PXRF characterisation of obsidian from central Anatolia, the Aegean and central Europe

Accepted Manuscript PXRF characterisation of obsidian from central Anatolia, the Aegean and central Europe Marina Milić PII:

S0305-4403(13)00290-2

DOI:

10.1016/j.jas.2013.08.002

Reference:

YJASC 3787

To appear in:

Journal of Archaeological Science

Received Date: 3 October 2012 Revised Date:

8 July 2013

Accepted Date: 2 August 2013

Please cite this article as: Milić, M., PXRF characterisation of obsidian from central Anatolia, the Aegean and central Europe, Journal of Archaeological Science (2013), doi: 10.1016/j.jas.2013.08.002. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT 1 PXRF characterisation of obsidian from central Anatolia, the Aegean and central Europe Marina Milić Institute of Archaeology University College London

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31-34 Gordon Square London WC1H 0PY United Kingdom

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[email protected]

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00 44 (0) 7503732120

Introduction

A wide range of scientific methods have been developed to analyse the origins of obsidian artefacts and raw materials, and by extension to investigate peoples’ movements and interactions. This paper deals with the capabilities of a portable X-ray fluorescence [pXRF] instrument to discriminate obsidian artefacts that were found on the sites located in a wide

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area incorporating the Balkans, Aegean and western Anatolia. The point of departure is the identification and study of a region(s) supplied by one or more obsidian sources forming, what one might term, overlap zones between different obsidian distributions (Figure 1). The artefacts found in these regions are products of obsidian outcrops in 1) central Anatolia

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(Göllü Dağ and Nenezi Dağ), 2) the Aegean (Adamas and Demenegaki on the island of Melos and sources on Antiparos and Giali), and 3) Central Europe (Carpathian 1 and Carpathian 2). The aim is to discriminate obsidian types that have been found in

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archaeological contexts in neighbouring geographical regions, particularly in the Aegean area, where multiple obsidian distributions occur during the Neolithic period. This actively leads us to the question of contacts, trade, choice and other social processes that these communities were involved in. Insert Figure 1 here Obsidian from more than one source is present in several assemblages from the above regions (cf. Çatalhöyük (Turkey) [Carter and Milić, 2013a], Vinča (Serbia) [Tripković and Milić, 2008], Keros in the Cyclades [Carter and Milić, 2013b], and so it became clear that some

ACCEPTED MANUSCRIPT 2 sites and/or regions had access to obsidian from more than one source (based on analytical work or visual inspection). For this present study, the use of PXRF was chosen as the most suited analytical method in order to sample the majority of artefacts in each assemblage. My intention has been to develop a field method that enables analyses of large obsidian

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assemblages that can capture the true variability of raw materials, along with the relationship between raw materials and the technological form in which they appear. Another aim is to systematically integrate social theory and scientific practice through practical work, using methods readily accessible to most archaeologists.

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Given that chipped stone assemblages often contain obsidian from multiple sources, whether the case is small-scale site-level project or large-scale, regional research, it is valuable to

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analyse a large sample of obsidian artefacts. Site-level analyses are typically looking for temporal and spatial pattern and changes in obsidian supply (e.g. Catalhoyuk [Carter et al., 2005]), studies at the regional scale typically aim to reconstruct exchange networks amongst groups of sites.

In this paper I will assess the usability of pXRF for the purposes outlined here through analysis of geological samples of known origin from the aforementioned three source regions to establish the parameters of trace element ranges for each as determined by the specific

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instrument in use. The next step is to analyse archaeological obsidians under the same conditions, thereby revealing the geological source from which the obsidian originated. This is used to address the directionality of connectivity between the communities that receive obsidian. This social perspective is based on the relative proportions of obsidians from

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different sources found at each archaeological site, and regional patterns across multiple sites. The specific details of the archaeological analyses will not be discussed here, being too

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extensive for this paper’s objectives, but they nonetheless serve to demonstrate the third strand in this paper that assesses the specific benefits of mass-sampling to archaeological interpretation (Freund, 2012).

Through tertiary scatter plots of strontium (Sr), zirconium (Zr) and rubidium (Rb) it is possible to separate the major obsidian types into distinct groups, while discrimination of the Adamas and Demenegaki sources on Melos is possible through iron (Fe) and titanium (Ti) contents. Two sub-sources within Carpathian 2 source could also possibly be separated using Ti and Fe, although a bigger sample is required to explore this further.

ACCEPTED MANUSCRIPT 3 1.1.

Validity of pXRF

This study of obsidian from the three volcanic regions is based on analyses undertaken solely using pXRF. This is a fast and non-destructive technology that has found considerable support in obsidian provenancing studies, and so far has been tested in almost all the obsidian

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using regions of the world (Craig et al., 2007; Golitko et al., 2010; Jia et al., 2010; Millhauser et al., 2011; Nazaroff et al., 2009; Phillips and Speakman, 2009; Sheppard et al., 2011; Tykot, 2010). In turn, there has been a healthy associated suite of literature critically reflecting upon the reliability of these ‘fast’ methods in archaeology and geology (Craig et al., 2007; Frahm,

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2012; Millhauser et al., 2011; Nazaroff et al., 2009; Shackley, 2011), that have also dealt with precision and comparability of pXRF to other methods, mainly to lab-based EDXRF but also INAA and PIXE. These inter-laboratory tests have shown the ability of pXRF instruments to

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effectively discriminate different sources, although the elemental concentrations reported were not always comparable to the results produced using other instruments without further calibration using regression analyses (Craig et al., 2007; Frahm et al., 2013; Millhauser et al., 2011; Nazaroff et al., 2009; Shackley, 2011). A critical issue for obsidian provenancing, however, is that each instrument, using the method described below, will independently, and consistently, provide the data that will allow investigator to come to the same

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archaeologically relevant conclusions, that is provenancing archaeological obsidians to specific geological sources (Frahm, 2012). The aim of this study is to test the validity of the INNOV-X pXRF (see below) for the discrimination of several obsidian sources conducted through multiple analyses of geological and archaeological materials of known provenance.

