FIRST ARCHAEOMETRIC CHARACTERIZATION OF ROMAN MILLSTONES FOUND IN THE AQUILEIA ARCHAEOLOGICAL SITE (UDINE,ITALY)*

An archaeometric study of all the Roman millstones preserved today in the National Archaeological Museum of Aquileia, the ancient capital of the X Regio Augustea –‘Venetia et Histria’ located on the Friuli plain (northeastern Italy), has been recently envisaged to define their geological–geographical provenance. We present here the results of the first step of the research, which is aimed at characterizing all of the definitely allochthonous lithologies. In order to carry out petrography on thin‐section and geochemical analyses, 10 small samples were picked out directly from Pompeian‐style millstones (catilli and/or metae) and rotary querns. Five different lithologies originating in various Italian regions were recognized: eight samples consist of pale‐ and dark‐grey lavas from the Venetian Volcanic Province, Vulsini Volcanic District (Latium), Etna Volcano and Pantelleria island (Sicily), whereas two samples were shown to be made of green garnet‐bearing schists (pietra ollare) from the Western Italian Alps. The presence of Alpine pietra ollare in northeastern Italy, used to produce pots and food containers, was established for numerous classical findings at Roman and Middle Age sites, but the analysed items represent the first evidence for the utilization of this kind of stone to produce mills during the Roman epoch.     

A MULTI‐ANALYTICAL APPROACH FOR THE CHARACTERIZATION OF COMMODITIES IN A CERAMIC JAR FROM ANTINOE (EGYPT)*

This paper describes a multi‐analytical chemical study performed on the original, almost totally conserved, content of a small ceramic jar from the Antinoe archaeological site (fifth to seventh centuries ad, Roman Egypt) and now belonging to the archaeological collection of the Istituto Papirologico ‘Girolamo Vitelli’ (Florence, Italy). Scanning electron microscopy with an energy‐dispersive X‐ray spectrometer (SEM–EDX), Fourier transformed infrared spectroscopy (FTIR) and X‐ray diffraction (XRD) were all used to characterize the inorganic components of the archaeological material. The organic substances were analysed using FTIR, direct exposure mass spectrometry (DE–MS) and gas chromatography – mass spectrometry (GC–MS). The inorganic component essentially consisted of halite (NaCl). Among the NaCl crystals, lamellar elements were identified. They were chemically characterized by carbonato‐apatite and showed a concentric morphology typical of the scales of small fish. The most prevalent organic constituents of the sample were monocarboxylic acids, α,ω‐dicarboxylic acids, and cholesterol and its oxidation products. The organic material composition was consistent with the occurrence of lipids of animal origin. In addition, diterpenes related to pine pitch were also identified. The overall results suggest that the material recovered in the small ceramic jar found in Antinoe is a residue of fish‐based pickles such as garum, muria, allex and liquamen, which were commonly used in Roman times.     

Portuguese Blue‐on‐Blue 16th–17th Century Pottery

Blue‐on‐blue (‘berettino’) sherds have appeared in numerous production and consumption archaeological excavations in Lisbon and other archaeological sites in Portugal (dated from the mid‐16th century to the beginning of the 17th century). The abundance of this interesting faience led us to compare it with similar pottery from other well‐known production centres in Italy, namely Liguria (Savona and Albisola), Spain (the Triana kilns) and the Low Countries. Differences in the diffraction patterns of the sherds' pastes from the four countries were observed. In most samples, cobalt blue silicate (cobalt olivine) was identified in the dark blue or light blue glazes through the use of micro‐Raman spectroscopy and diffuse reflectance spectra. A remarkable difference in the calcite contents of the Lisbon and Seville pottery sherds was observed, in accordance with previous observations of high calcite contents of Seville ceramics. A comparison was also made for all of the blue‐on‐blue sherds studied here with many other 16th–17th century sherds from Lisbon using bivariate plots of K/Si versus Ca/Si. Lisbon and Seville pottery behave very differently, whereas sherds from Italy and the Low Countries occupy intermediate positions.     

