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.     

Dating of 4th millennium BC pile-dwellings on Ljubljansko barje,Slovenia

We present absolute dates of seven late Neolithic pile-dwellings on Ljubljansko barje, Slovenia. They were settled from ca. 3600 to 3332 (±10) and from 3160 to 3071 (±14) cal BC, as shown by investigations of wood using dendrochronology and radiocarbon wiggle-matching. We defined eleven periods of intensive tree felling (and building activities) and one major settlement gap (when no trees were felled) from 3332 to 3160 cal BC. A major settlement gap presumably also followed after 3071 cal BC (i.e., after the end date of the investigated sites). Our investigations included over 2500 pieces of wood, mainly from the piles on which the dwellings were built. Among important wooden artefacts were a wheel with axle (one of the oldest preserved wheels in the world) and two dugout canoes, all from the settlement phase from 3160 to 3100 cal BC. As shown by parallel studies, the economy in the sites was characterized by copper metallurgy, skilful wood processing and use, cultivation of domestic plants, gathering of wild plants, animal husbandry, hunting and fishing. The settlements were contemporaneous with a number of sites in the north of the Alps, the younger ones coincided with the lifetime of the Neolithic Iceman (Ötzi). Since Ljubljansko barje has a strategic position at the crossroads between western central and (south) eastern Europe the presented absolute dates provide a basis for their comparison with other dated contemporaneous sites (in the west), to revise the chronology of similar sites in the (south) east (which are not yet exactly dated), and to evaluate their interconnection and roles in cultural development in prehistory.     

Polished Stone Axes in Caput Adriae from the Neolithic to the Copper Age

This paper reports the results of a long-term project on the stone axes from Caput Adriae. Available data show that jade axes originating in the western Alps reached the Neolithic groups of Friuli Venezia Giulia and coastal Istria as early as the second half of the 6th millennium BC, during the Danilo/Vla?ka culture. The exchange of this and other classes of lithic artefacts testifies that in this period this area was fully integrated into long-distance exchange systems that used mainly coastal routes. These systems would have continued in the 5th millennium BC, as indicated by a few oversized jade axe blades and other materials. Far from the coast, jade axes entered central Slovenia, probably reaching sites of the Sava Group of the Lengyel culture in the first half of the 5th millennium BC. In roughly the same period, shaft-hole axes made of Bohemian metabasites (BM) spread over central and southeastern Europe, crossed the Alps and reached Italy. According to different Neolithic traditions, during the 5th millennium BC Europe appears to be divided into a jade-using western area and a central-eastern BM-using one. During the 4th millennium BC, the exchange networks of Caput Adriae are increasingly influenced by the eastern Alpine and Balkan world, where the raw material sources of the main groups of shaft-hole axes are located. The association of the rocks used for axe production and copper ore suggests that the changes in raw material exploitation strategies during the Copper Age were probably related to the development of the first metallurgy.     

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.     

SYNCHROTRON FTIR MICRO‐SPECTROSCOPY APPLIED TO THE STUDY OF POLISHED SERPENTINITE ARTEFACTS: A NON‐DESTRUCTIVE ANALYTICAL APPROACH

In prehistory, serpentinite was one of the most frequently used raw materials to produce polished stone artefacts. Several conventional analytical techniques can be applied to identify the serpentine minerals, but their application generally requires a powdered sample. This implies that the artefacts to be analysed must be damaged, and the possibility of analysing a mixture of different serpentine polytypes is high. The use of spatially resolved techniques is therefore a necessity to overcome this problem. Several thin sections of serpentinitic rocks and prehistoric axes have been analysed by synchrotron radiation Fourier transform infrared micro‐spectroscopy. The spectra were acquired directly on specific points of polished stone artefacts and this allowed the recognition of the different polytypes of serpentine minerals without causing any damage to the objects. The results show the infrared micro‐spectroscopy technique to be a useful tool for the characterization of archaeological lithic material.     

New applications of LA–ICP–MS for sourcing archaeological ceramics: microanalysis of inclusions as fingerprints of their origin

This paper presents the latest methodological advances using the LA‐ICP–MS technique for differentiating the origin of petrographically and chemically similar ceramic raw materials. Based on several examples form the Armorican Massif (France), from a chronological period extending from the Neolithic to the Second Iron Age, we will show that the comparison of the chemical signatures of minerals included in fired clay with those from clay and source rocks enables us to distinguish productions and to accurately trace the sources of the raw materials used by potters.     