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The geological samples were acquired at the quarries and the results were compared to the published data from other methods. The inter-laboratory study involved the common analysis of 16 archaeological artefacts from Çatalhöyük (Turkey) provenanced using EDXRF, PIXE,

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ICP and pXRF, and 10 source samples from Carpathian 1 and 2 analysed with EDXRF and pXRF.

1.2.

Mass-sampling

PXRF has greater restrictions than lab-based analytical equipment for characterising obsidian, and this limits certain applications for specifically scientific analyses (Shackley, 2011). The technology can, however, produce highly replicable results (precision) in ideal contexts, though being a hand-held device, practice-based precision relates to the actual performance of the user as well as the instrument.

ACCEPTED MANUSCRIPT 4 Scientific intentions aside, our research is often constrained by bureaucracy in terms of gaining permission to export items to laboratories to conduct analyses. Being a common issue in the areas considered in this paper, this has often led to analyses of essentially “random” pieces. These may fulfil bureaucratic criteria (‘non museum quality’), but often lack techno-

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typological diagnostics, whereby we tend to talk in reductionist terms of “samples” rather than characteristic “artefacts” (Carter, 2008, p. 226). These sampling protocols can have major implications upon the kinds of questions we are able to ask of our material (Carter et al., 2006; Molloy et al., forthcoming). Bigger picture stories, such as those created by Renfrew and his colleagues in the 1960s, were based on examination of assemblages from

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dozens of sites. Over the past 50 years the development of various analytical methods has allowed us to understand which obsidian is circulating in these regions. Building upon this

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previous work, the aim of mass sampling of archaeological obsidian is to move forward in the range of social questions that we can answer (Freund, 2012). The goal of this new research is not to search for rare ‘exotic’ pieces but to quantify and qualify entire assemblages as close to in toto as practicable. This is done by determining raw material provenance ratios, followed by the chaîne opératoire of objects in their contextual and regional setting (e.g. Briois et al., 1997; Carter and Kilikoglou, 2007; Carter et al., 2006; Freund and Tykot, 2011). Through this we can begin to assess preferential access to, or desire for, specific sources at each

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particular site, and discern chronological and geographical variability from local, to regional to macro-regional scales. Arguably then, the greatest value of pXRF lies in the logistical reality of it being possible to bring it to storage locations and mass-sample artefacts.

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A disadvantage of the pXRF technique is the size and morphology of some archaeological artefacts we sometimes deal with (Liritzis and Zacharias, 2010; though see Frahm, 2012). The geological source material analysed in this study is large enough to allow the screen of

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the analyser to be entirely covered to enable consistent results. However, when examining archaeological pieces, they were often thinner, smaller and irregular (e.g. very thin and narrow bladelets and debris). Davis et al. (2011) have shown using lab-based XRF techniques that dealing with such small, thin artefacts can have an effect upon the precision and accuracy of analyses. This was taken into account when selecting artefacts for analysis and further quality control of results was possible insofar as outliers from known clusters could be readily identified, characterised as problematic readings if the artefacts were of sub-optimal morphology, and removed from the data-set.

ACCEPTED MANUSCRIPT 5 2. Background to the source regions Since the early work of Cann and Renfrew (1964), there have been a large number of projects dedicated to obsidian studies in central Anatolia, the Aegean and Carpathians, work that has provided us with a solid evidential basis for understanding the composition of these

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archaeologically significant sources (Williams-Thorpe et al., 1984; cf. Kilikoglou et al., 1996; J. L. Poidevin, 1998). 2.1.

Central Anatolia

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A number of obsidian sources are known in central Anatolia (Cappadocia), of which the most significant archaeologically are the massifs of Göllü Dağ and Nenezi Dağ (Figure 1). In the past two decades, these complex sources have been mapped and characterised in detail, and

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their products discriminated through the use of OES, SEM-EDS, EDXRF, LA-ICP-MS and PIXE (Binder et al., 2011; Cauvin et al., 1998; Gratuze, 1999; J. L. Poidevin, 1998; Poupeau et al., 2010). These Cappadocian sources were exploited from significant distances away from the Epi-Palaeolithic onwards (from c. 17,000 cal BC (Carter et al., 2011), with raw materials and workshop manufactured implements circulating throughout Anatolia, Cyprus and the Levant. Small quantities of these Cappadocian obsidians are also attested in Western

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Anatolian and Aegean islands from the late Neolithic onwards (late 7th millennium BC), as far west as Crete and the Cyclades (Bellot-Gurlet et al., 2008; Bergner et al., 2009; Carter and Kilikoglou, 2007; Milić, in prep.; Pernicka et al., 1999). The Aegean

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2.2.

The most archaeologically significant obsidian sources of the Aegean are located on the islands of Melos and Antiparos in the Cyclades and Giali in the Dodecanese (Figure 1).

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Melos represents the major obsidian complex in the Aegean with two main outcrops Demenegaki and Adamas (also known as Sta Nychia), which were extensively used in prehistory (Carter, 2009; PerlЀs, 1992; Renfrew et al., 1965; Torrence, 1986). Located only ca. 9 km apart ATCF, these sources produced obsidian of similar knapping quality and elemental composition (Torrence, 1986, p. 96). The discrimination of the two Melian sources has been achieved using techniques such as OES, NAA, XRF, ICP-AES and SEM-EDS (Acquafredda and Paglionico, 2004; Aspinall et al., 1972; Kilikoglou et al., 1996; Liritzis, 2008; Shelford et al., 1982), with the most commonly used method being NAA using the relative concentration of scandium (Sc) (Aspinall et al., 1972; Kilikoglou et al., 1996).