A STUDY ON LATE MEDIEVAL TRANSPARENT‐GLAZED POTTERY AND ARCHAIC MAJOLICA FROM ORVIETO (CENTRAL ITALY)*

Nineteen samples of medieval transparent‐glazed pottery and archaic majolica from Orvieto (central Italy) were studied. They were classified by archaeological criterion as follows: five transparent‐glazed fragments with green and brown decorations (first half of the 13th century), eight green transparent‐glazed fragments (13th century) and six tin‐glazed fragments with green and brown decorations (second half of the 13th century). SEM–EDX, XRD (the Rietveld method) and XRF were used to characterize the chemical and mineralogical compositions both of the bodies and the coatings. In all of the samples, the paste is Ca‐rich with CaO contents as high as 13–20 wt%. The mineralogical composition is compatible with a firing temperature of about 950°C, which is the typical temperature reached in a wood kiln. No difference was observed between the bodies of transparent‐ and tin‐glazed pottery. In the case of transparent glazes, the burial conditions lead to heavy weathering of the samples. However, on the basis of the analyses carried out in non‐weathered areas, the typical composition is PbO 55–65 wt%, SiO₂31–35 wt%. In tin glazes, the tin is scattered on the mass of the glaze as SnO₂crystals with a concentration of 7–14 wt%. Concerning the decorations, it is established that the green colour is due to the presence of copper, while manganese is responsible for the brown colour. These pigments, which represent the typical colours of ‘archaic majolica’, are spread through the glaze homogeneously, apart from one case in which there is clear evidence of manganese oxide crystals.     

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’.     

NEOLITHIC ‘GREENSTONE’ AXE BLADES FROM NORTHWESTERN ITALY ACROSS EUROPE: A FIRST PETROGRAPHIC COMPARISON*

Neolithic polished stone axe blades, manufactured with uncommon lithologies such as Alpine eclogites, jades and other HP metaophiolites, were exploited from primary and secondary occurrences in Piemonte and Liguria and dominate the north Italian and south‐east French polished stone blades used as functional tools (for deforestation and woodworking). In other European countries the same lithologies are found less frequently or only occasionally as axe blades; in north‐west Europe they were frequently used for manufacturing ceremonial axes that have shapes that are not present in the Italian Neolithic tradition. This paper undertakes a preliminary examination of the case, prevalently from a petrographic point of view, comparing the well‐established Italian petroarchaeometric knowledge with the rather poorer petrographic basis of the European eclogite/jade axes. A provisional picture of the distribution of these axes in Europe is provided and some interim interpretations and open problems are discussed.     

ARTIFICIAL OR NATURAL ORIGIN OF HEMATITE‐BASED RED PIGMENTS IN ARCHAEOLOGICAL CONTEXTS: THE CASE OF RIPARO DALMERI (TRENTO,ITALY)

This study concerns those crystallographic and microstructural features that can provide indications on the actual origin of red pigments based on hematite (Fe₂O₃). The main features of natural and artificial hematite are recalled and used to discuss the results obtained from the characterization of red‐ochre samples coming from the Palaeolithic site of Riparo Dalmeri, a rock‐shelter located in northeastern Italy, dated to 13 000 cal. bp , and notorious for the presence, among the other finds, of red‐painted calcareous stones. Painting and the treatment of leather and hides obtained from the intensive hunting activity were the main uses of the hematite‐based red‐ochres at Riparo Dalmeri. It turns out that hematite was mostly obtained from the thermal treatment of goethite, which, unlike hematite, was and still is widely available in the neighbourhood of the site.     

The Chemical Composition and Production Area of Early Western Zhou Proto‐Porcelain Unearthed from Yejiashan Cemetery,Suizhou, China

The bodies and glazes of 27 early Western Zhou proto‐porcelain samples from Yejiashan cemetery, Hubei Province, were analysed using LA‐ICP–AES, SEM, XRD, a thermal expansion instrument and other analytical methods. The results indicated that the bodies of all samples were characterized by high silicon and low aluminium, and were made with porcelain stone raw materials found in the south of China. The glazes are typical of high‐temperature calcium glazes of the CaO (MgO) – K₂O (Na₂O) – Al₂O₃ – SiO₂ series, with relatively high Mn and P content, which was probably caused by the addition of plant ashes. The physical properties and phase compositions of Yejiashan proto‐porcelain show that firing processes were still in the early stages of development in ancient China. Multivariate statistical analyses indicated that Yejiashan proto‐porcelain might have come from the Deqing area, in Zhejiang Province. These results provide new archaeological evidence for research on issues related to material flow in the Western Zhou dynasty.     