A COMBINED MULTI‐ANALYTICAL APPROACH FOR THE STUDY OF ROMAN GLASS FROM SOUTH‐WEST IBERIA: SYNCHROTRON μ‐XRF,EXTERNAL‐PIXE/PIGE AND BSEM–EDS

An integrated, multi‐analytical approach combining the high sensitivity of SR‐μXRF, the light element capability of PIXE/PIGE under a helium flux and the spatial resolution of BSEM + EDS was used to characterize chemical composition and corrosion of glass samples (first to fourth centuries ad ) from an important, but scarcely investigated, Roman region of south‐west Iberia (southern Portugal). The geochemical trends and associations of major, minor and trace elements were investigated to shed light on production techniques, the provenance of raw materials and decay mechanisms. The results, while confirming a production technique common to Roman glasses throughout the Empire—that is, a silica‐soda‐lime low‐Mg, low‐K composition, with glass additives as colouring and/or decolouring agents (Fe, Cu, Mn, Sb)—show at one site high Zr–Ti contents, suggesting a more precise dating for these glasses to the second half of the fourth century. The Ti–Fe–Zr–Nb geochemical correlations in the pristine glass indicate the presence of minerals such as ilmenite, zircon, Ti‐rich Fe oxides and columbite in the sands used as raw materials for the glass former: these minerals are typical of granitic‐type source rocks. The unusually high K content in the corrosion layers is consistent with burial conditions in K‐rich soils derived from the alteration of 2:1 clays in K‐bearing rock sequences.     

SHAFT‐HOLE AXES FROM CAPUT ADRIAE MADE FROM AMPHIBOLE‐RICH METABASITES: EVIDENCE OF CONNECTIONS BETWEEN NORTHEASTERN ITALY AND CENTRAL EUROPE DURING THE FIFTH MILLENNIUM BC

Here we show the results of a study concerning a small group of shaft‐hole axes found in northeastern Italy, made from amphibole‐rich metabasites, fine‐grained and free of phenoblasts. The main mineral phases are amphibole, ranging from actinolite to hornblende, and plagioclase (An_10–15 and An_70–77). The amphiboles generally show a needle shape and are often radially arranged. Quartz is present in thin veinlets, while ilmenite is widespread in small patches. The petrographic and geochemical features suggest that the axes originate from the southern thermal aureole of Tanvald granite in northern Bohemia. In accordance with this provenance, the typology of the tools shows similarities with the perforated shoe‐last axes spread across Central Europe during the fifth millennium bc and made from similar raw material. For the first time, these axes give evidence of long‐distance (about 800 km) contacts between northeastern Italy and Central Europe during the Neolithic.     

Flint and Quartzite: Distinguishing Raw Material Through Bone Cut Marks

Since the 1980s, several experimental analyses have been able to differentiate some lithic tool types and some of their raw materials according to the morphology of cut marks imprinted by such tools when used for butchering activities. Thus, metal tool use has been differentiated in contexts with an abundance of lithic tools, or even the use of hand axes has been documented in carcass processing, in contrast with simple unretouched or retouched flakes. As important as this information is, there are still other important aspects to be analysed. Can cut marks produced with different lithic raw material types be differentiated? Can cut marks made with different types of the same raw material type be characterized and differentiated? The objective of this study is to evaluate if cut marks resulting from the use of different flints and different quartzites are distinguishable from each other. In the present work, an experimental analysis of hundreds of cut marks produced by five types of flint and five varieties of quartzite was carried out. Microphotogrammetry and geometric–morphometric techniques were applied to analyse these cut marks. The results show that flint cut marks and quartzite cut marks can be characterized at the assemblage level. Different types of flint produced cut marks that were not significantly different from each other. Cut marks made with Olduvai Gorge quartzite were significantly different from those produced with a set comprising several other types of quartzites. Crystal size, which is larger in Olduvai Gorge quartzites (0.5 mm) than Spanish quartzites (177–250 μm), is discussed as being the main reason for these statistically significant differences. This documented intra‐sample and inter‐sample variance does not hinder the resolution of the approach to differentiate between these two generic raw material types and opens the door for the application of this method in archaeological contexts.     

The Copper CHARM Set: A New Set of Certified Reference Materials for the Standardization of Quantitative X‐Ray Fluorescence Analysis of Heritage Copper Alloys*

This paper introduces a new set of certified reference materials designed to aid scientists and conservators working in cultural heritage fields with quantitative X‐ray fluorescence analysis of historical and prehistoric copper alloys. This set has been designated as the Copper CHARM Set (Cultural Heritage Alloy Reference Material Set). The Copper CHARM Set is designed to be used by a wide range of museum‐, art‐ and archaeology‐oriented scientists and conservators to help improve the accuracy and range of their calibrations for quantitative ED–XRF spectrometry of copper alloys, and also increase the number of elements that can routinely be quantified. In addition, the common use of a single core set of the reference materials is designed to significantly improve inter‐laboratory reproducibility, allowing greater data sharing between researchers and thus furthering possibilities for collaborative study.     