ACCEPTED MANUSCRIPT 6 Shelford et al. (1982) have shown XRF to be successful for discriminating the two sources using major elements. More recently, through pXRF technology, the Adamas and Demenegaki sources were separated on the basis of Ti and Fe content (Frahm et al., 2013; Liritzis, 2008). Unfortunately, since the early 1980’s when the two Melian sources could be

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distinguished, there have been very few larger-scale obsidian characterisation studies of archaeological obsidian from in the Aegean region.

Obsidian from Antiparos was not used widely in prehistory; while the raw material is of good quality the small size of the nodules (<5cm long) restricted its use for making artefacts

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(Carter and Contreras, 2012; Renfrew et al., 1965, p. 232).

Giali is a small island in the Dodecanese that was a source of distinctive white-spotted

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obsidian. When knapped, it is highly translucent (giali means glass, in modern Greek) with crystalline inclusions that gave this obsidian poor knapping qualities due to unpredictable fracturing patterns, although in the archaeological record it appears in the form of carved / ground vessels manufactured from the Middle Bronze Age (Bevan, 2007; Carter, 2009; Renfrew et al., 1965), while it was rarely if ever used for tool manufacture in the immediate

2.3.

The Carpathians

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region during later Neolithic.

The Carpathian sources are located in modern-day Hungary and Slovakia in central-eastern

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Europe (J. Nandris, 1975; Rosania et al., 2008; Williams and J. Nandris, 1977). Another source area has recently been explored in the eastern Carpathians in today’s Ukraine (Rosania et al., 2008), though this does not relate to this paper since the distribution of this obsidian is

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still not documented in archaeological contexts. A large number of samples have been analysed from these regions using NAA, EDS, XRF, PIXE, PIGE and recently, PGAA (Biró et al., 1986; Biró, 2006; Oddone et al., 1999; Rózsa et al., 2006; Thorpe, 1978; WilliamsThorpe et al., 1984). The results permitted the separation of the Carpathian sources into the Zemplin Hills sources in eastern Slovakia (Carpathian 1) and the Tokaj Mountain sources in north-eastern Hungary (Carpathian 2), with the latter subsequently discriminated into two sub-groups, Erdıbénye C2E and Tolcsva C2T (Biró et al., 1986; Williams-Thorpe et al., 1984).

ACCEPTED MANUSCRIPT 7 Unlike the other sources discussed in this paper, today only small nodules can be found in soil matrices at the major Carpathian sources. The geological context is often in secondary deposits, in which obsidian occurs as clasts rather than flows (Williams and J. Nandris, 1977). The deposits that were exploited in prehistory no longer exist due to natural erosional

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processes and more recent intensive cultivation (Nandris, 1975; Oddone et al., 1999). The small size of tools (and cores) from these deposits suggest, but do not prove, that the choice of tool size was dictated by the geological formation process that did not produce flows that

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could be quarried in the same way as in the Aegean and Anatolia.

3. Multiple distributions and their archaeological significance

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The mapping of obsidian circulation through time and space is a typical means of displaying and interrogating social behaviour and processes, in particular trade/exchange, as most clearly and influentially outlined in the fall-off curves and supply/contact zone models of Renfrew, Dixon and Cann (1968).

In this study I demonstrate discrimination of obsidian from the main sources of the Aegean, Carpathians and central Anatolia, because they all appear, in various frequencies, on sites in

Anatolia.

3.1.

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Insert Figure 2 here

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the Neolithic Aegean and surrounding mainland, in the Balkans and western parts of

Overlaps between the Carpathian, Aegean and central Anatolian obsidian in the

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Neolithic period

The circulation of raw materials from each source region has overlaps with the neighbouring region at the edges of their distributions (Figure 1). The appearance of obsidian from more than one source is documented throughout prehistory, although the emphasis here is on the Neolithic period of late 7th / beginning of 6th to the 5th millennium BC. The overlap of Carpathian and Aegean obsidian is currently known only at the sites of Mandalo (Kilikoglou et al., 1996) and Dispilio (Milić, in prep.) in western Macedonia, Greece. In turn, the appearance of Aegean and central Anatolian material is commonly

ACCEPTED MANUSCRIPT 8 witnessed in western and north-western Anatolia and northern/eastern Aegean, as for example at several locations in Izmir region (Morali [Renfrew et al., 1965], Ulucak, [Milić, in prep.; Çilingiroğlu, 2011], Ege Gübre and Yeşilova [Milić, in prep.], Çukariçi Höyük [Bergner et al., 2009] and Dedecik-Heybelitepe [Herling et al., 2008)], in the Troad (Troy

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[Pernicka et al., 1999], Coşkuntepe [PerlЀs et al., 2011] and Gülpinar [Milić, in prep.] and Uğurlu on Gokçeada [Milić, in prep.] and Marmara region (Barcin Höyük, Aktopraklık, Pendik and Fikirtepe [Milić, in prep.]). Finally, tiny quantities of obsidian from both Göllü Dağ and Melos were found further north in Thrace at Hoca Çeşme (Milić, in prep.). One piece out of 13 in total at Sitagroi was assigned to Göllü Dağ, although it is unstratified and

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possibly of EBA date ((Renfrew and Aspinall, 1990, p. 266) (Figure 2). The most eastern penetration of Melian raw material inland into Anatolia and its overlap with central Anatolian

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obsidian distribution has been identified at late Chalcolithic Aphrodisias (Blackman, 1986). In the Aegean islands, chipped stone assemblages were dominated by Melian products, though small amounts of obsidian from central Anatolia have been noticed usually on the basis of macroscopic examination (cf. Chios [pers. obs.], Dodecanese [Sampson, 1987],

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Cyclades [Carter and Milić, 2013] and Crete [Panagiotaki, 1999]).