Modeling of hydrogen production by serpentinization in ultramafic‐hosted hydrothermal systems: application to the Rainbow field

The production of hydrogen by serpentinization in ultramafic‐hosted hydrothermal systems is simulated by coupling thermodynamic and dynamic modeling in the framework of a thermo‐hydraulic single‐pass model where a high‐temperature hydrothermal fluid moves preferentially through a main canal of high permeability. The alteration of ultramafic rocks is modeled with a first‐order kinetic formulation, wherein the serpentinization rate coefficient, K_r, takes the form: K_r = A exp(?α(T ? T₀)²). In this formulation, α determines the temperature range of the reaction and T₀ is the temperature at which the serpentinization rate reaches its maximum. This model is applied to the Rainbow hydrothermal system, which is situated on the Mid‐Atlantic Ridge, and characterized by a high temperature, a high mass flux, and a very high hydrogen concentration. The results show that a first‐order kinetic law gives a useful representation of the kinetics of serpentinization. The estimated value for the parameter A in the temperature‐dependent formulation of the serpentinization rate coefficient lies in the range (1–5) × 10^?11 s^?1. This effective parameter is several orders of magnitude lower than the values obtained from small grain‐size experiments, but in agreement with other published modeling studies of natural systems. Numerical simulations show that the venting site is able to produce the observed high concentration of hydrogen during the whole continuous lifetime of the Rainbow site.     

Muslim‐Christian Relations in Medieval Southern Italy

Abstract: This article examines the nature of relations between Muslims and Christians in southern Italy during the thirteenth century. In response to uprisings in Sicily, the emperor Frederick II transferred an estimated 20,000 Muslims to the city of Lucera in Apulia. Outside the Iberian Peninsula, Lucera came to have the largest Muslim population of any city in western Europe. Although the formation of the colony led to competition for resources between its inhabitants and the local Christian population, the members of the two religious communities often traded and collaborated. Social mobility was possible for the Lucerine Muslims, particularly through military service. Like Christians and Jews living in the dar al‐Islam, the Muslims of Lucera had a protected status, and they paid a tax called the jizya. They remained free to practice their religion. The heavy taxes paid by the Muslim colony at Lucera during its almost eighty‐year existence made it a valuable asset to the Hohenstaufen and Angevin crowns. Nevertheless, the settlement was dismantled in 1300 on the order of the Angevin king, Charles II, who gave a religious justification. The colony's history provides insight into the complex relations between Muslims and Christians in medieval Mediterranean Europe.     

ARCHAEOMETRIC STUDY OF PROTOHISTORIC GRINDING TOOLS OF VOLCANIC ROCKS FOUND IN THE KARST (ITALY–SLOVENIA) AND ISTRIA (CROATIA)*

This paper presents the results of the archaeometric study of 30 grinding tools found in the Karst plateau (an area that spreads from the northeastern border of Italy to Slovenia) and in the Istria peninsula (Croatia). The petrographic and geochemical characteristics of the artefacts indicate that most of them would be made of trachytic volcanites extracted from the Euganean Hills, near Padua (Veneto). It is known that trachytic rocks from this area had been widely exploited in northern Italy during protohistoric times, but these data considerably enlarge the area of diffusion of saddle‐querns made of these rocks, extending it to Istria. Additionally, the likely provenance from Mount Etna of few other pieces of mugearites and hawaiites represents a new element, to be fully evaluated in the context of trans‐Adriatic exchange/trade connections. Analytical data and possible archaeological inferences are presented in detail in the text.     