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.     

Production Technology for Copper‐ and Cobalt‐Blue Vitreous Materials from the New Kingdom Site of Amarna—A Reappraisal*

Previously published data on the chemical compositions and microstructures of copper‐ and cobalt‐blue frit, glass and faience from the New Kingdom site of Amarna in Egypt ( Shortland 2000 ) are summarized. The data are then used to infer the raw materials and processes employed in the production of these vitreous materials. The results suggest that crushed quartz pebbles were the source of the quartz for all the materials, but that different sources of alkali, both natron and a range of plant ashes, were used in the production of each material. It seems probable that the cobalt‐rich alum colorant was pre‐treated before use by precipitating cobalt hydroxide from a solution of the alum by the addition of natron. It is further hypothesized that cobalt‐blue glass was produced by melting the cobalt‐blue frit together with additional plant ash and possibly quartz. Finally, it is suggested that, in glazing the cobalt‐blue Variant D faience first produced in the 18th Dynasty, the efflorescence or application method was selected according to object type.     

Reconstructing Regional Trajectories: the Provenance and Distribution of Archaic to Hellenistic Ceramics in Central Pisidia (South‐west Turkey)

Analytical ceramic studies offer the opportunity to determine cultural development and change on the basis of origin and use of raw materials. In this particular study, an archaeometric approach on ceramics in central Pisidia contributes to the discussion of contact and exchange between indigenous communities and several cultural spheres of influence on a long‐term timescale (eighth to second centuries bce ). Morphological data as well as mineralogical (optical microscopy; n = 273) and chemical composition (by ICP–OES/MS; n = 122) of ceramics and raw materials show distinct resource zones for the production and distribution of ceramics in this connecting region of Anatolia. The use of trace element profiles (REE, HFSE, LILE and TTE) in particular is regarded as instrumental in detailing high‐resolution provenancing of ceramics. The ceramic provenance indicates different patterns of material interactions during the Archaic, Classical and Hellenistic periods. A significant increase in regional interaction occurs coinciding with the development of pottery activities at Sagalassos.     

The Experimental Study of Palaeolithic Heat‐Treatment Technology: A Case from the Shuidonggou Rock Resources,North‐West China

The application of heat‐treatment technology on lithic raw materials is an important feature of early modern human behaviour. The evidence of heat‐treated stone artefacts discovered at Localities 2 and 12 of the Shuidonggou Late Palaeolithic site, North‐West China, provides an important example for studying this technology among ancient humans in Asia during the Late Palaeolithic. The mechanism and effects of heat treatment on raw materials and the role of this technology in producing stone tools were studied by means of a simulation experiment and related analytical methods. These facilitated an in‐depth analysis of the heat‐treatment activities of the Shuidonggou occupants and their implications for cognitive ability and survival strategies of human populations at that time.     

CLAY RESOURCES AND TECHNICAL CHOICES FOR NEOLITHIC POTTERY (CHALAIN,JURA, FRANCE): CHEMICAL,MINERALOGICAL AND GRAIN‐SIZE ANALYSES*

Many authors have considered pottery manufacturing constraints and sociocultural elements as factors in change in past civilizations over time. The main issue of this research is to better understand the reasons for changes, or choices, in pottery raw materials. The very precise and detailed stratigraphy and cultural succession of occupations is based on dendrochronological data from the lake‐dwelling sites of Chalain (Jura, France). Petrographic, palaeontological and chemical analyses were used to determine the nature and origins of the raw materials used by the Neolithic potters. Stratigraphy and dendrochronological data were used to reconstruct in detail the evolution dynamics of fabric changes. Several raw material sources were identified for many of the pottery groups. Each of them was sampled for qualitative experimental tests of pottery forming. The experimental results show a high variability between the sediments tested. This variability was quantitatively estimated by XRF, XRD, the Rietveld method, calcium carbonate quantification and laser grain‐size analyses of matrices, indirect measures of plasticity. These analytical results allow a better understanding of the differences observed in the experimental tests. On the basis of these experimental and analytical results, changing parameters such as pottery manufacturing constraints, mineralogical characteristics of raw materials and sociocultural factors are considered. In conclusion, all the social and technical parameters, in each archaeological context, must be taken into account for a better understanding of the changes occurring throughout the chronological sequence.     