3.1. Spatial and chronological significance

Regional approach of this project permits the investigation of patterns arising from the study

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of many sites, thereby diminishing the risk of accentuating differences in a single assemblage and having the potential to reflect patterns rather than exceptions. Overlaps in raw material distribution were not part of uniform and parallel distribution and exchange systems, but in

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most areas were represented by the presence of a ‘main’ raw material from one source accompanied by sporadic or occasional pieces from another. The frequency of one or more obsidian types varies from site to site, and therefore these overlaps need to be considered on a micro-regional scale. A good example is western Anatolia, where during the Neolithic period, the presence of Melian obsidian and central Anatolian varies in different areas. Melian is much more frequent in the region of Izmir and in the Troad, while in the Marmara in the north-west, the more common sources are central Anatolian types (Milić, in prep.). Furthermore, the sites within each of these micro-regions will have different frequencies of obsidian in total and variety of obsidian types (e.g. at Çukariçi Höyük the total amount of

ACCEPTED MANUSCRIPT 9 obsidian is 87% [B. Horejs pers com.] while relative proportion of obsidian to other raw materials in neighbouring Ulucak is less than 1% [K. Cooney pers.com]). In the case of tell and multi-period sites, the frequency of one or more obsidian types can be observed through their different stratigraphic sequences and time periods (e.g. pers. obs. at Ulucak). Detailed

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study of obsidian assemblages at Çatalhöyük (central Turkey) has shown that the occurrence of Göllü Dağ and Nenezi Dağ obsidian changed radically through time, despite the fact that the sources were equidistant from the settlement (Carter et al., 2005). Likewise, the procurement of the two nearby Melian sources Adamas and Demenegaki might be considered as the same social action, given that their setting on an island required similar efforts and

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organisation (Torrence, 1986). For these reasons it is important from an archaeological perspective to use a method that enables sufficient data to be employed to achieve greater

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statistical validity of the results produced.

Figure 2 shows sites that belong to 7/6th and 5th millennia BC located in the areas of overlaps of different source groups and general patterns with the percentage of obsidian from each source area. This could be analysed further according to specific chronological time frames (e.g. Early Neolithic, Middle Neolithic, Late Neolithic, Chalcolithic, etc.) and more detailed presence of various sources (e.g. Gollu Dag and Nenezi Dag in central Anatolia; Adamas and Demenegaki in Melos; C1 and C2 in the Carpathians). The intention here is to demonstrate

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the general pattern of directionality of communication, and so this more detailed treatment is not pursued.

Sample selection and the analyses

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4.

A total of 52 geological samples were analysed from eight sources: Göllü Dağ - seven pieces (Bogazköy - two, Kömürcü - two and Kayırlı – three), Nenezi Dağ – five, Melos Adamas -

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eight pieces, Melos Demenegaki - eleven, Giali - five, Antiparos – one, Carpathian 1 – seven and Carpathian 2 – eight pieces (analysed on location). Insert Figure 3 here 4.1.

The analyses

The analyses were undertaken using a handheld Olympus Innov-X Delta XRF device. The model operates a 40kV and is equipped with the Delta Rhodium (Rh) anode X-Ray tube, and uses a Silicon Drift Detector. For the purpose of obsidian sourcing, the instrument was set to the ‘Soil setting’ using three-beam mode to record a wide range of elements. The “3 beam”

ACCEPTED MANUSCRIPT 10 soil mode records heavy metals, transitional metals and light elements with each of the beams. Here, the results of nine elements (Ti, Mn, Fe, Zn, Rb, Sr, Zr, Ba, Pb) are detailed, however, the main focus is on the three trace elements Rb, Sr and Zr. These are commonly used in obsidian provenancing for clustering the source groups. All the data is processed in

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comma-delimited Excel files including calculated error ranges. The quantification is based on Compton peak normalisation, with results given as ppm.

Each sample was analysed for 10 seconds per beam giving 30 seconds of total exposure time per sample. Repeated examinations of the samples using different times 20, 30 and 60 seconds per beam shown that 10 seconds per beam analyses produced matching results

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(Figure 4).

All the geological samples were analysed as a whole, with no preparation required, apart

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from simple cleaning. The objects were positioned to cover as much as possible of the pXRF scanning screen, usually reading the most flat surface of artefacts to ensure that the greatest amount of X-rays would be returned from the sample (issues of geometry / flat surfaces also detailed in Davis et al., 1998). The Innov-X Delta instrument has a screening window about 10 mm in diameter, while the X-ray source excites a target circle with an 8 mm diameter. Insert Figure 4 here

The results

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4.2.

The results of nine elements are shown in Table 1, however, the trace elements Rb, Sr and Zr proved to be the most informative for separating all the reference samples into distinct groups

Source

Ti (ppm) 298 312 229 307 237 417 573 773 812 514 859 807 843

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Göllü Dağ Göllü Dağ Göllü Dağ Göllü Dağ Göllü Dağ Göllü Dağ Göllü Dağ Nenezi Dağ Nenezi Dağ Nenezi Dağ Nenezi Dağ Nenezi Dağ Melos Adamas

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(Figure 3). Their range and mean value are shown in Table2. Mn (ppm) 466 430 463 455 421 425 344 497 455 456 439 431 440

Fe (ppm) 4414 3891 4225 4066 3868 3949 4196 6653 6093 5557 6779 6203 5821

Zn (ppm) 20 17 16 14 17 14 20 34 33 29 32 34 28

Rb (ppm) 194 179 187 178 176 168 166 158 148 143 155 156 107

Sr (ppm) 11 11 12 14 8 14 16 99 100 97 99 98 102

Zr (ppm) 76 75 74 75 76 71 69 137 137 132 137 135 105

Ba (ppm) 124 117 142 123 107 130 159 380 374 413 420 396 405

Pb (ppm) 27 26 25 31 24 26 23 37 33 31 36 32 18

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112 111 110 108 103 111 105 97 97 95 98 95 91 98 99 96 98 103 122 124 118 122 121 155 154 163 156 172 168 173 174 185 164 181 165 173 176 174 367