Lead‐Glazed Rustiques Figulines (Rustic Ceramics) of Bernard Palissy (1510–90) and his Followers

The glaze chemistry of a group of rustiques figulines attributed to the renowned French potter Bernard Palissy (1510–90), or to his followers and imitators, has been determined non‐destructively using PIXE and PIGE analyses. The glazes are all lead silicates, the colourants being transition metal oxides—CuO, CoO, MnO and Fe₂O₃—with a small addition of SnO₂ to some of the glazes being common. Some distinction can be made between the various fabricated objects based on details of the overall composition and on the concentrations of the various colourants. The presence of B₂O₃ in any glaze, even in quantities as small as 0.1–0.3%, indicates a post‐16th century production. Additionally, B₂O₃ in larger quantities, a few per cent or greater, very probably indicates an 18th–19th century production. However, at least one object known to be of 19th century production contains no B₂O₃.     

Chemical characterization of ancient pottery from sudan by x‐ray fluorescence spectrometry (xrf), electron microprobe analyses (empa) and inductively coupled plasma mass spectrometry (ICP–MS)*

Sixty‐four sherds and seven natural clays from prehistoric sites in northwestern Sudan have been submitted to petrological and chemical analysis using XRF spectrometry, EMPA and ICP–MS. According to their texture, the sherds form five different groups. The high contents of P₂O₅ (more than 0.5 wt%) discerned in 19 samples and the variation of the P₂O₅ content in two samples of the same vessel can be explained by post‐depositional processes or by the ancient organic contents (e.g., milk) of the vessel. Chemical classification of the pottery bulk suggests that vessels were made locally, as only sherds from the same area show homogeneity of data.     

MINERALOGICAL AND PETROLOGICAL INVESTIGATIONS OF EARLY BRONZE AGE COPPER‐SMELTING REMAINS FROM THE KIECHLBERG (TYROL,AUSTRIA)

The prehistoric settlement on the Kiechlberg hilltop is located a few kilometres to the north‐east of Innsbruck, in the Tyrolean Inn Valley. Despite its rather isolated location, a multiphase settlement between the fifth and the second millennium bc was confirmed by archaeological investigations in 2007 and 2008. Metallurgical artefacts, such as copper ore fragments, copper slag and raw copper, as well as finished copper and bronze artefacts, are concentrated mainly in Late Copper Age to Middle Bronze Age layers. The chemical compositions of the slag and raw metals confirm Fe—Zn tetrahedrite–tennantite (fahlore) smelting. The ore was most probably imported from the 30–50 km distant copper ore deposits (mainly fahlore) of Schwaz–Brixlegg, in the Lower Inn Valley. The small amount of slag and the presence of slagged and thermally altered ceramic fragments suggest copper production in small‐scale workshops. Most probably, sulphide‐rich ores were smelted in crucibles in a hearth fire. The process was relatively reducing below the 2Sb + 1.5O₂ → Sb₂O₃ reaction (?8.5 log fO₂ at 1100°C), producing Sb‐rich (>10 wt% Sb in metal) raw copper. Inhomogeneous slag remains containing high amounts of sulphide and metal inclusions suggest a poor separation of the metal, matte (copper sulphide) and silicate/oxide melt during the smelting process.     

Glass on the Amber Road: the chemical composition of glass beads from the Bronze Age in Poland

The article discusses the chemical composition of 56 glass samples from 52 beads found in Poland at 13 archaeological sites (mainly cemeteries). The artefacts have been dated to the II–V period of the Bronze Age (=phases BzB–HaB; c. 1600–750/700 bc). The LA-ICP-MS method was applied. Two groups were distinguished in this assemblage based on a comparison of the MgO to K₂O ratio in glass: (i) high magnesium glass (HMG)—23; and (ii) low magnesium and high potassium glass (LMHK)—33 (29 matrix glass specimens and 4 decorative). In southern Poland, beads made of HMG and LMHK are often found in the same cemeteries. Analyses have shown that HMG was most probably made in Mesopotamia and that at least one cobalt glass is of Egyptian provenance. LMHK glass was made in Europe, most probably in Italy. Also, Italy was the most probable transit point for artefacts made of HMG en route to East-Central Europe.