Aspects of the Production of Cobalt‐blue Glass in Egypt

Cobalt‐blue glass of the Near and Middle Eastern Late Bronze Age has long been recognized as compositionally distinct from other contemporary glasses (Sayre 1967; Lilyquist et al. 1993). It has been suggested recently by Shortland and Tite (2000) that this chemical distinction reflects the use of Egyptian raw materials for making these glasses, different from those used to make glass in Mesopotamia, or its manufacture by Mesopotamian workmen, possibly in Egypt. This assumed that cobalt‐bearing alum from the Western Oases and mineral natron from the Wadi Natrun were used for the cobalt‐blue glass, while the other, probably Mesopotamian, glasses were made using plant ash as the main alkali source. This note discusses some technical aspects of the possible ways in which the cobalt could have been added to the glass, and how this relates to the likely raw glass used in its making. Combining earlier suggestions by Noll (1981) and Brill in Lilyquist et al. (1993), an alternative explanation of the chemical characteristics is suggested, maintaining that all the glasses under discussion were made using plant ash. Differences in alkali concentrations probably reflect different soil and plant chemistries, and the colorant was probably added to the glass after being precipitated from the alum as a complex cobalt aluminium hydroxide.     

Complex raw materials and the supply system: Mineralogical and geochemical study of the jade artefacts of the Longshan Culture (2400–2000 bce) from Sujiacun site in coastal Shandong,China

X‐ray fluorescence (XRF), X‐ray diffraction (XRD) and Raman spectroscopy were employed to analyse the chemical compositions and phase structures of nine pieces of jade artefacts unearthed from Sujiacun, a Longshan Culture (2400–2000 bce ) site in coastal Shandong, eastern China. The results of the analyses indicated these samples were primarily made from multiple raw mineral materials, including antigorite, actinolite, clinochlore, turquoise and muscovite. No nephrite was recovered from the Sujiacun site. This is strikingly different from other top‐ranking settlements of Longshan Culture, such as Dantu, Liangchengzhen and Xizhufeng, in which nephrite was the main material of jade artefacts. This may reflect the distinctions in the supply system of jade raw materials among different rankings of Longshan period sites. In addition, laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) was used to analyse the composition of the rare earth elements of serpentine jade. These preliminary results were compared with published data on the composition of serpentine jade and it was found that the Sujiacun serpentine jade artefacts were likely sourced from the Taishan jade deposit.     

AN ELEMENTAL AND LEAD‐ISOTOPIC STUDY ON BRONZE HELMETS FROM ROYAL TOMB NO. 1004 IN YIN RUINS

Lead isotope and element composition analyses were performed by thermal ionization mass spectrometry (TIMS) and inductively coupled plasma optical emission spectroscopy (ICP–OES) on bronze helmets from royal tomb No. 1004 at Yin Ruins, the last capital of China's Shang Dynasty (17th to 11th centuries bc ). The data show that the copper‐based alloy helmets can be divided into two categories: tin bronze and leaded tin bronze; and the lead isotope ratios for both categories are in the range of highly radiogenic lead (HRL). This result offers some important clues to answering questions concerning the provenance of raw metal materials, as well as the chronology of this famous royal tomb.     

INCISED SLIPWARE PRODUCTION AT CASTELFIORENTINO (FLORENCE): THE ‘VIA BERTINI’ SITE (15TH–17TH CENTURIES)*

This study deals with the physical–chemical and mineralogical–petrographic investigations (OM, SEM–EDS, EPMA, ICP, XRpD, Mössbauer and IR) conducted on first‐ and second‐firing wasters belonging to two types of incised slipware (sgraffito), manufactured at Castelfiorentino between the late 15th and the early 17th centuries. Raw materials, colouring agents and firing products were analysed in order to establish the production technology of the ceramic coatings, by means of detailed microtextural and chemical investigations. The pottery underwent two firing processes: the firing of the white slip‐coated ceramic body and a further firing after application of the glaze. The homogeneity of the raw materials, white slip and glaze is remarkable, and demonstrates the use of well‐established recipes with a constant supply of raw materials from the same places. Highly efficient kiln management during both firings is revealed by body–glaze interface reactions.     

PHYSICOCHEMICAL COMPOSITIONAL ANALYSIS OF CERAMICS: A CASE STUDY IN KENTING,TAIWAN*

The composition of ceramics does not just reflect the component of some specific, unprocessed, geological, raw material source, but also certain forms of human behaviour involved in its manufacture. The purpose of this research project is to apply the acid‐extraction chemical method, complemented by a thin‐section petrographic study, to the compositional analyses of certain local ceramic collections (mainly from several sites in the southern Taiwan area). The results present the raw materials that the ceramic manufacturers of the two cultural traditions (O‐laun‐pi Phase II and Phase III–IV), which overlapped temporally, used. These materials came from the same sources, but the ceramics were manufactured in different ways. Particularly, the people of O‐laun‐pi Phase III–IV also procured certain materials from either local sources or from somewhere in eastern Taiwan to make their pots. The results also indicate that there might have been a variation in terms of their manufacture among sites of the same cultural tradition.