97 99 103 107 98 93 98 109 105 105 109 108 106 114 110 114 111 114 62 60 66 64 61 73 76 77 65 73 75 64 71 75 70 71 72 72 73 74 10

111 108 110 107 104 109 102 117 110 112 109 114 112 108 121 115 119 121 99 94 97 95 96 69 69 63 62 68 74 67 128 122 129 126 118 123 128 133 128

280 338 369 322 310 336 407 339 315 378 255 312 309 304 358 315 323 365 509 552 420 520 475 359 326 280 420 305 351 307 367 408 416 459 407 461 385 572 153

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26 25 24 27 24 27 21 20 20 27 33 29 27 25 32 32 27 22 18 21 17 18 20 23 21 23 22 22 22 20 46 46 32 37 35 36 43 38 24

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5672 5882 5859 5583 5460 5171 5618 7231 6902 6997 7166 6849 6824 7191 7276 6873 7056 7218 5111 4552 4221 4513 4484 5536 5404 5261 4768 5187 5456 5483 11671 7335 7315 7512 7052 7108 12551 11361 4206

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400 446 442 412 392 417 427 354 399 390 381 379 369 374 432 374 384 412 251 257 219 239 212 300 282 305 291 326 308 340 421 258 300 289 286 296 278 292 509

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830 954 892 827 830 874 913 1158 1146 1162 1125 1113 1145 1294 1125 1149 1163 1206 776 674 560 544 510 232 188 223 231 231 229 170 1701 364 682 327 326 331 2356 2032 439

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Melos Adamas Melos Adamas Melos Adamas Melos Adamas Melos Adamas Melos Adamas Melos Adamas Melos Demenegaki Melos Demenegaki Melos Demenegaki Melos Demenegaki Melos Demenegaki Melos Demenegaki Melos Demenegaki Melos Demenegaki Melos Demenegaki Melos Demenegaki Melos Demenegaki Giali Giali Giali Giali Giali Carpathian 1 Carpathian 1 Carpathian 1 Carpathian 1 Carpathian 1 Carpathian 1 Carpathian 1 Carpathian 2 Carpathian 2 Carpathian 2 Carpathian 2 Carpathian 2 Carpathian 2 Carpathian 2 Carpathian 2 Antiparos

Table 1 – The concentrations of elements (Ti, Mn, Fe, Zn, Rb, Sr, Zr, Ba, Pb) as determined by pXRF in ppm

Source Göllü Dağ mean Nenezi Dağ

Rb (ppm) 166-194 178 143-158

Sr (ppm) 8-16 12 97-100

Zr (ppm) 69-76 74 132-137

16 15 14 16 14 14 18 17 15 16 15 13 16 19 10 15 19 15 24 20 21 19 21 33 31 32 27 38 33 38 34 39 28 42 27 27 38 33 57

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152 103-112 108 91-103 97 367

99 93-107 100 105-114 110 10

136 102-111 107 108-121 114 128

Giali mean Carpathian 1 mean Carpathian 2 mean

118-124 121 154-173 163 164-185 175

60-66 63 64-77 72 71-76 73

94-97 96 62-74 67 118-140 127

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mean Melos Adamas mean Melos Demenegaki mean Antiparos

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Table 2 – The range and mean values of Rb, Sr and Zr in obsidian from the sources Central Anatolia

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4.3.

If we consider the source regions separately we can see that Nenezi Dağ and Göllü Dağ have distinct differences in concentration of some elements, with characteristic (comparatively) low Sr in Göllü Dağ obsidian (8-16 ppm). Zr is also present in a distinctly lower quantity in Göllü Dağ (65-100 ppm) while it is considerably higher at Nenezi Dağ (130-160 ppm).

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Characterisation work on geological and archaeological artefacts from Cappadocia has been conducted using other techniques, allowing comparison of the different methods (Hancock and Carter, 2010; Poupeau et al., 2010). Firstly, archaeological material from Çatalhöyük (Turkey) has been tested using lab-based EDXRF (UC Berkeley), PIXE (CR2PA, Paris), ICP-MS (Grenoble) and finally pXRF. Table 3 shows the results of Rb, Sr and Zr using these

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techniques on the same artefacts (also demonstrated in Figure 5):

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Sample Technique EDXRF ICP-MS PXRF EDXRF ICP-MS PXRF EDXRF ICP-MS PXRF EDXRF ICP-MS

Rb ppm 192 181 172 201 182 183 193 187 177 167 164

Sr ppm 18 12.2 12 17 9.2 14 19 12.5 13 104 95.9

Zr ppm 78 79.0 71 75 73.1 73 75 80.2 81 140 147

Source Göllü Dağ Göllü Dağ Göllü Dağ Göllü Dağ Göllü Dağ Göllü Dağ Göllü Dağ Göllü Dağ Göllü Dağ Nenezi Dağ Nenezi Dağ

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PXRF 155 103 137 Nenezi Dağ 032 EDXRF 166 107 136 Nenezi Dağ ICP-MS 167 95.8 149 Nenezi Dağ PXRF 147 97 132 Nenezi Dağ 301 EDXRF 168 112 147 Nenezi Dağ PXRF 158 102 136 Nenezi Dağ 310 PIXE 176 130 137 Nenezi Dağ PXRF 150 100 128 Nenezi Dağ 322 PIXE 160 119 135 Nenezi Dağ PXRF 150 95 132 Nenezi Dağ Göllü Dağ 329 PIXE 187 15 73 Göllü Dağ PXRF 176 14 74 341 PIXE 173 114 148 Nenezi Dağ PXRF 152 96 132 Nenezi Dağ Göllü Dağ 352 EDXRF 187 17 87 Göllü Dağ PIXE 187 16 70 Göllü Dağ PXRF 178 14 76 360 PIXE 175 107 141 Nenezi Dağ PXRF 156 102 135 Nenezi Dağ 361 PIXE 169 116 150 Nenezi Dağ PXRF 155 100 130 Nenezi Dağ Göllü Dağ 365 PIXE 192 15 77 Göllü Dağ PXRF 178 12 73 Göllü Dağ 368 PIXE 188 14 74 Göllü Dağ PXRF 169 13 76 372 PIXE 163 107 140 Nenezi Dağ PXRF 158 100 137 Nenezi Dağ Table 3 – Concentration of Rb, Sr and Zr in 16 archaeological artefacts from Çatalhöyük (Turkey) examined by EDXRF (UC Berkeley), PIXE (CR2PA, Paris), ICP-MS (Grenoble) and pXRF Insert Figure 5 here

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Secondly, the results of analyses of the geological samples from Göllü Dağ and Nenezi Dağ that were produced with pXRF are compared to the published results of the same sources (Carter and Shackley, 2007; Poupeau et al., 2010). Table 4 and Figure 6 demonstrate that the mean concentration of Rb as measured by pXRF is lower than that measured by PIXE and EDXRF at both Göllü Dağ and Nenezi Dağ, while Sr and Zr contained concentrations comparable to other techniques (for comparisons see also Hancock and Carter, 2010).

Source Göllü Dağ

Method PIXE mean

Rb (ppm) 165-236 190

Sr (ppm) 0-17 11

Zr (ppm) 56-90 74

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167-245 203 173-186 181 166-194 178 179-191 171 156-205 174 154-160 157 143-158 152

17-32 24 9-12 10 8-16 12 115-130 107 100-120 108 90-97 93 97-100 99

73-92 83 70-73 71 69-76 74 125-179 145 126-155 137 136-139 138 132-137 136

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Nenezi Dağ

EDXRF mean ICP-MS mean PXRF mean PIXE mean EDXRF mean ICP-MS mean PXRF mean

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14

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Table 4 - The range and mean values of Rb, Sr and Zr in Göllü Dağ and Nenezi Dağ sources as determined by EDXRF (UC Berkeley), PIXE (CR2PA, Paris), ICP-MS (Grenoble) and pXRF Insert Figure 6 here

4.4.

The case of Melos

The Melian and other two Aegean sources were well discriminated from the other types in

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Figure 3. In the cases of Antiparos and Giali the situation is also quite clear. PXRF analyses of a small nodule from Antiparos gave readings of Rb (367 ppm), Sr (10 ppm), and Zr (128 ppm) which clearly chemically separated this source from the others analysed. Likewise, the ‘spotty’ Giali glass created a distinctive cluster on the diagram with the Rb (118-124 ppm), Sr

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(60-66 ppm) and Zr (94-97 ppm).

Turning to the Melian sources of Adamas and Demenegaki, these two also formed a cluster

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that stands apart from the other source groups with the elemental value ranges Rb (91-112 ppm), Sr (93-114 ppm) and Zr (102-121). However, scatter plots of Rb, Sr and Zr were unable to separate Adamas from Demenegaki, as their concentrations were almost identical (Figure 3). If we take them apart, Adamas has quantities of Rb (103-112 ppm), Sr (93-107 ppm), Zr (102-111 ppm) while this is slightly different from Demenegaki which has Rb (91103 ppm), Sr (105-114 ppm), Zr (108-121 ppm). Here, it was necessary to plot other elements in order to separate two obsidian types with greater certainty, these were titanium (Ti) and iron (Fe) (Figure 7). The samples analysed produced concentrations ranging for

ACCEPTED MANUSCRIPT 15 Adamas Ti (827-954 ppm) and Fe (5171-5882 ppm), and for Demenegaki Ti (1113-1294 ppm) and Fe (6824-7276 ppm). Insert Figure 7 here

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Shelford et al. (1982) were the first to suggest the use of major elements to discriminate the Melian sources. Liritzis (2008) published scatter plots (Fe-Ti-Sr) also using a portable EDXRF method for the separation of Melian obsidian (). The average values of Ti and Fe of Melian sources are for Adamas Ti (770-870 ppm) and Fe (7500-9000 ppm) and for

Method EDXRF PXRF

mean Demenegaki mean

EDXRF PXRF

mean

Ti (ppm) 770-870 820 827-954 870 1000-1114 1058 1113-1294 1162

Fe (ppm) 7500-9000 8234 5171-5882 5633 10200-11300 10516 6824-7276 7053

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Source Adamas mean

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Demenegaki Ti (1000-1114 ppm) and Fe (10200-11300 ppm) (Table 5):

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Table 5 – Ti and Fe ppm range and mean values produced by pXRF studies of Liritzis (2008) and this study The concentration of Fe drastically deviates in two procedures although their values consistently differ, enabling discrimination of the two sources in both cases. In this instance, a systematic error is evident, with calibration factor of 1.46 – 1.49. This can be ascribed to

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the instrument’s software providing precision but not absolute accuracy. The data is “internally consistent” and has systematic deviation from the readings of Liritzis 2008 (both Fe and Ti are reported in ppm), so when source data and object are compared it is going to

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give the same values but to make it comparable to other modes of analyses the data needs to be calibrated. 4.5.

The Carpathians

Analyses of 15 central European samples show that the source groups can be clearly separated into C1 and C2 (Figure 3). The pXRF reading of Carpathian obsidian demonstrated the following concentrations for Carpathian 1 - Rb (156-173 ppm), Sr (64-77 ppm) and Zr (62-74) while in Carpathian 2 - Rb (164-185 ppm), Sr (71-76 ppm) and Zr (118-140). The higher quantity of Zr in Carpathian 2 was the main discriminant of the two sources.

ACCEPTED MANUSCRIPT 16 Ten samples (five from C1 and five from C2) out of those 15 have also been analysed with the EDXRF instrument at MAX laboratory, McMaster University (Canada). The results of the pXRF show that the values for Rb are slightly lower than those produced by EDXRF, as was the case in central Anatolian obsidian. The quantities of the other two trace elements are

PXRF mean Carpathian 2 mean

EDXRF PXRF

mean

Rb (ppm) 174-185 180 154-173 163 174-197 190 164-185 175

Sr (ppm) 66-81 74 64-77 72 67-76 73 71-76 73

Zr (ppm) 75-80 78 62-74 67 125-148 138 118-140 127

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Method EDXRF

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Source Carpathian 1 mean

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compatible (Table 6; Figure 8):

Table 6 – The range and mean value of Rb, Sr and Zr in Carpathian 1 and Carpathian 2 source samples determined by EDXRF (MAXlab, McMaster University) and pXRF As with the Melian sources at Adamas and Demenegaki, it was nonetheless clear that two sub-sources within Carpathian 2 were represented in the pXRF analyses through the different

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values for Ti and Fe (Table 7). However, as the obsidian in these areas is in secondary contexts, in order to clarify the exact range and geographical location of sub-sources within the two proposed C2 flows [C2T and C2E] (Biró et al., 1986; see Williams-Thorpe et al., 1984), an extensive fieldwork program and systematic analyses of larger sample, as well as comparison with the results produced by different techniques (cf. Biró, 2006) would be

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required, and goes beyond the parameters of this specific study.

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Insert Figure 8 here

Source Carpathian 2* Carpathian 2 Carpathian 2 Carpathian 2 Carpathian 2 Carpathian 2 Carpathian 2* Carpathian 2*

Ti (ppm) 1701 364 682 327 326 331 2356 2032

Fe (ppm) 11671 7335 7315 7512 7052 7108 12551 11361

ACCEPTED MANUSCRIPT 17 Table 7 – The ppm concentration of Ti and Fe showing two distinct Carpathian 2 groups. The samples marked with asterisk could be ascribed to one group 5. Visual discrimination of obsidian

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The chemical characterisation has been done in conjunction with macroscopic (visual) discrimination, which relies on first-hand knowledge of the visual properties of obsidian sources that are expected in an area. The study of obsidian provenance has often involved macroscopic discrimination of obsidian artefacts using the naked eye. Even though it can be difficult and unreliable as a technique for differentiating types, remarks on physical

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properties are nonetheless commonly found in the literature (Braswell et al., 2000; Carter et al., 2008). In their early studies Cann and Renfrew (1964) referred to the results of chemical

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characterisation and visual properties of the various obsidian sources. They used visual characteristics as a means of discriminating source materials that could not – at that time - be discriminated chemically. At Çatalhöyük (Turkey), the macroscopic examinations of the entire assemblage (over 10 000 artefacts) has been done after which a sample was analysed with pXRF which confirmed the accuracy of the visual examination was over 95% (Milić et al., n.d.).

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The sources concerned in this study have distinct macroscopic properties and some of the

Source

Macroscopic characteristics Completely transparent or transparent with dark blue sprinkles. A variety is with white sprinkles Grey opaque or semi-transparent, sometimes with darker stripes or ‘stains’ inside Grey matt opaque occasionally semi-transparent stripy

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Göllü Dağ

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most common are listed here in Table 8:

Nenezi Dağ

Melos (Adamas and Demenegaki) Giali Carpathian 1 Carpathian 2

Transparent with white spherulites Generally very glossy and transparent, occasionally with some darker tinge Grey matt opaque occasionally semi-transparent

Table 8 – Description of the typical visual characteristics of obsidian from the analysed sources

ACCEPTED MANUSCRIPT 18 The image below (Figure 9) shows the colour variation of obsidian found in archaeological contexts that belong to these geological groups. According to the colour and transparency, obsidian from Nenezi Dağ, Melos (both sources) and Carpathian 2 show visual similarities being grey matt sometimes semi-transparent, while Göllü Dağ is completely transparent and

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is closely comparable visually to Carpathian 1.

Insert Figure 9 here

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6. Discussion: Archaeological significance of PXRF for obsidian studies

Obsidian characterisation studies have developed over the past 50 years into a powerful tool

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in archaeological research. It has long been employed by archaeologists as a proxy for analysing people’s movements and mapping long distance contacts (see also Hallam et al., 1976; Renfrew et al., 1968; Tykot, 2002; Williams-Thorpe et al., 1984). Obsidian characterisation studies have become the “success story in archaeological science” (WilliamsThorpe, 1995) with intensive surveys of source areas and the development of powerful techniques that could discriminate various obsidian types and sub-types with high precision. The emergence of pXRF instrumentation provides a non-destructive, fast and (comparatively)

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cheap resource but, perhaps more importantly, one better suited to the practical realities of archaeological research using a multi-regional and cross-border approach. A highly specialised scientific field of investigation has progressed to a much more “user friendly” system whereby data can be gained far more readily through software driven algorithms not

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manual mathematics, making it more accessible to non-specialist, if suitably trained, researchers. With the growing acceptance that this technology produces reliable results, the

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challenge is becoming one of applications whereby the scientific analyses can address issues that relate also to agendas in social theory (Freund, 2012; Molloy et al., forthcoming).

Some authors (cf. Craig et al., 2007; Nazaroff et al., 2009; Millhauser et al., 2011; Shackley, 2011; Sheppard et al., 2011; Frahm, 2012) have already discussed the capability in source determination and comparability of pXRF data to other analytical techniques. Analyses of geological samples from eight sources of at least 12 compositionally distinct types and concentrations of Rb, Sr and Zr produced by Innov-X pXRF were able to divide Göllü Dağ, Nenezi Dağ, Melian, Giali, Antiparos, Carpathian 1 and Carpathian 2 sources into separate clusters. In addition, bivariate plotting of Ti and Fe was successful in discriminating the two

ACCEPTED MANUSCRIPT 19 elementally and macroscopically related sources Adamas and Demenegaki on Melos, as well as two outcrops in Carpathian 2 source. The values of Rb, Sr and Zr are comparable to the other analytical methods as shown through analyses of Çatalhöyük and Carpathian

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assemblages previously examined by lab-based instruments.

The achievements of the method

The administrative and bureaucratic, as well as academic realities of sampling have impact on the applicability of many fields of artefact research and analyses. Destructive and expensive

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methods may not be suited to the generation of statistically valid data-sets, while the aggregate of many samples using pXRF allows different aspects to be explored on the basis

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of data quantity. This allows more archaeologically nuanced questions to be addressed that relate to the character of mobility from a regional perspective, with considerably greater confidence than the research and sampling parameters that have often gone hand in hand with lab-based analytical methods. Specifically, it would be possible to look at the patterns that emerge in the use of different obsidians at a site and in a region, and through multi-scalar analyses we might be able to see where patterns change as we progress from discussion of patterning at level of the household to issues of connectivity on regional scales. Equally, as

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well as consideration of spatial patterning, it becomes possible to address the relations between technological choice, practice, and obsidian procurement The different procurement and consumption patterns visible at groups of sites located in western Anatolia are one example of how this might work on the larger scale (Figure 2). In the case of the appearance

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of exceptional obsidian finds at specific sites (e.g. Dispilio or Mandalo in northern Greece),

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this could be related to the local connections of a small community or family groups.

Despite the scale of these aims, it has not been my intention here to present an overly positivist argument promoting the benefits of pXRF for artefact studies, but I have been more focussed on the potential of the method of technologically and spatially selective mass sampling that it allows. Alongside the traditional search for the rare (“exotic”) pieces and long distance distributions, we may also explore a) the frequency of obsidian relative to other raw materials in complete assemblages, b) the frequency of different obsidian types in multiple distributions, i.e. when more than one source is represented, c) the chaîne opératoire of existing obsidian types, d) obsidian frequencies at neighbouring and contemporary

ACCEPTED MANUSCRIPT 20 settlements, e) the procurement and consumption of obsidian on a micro and macro regional basis.

In my on-going research, the high resolution data analysis of obsidian origins and use at key

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study sites is being used to trace connectivity in the above regions, thus addressing aspects of the process of Neolithisation and colonisation, but also the ways in which agents / agencies within different distribution networks and systems engaged with each other. The context of the research presented here is therefore to characterise how peoples interacted in prehistory, what choices they made, and aspects of their perception of geographic boundaries and

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obstacles. We are under the horizon of being able to overtly socialise our understanding of circulation patterns through scientific analyses, but the method discussed in this paper

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demonstrates that this new technology allows new sampling regimes that give access to sufficiently large archaeological data-sets to allow regional distribution models to be more robustly created.

Acknowledgements

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The Central Anatolian and the Aegean obsidian source samples were provided by Tristan Carter (McMaster University), while some additional Melian obsidian was analysed in Cambridge University with the permission of Colin Renfrew. Artefacts previously analysed by alternative techniques were kindly leant to me by Tristan Carter, François-Xavier Le Bourdonnec, Gérard Poupeau and Steven, M. Shackley. Thank to Marcos Martinon-Torres

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and Barry Molloy for advice on earlier versions of the text, and to the two anonymous

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referees for their insightful and helpful comments.

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Figure captions

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1 – Major obsidian sources in central Anatolia, the Aegean and the Carpathians and related artefact distribution zones (by author)

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2 – Relative proportion of obsidian at archaeological sites discussed in the text (by author) 3 – Three-dimensional scatter plot of Rb, Sr and Zr illustrating the discrimination of the sources using pXRF (by author)

4 – Three-dimensional scatter plot of Rb, Sr and Zr showing the discrimination of the sources using 30, 60 and 90 seconds exposures (by author)

5 – Three-dimensional scatter plot of Rb, Sr and Zr showing the discrimination of 16 archaeological artefacts from Çatalhöyük (Turkey) examined by g EDXRF, ICP, PIXE and

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pXRF (by author)

6 – Three-dimensional scatter plot showing the mean values of concentrations of Rb, Sr and Zr in Göllü Dağ and Nenezi Dağ sources as recorded EDXRF, ICP, PIXE and pXRF (by author)

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7 – Two-dimensional scatter plot of Ti and Fe discriminating the two Melian sources – Adamas and Demenegaki (by author)

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8 – Three-dimensional scatter plot of Rb, Sr and Zr showing the discrimination of Carpathian 1 and Carpathian 2 with EDXRF and pXRF (by author) 9 – Typical visual characteristics of relevant obsidian from sources in central Anatolia, the Aegean and the Carpathians (by author)

Table captions 1 – The concentrations of elements (Ti, Mn, Fe, Zn, Rb, Sr, Zr, Ba, Pb) as determined by pXRF in ppm 2 – The range and mean values of Rb, Sr and Zr in obsidian from the sources

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5 – Ti and Fe range and mean values produced by pXRF studies of Liritzis (2008) and this

6 – The range and mean value of Rb, Sr and Zr in Carpathian 1 and Carpathian 2 source samples determined by EDXRF (MAXlab, McMaster University) and pXRF

7 - Table 7 – The ppm concentration of Ti and Fe showing two distinct Carpathian 2 groups.

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The samples marked with asterisk could be ascribed to one group

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8 – Description of the typical visual characteristics of obsidian from the analysed sources

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Successful pXRF discrimination of obsidian from central Anatolia, the Aegean and the Carpathians

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New questions through the ability to mass sample, potentially entire obsidian assemblages Multi-scalar approach to obsidian distribution, particularly in overlap areas

Investigation of directionality and intensity of Neolithic exchange and communication

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networks