Management systems of adhesive materials throughout the Neolithic in the North-West Mediterranean

https://doi.org/10.1016/j.jas.2020.105309Get rights and content

Highlights

  • Evolution of natural substances exploited as adhesives throughout the Neolithic.

  • Diversity of materials used: birch bark tar, coniferous resins, bitumen, beeswax.

  • Birch bark tar is mainly used in the NW Mediterranean for different purposes.

  • Variable and/or complex adhesive production systems and supply networks.

Abstract

Plant resins, tars and organic fossil substances provide valuable insights into the ecological, environmental and cultural contexts of ancient societies. Their study offers evidence of past know-how, production systems, socio-economic networks and mobility. In this paper, we present new data from 16 sites located in the North-West Mediterranean that provide new insights into the exploitation of these substances for their adhesive and hydrophobic properties throughout the Neolithic (6000-2500 cal BCE). The substances investigated are discussed in the light of their molecular composition, their uses and manufacturing processes. Spatial analyses were also performed to elucidate raw material procurement strategies.

This study considerably increases the body of data available from the Mediterranean and tells a diachronic story of adhesive production and use throughout the Neolithic, highlighting the variability and complexity of production systems and supply networks at different spatial scales. While most adhesive and hydrophobic substances were probably collected locally, birch bark tar was very likely transported across long distances to reach Mediterranean coastal sites. Birch bark tar exploitation intensified in South-Eastern France during the Middle Neolithic, while the Late Neolithic is characterised by a diversification of the substances employed and their range of uses: bitumen, birch bark tar (pure or mixed with Pinaceae resin, beeswax and possibly fat/oil) were important materials that were used for a variety of purposes. Pure Pinaceae exudates were exclusively employed for waterproofing pottery. We also highlight the standardisation of birch bark tar production for adhesive manufacture observed in Provence during the first part of the 4th millennium cal. BCE.

Introduction

Plant resins, tars and organic fossil substances (e.g. bitumen) have been exploited since the Middle Palaeolithic (Boëda et al., 1996, 2008; Grünberg et al., 1999; Hauck et al., 2013; Mazza et al., 2006; Nardella et al., 2019; Niekus et al., 2019). Their role as a hallmark of cognitive sophistication remains a matter of debate (Schmidt et al., 2019). Very recently, it was demonstrated that birch bark tar can represent a new source of ancient DNA that reveals the genetic characteristics of those who chewed it (Jensen et al., 2019; Kashuba et al., 2019).

These substances are multifunctional materials that were used since Prehistory for their adhesive and hydrophobic properties, among other things (Table S1). In the archaeological record, they are usually discovered as elements used to haft tools or to mend ceramic vessels, as waterproofing agents (Aveling and Heron, 1998a; Bonfield et al., 1997; Connan, 1999; Connan and Van de Velde, 2010; Evans and Heron, 1993; Langlois et al., 2005; Mitkidou et al., 2008; Regert, 2001; Regert, 2004; Regert et al., 1998), or even as aesthetic components of various objects (including for colour) (Bosquet et al., 2001; Connan et al., 2004; Rageot et al., 2016; Regert et al., 2019; Sauter et al., 2002; Urem-Kotsou et al., 2018). Plant exudates and tars may also have been employed in medicinal practices, such as dental care (Aveling and Heron, 1999; Evans and Heron, 1993; Stern et al., 2006), or used for their odoriferous properties (Lucquin et al., 2007; Marangou and Stern, 2009; Mathe et al., 2004; Stern et al., 2003).

Although plant exudates and tars provide valuable insight into the ecological, environmental and cultural contexts of ancient societies, their informational potential is generally underestimated and not fully tapped. In large part, this can be explained by the fact that organic residues are prone to degradation, they do not present any characteristic morphology in archaeological contexts, and the chemical analyses applied to these substances are not always appropriate (for a more detailed state of the art, see S1).

Adhesive materials from Palaeolithic contexts are particularly scarce. In Europe, only 15 analyses based on the reliable molecular characterisation of adhesive substances are available. Birch bark tar (from Central Italy to the Netherlands) (Grünberg et al., 1999; Mazza et al., 2006; Niekus et al., 2019) and Pinaceae resin (in Southern Italy) (Degano et al., 2019) have been identified as hafting adhesives. In the Levant, bitumen was commonly used for the same purpose (8 analyses) (Boëda et al., 1996, 2008; Hauck et al., 2013). During the Palaeolithic, in most cases, adhesives were made from raw materials that were locally available in significant quantities (birch/Pinaceae forests or bitumen sources).

More evidence is available in Europe from the 6th millennium cal. BCE onwards. In total, 234 samples from 37 sites dated to 6000-2500 cal. BCE have been analysed at the molecular scale using GC-MS or LC-MS/MS methods (Fig. 1; for a detailed list of sites, see Table S1). The relative abundance of samples from the Holocene can be ascribed to better preservation of organic matter from more recent periods and/or more favourable preservation contexts, particularly at Northern European wetland Mesolithic sites (Aveling and Heron, 1998b, 1999; Stern et al., 2006). Favourable conditions are also observed at 10 Neolithic sites (mostly wetland sites from central Europe), which represent 63% of all Neolithic sites analysed and 87% of all samples analysed from North of the Alps and in the alpine regions (Aveling and Heron, 1998b; Bleicher et al., 2015; Evans and Heron, 1993; Hayek et al., 1990; Heron et al., 1991; Mirabaud et al., 2009; Regert et al., 1998, 2000; Sauter et al., 2000)(Table S1). The emergence of ceramic technology may also have contributed to the increase in the amount of material that have been studied. Although bitumen, birch bark tar, Pinaceae resins and beeswax can be preserved as free lumps in the soil (S1) (Rageot et al., 2016, 2019b), other lipidic additives (e.g. fats and oils) are more prone to degradation due to bacterial activity, unless trapped in the clay matrix of ceramics. Notably, pottery could also have provided a wider range of uses/applications for adhesive and hydrophobic materials (Drieu et al., 2018; Rageot et al., 2016, 2019a), whereas their function cannot be inferred when they were associated with a perishable support material.

To date, research on adhesives north of the Alps and in the alpine regions (99 samples from 20 sites) seems to show an interesting continuity of the use of pure birch bark tar up until the first part of the 4th millennium cal. BCE (Table S1, Fig. 1). Birch bark tar was mostly used for its adhesive properties, especially for hafting tools and repairing ceramics, but it was also employed for decorative purposes and chewed (possibly as a form of dental care). In the early 4th millennium cal. BCE, several other substances began to be used for their adhesive properties in addition to pure birch bark tar, namely bitumen, animal glue and a multicomponent material including birch bark tar and Pinaceae resin, as well as other plant tars. Currently, data from regions South of the Alps (135 samples from 17 sites) are mostly restricted to South-Eastern Europe and the Adriatic, from 15 sites dated to the 6th millennium. Bitumen was used in Abruzzo and Apullia (Nardella et al., 2019) for its adhesive properties (stone tool hafting). In the Balkans and the Northern Aegean different adhesive substances and functions are observed, as illustrated by the use of birch bark tar and Pinaceae tar/resins for ceramic reparation, coating and decoration, and possibly for their odoriferous properties (Marangou and Stern, 2009; Mitkidou et al., 2008; Urem-Kotsou et al., 2018). In sum, considering the European Neolithic on the whole, our knowledge of use of adhesives has been limited to specific and isolated chronocultural contexts. Indeed, prior to this study, only two Neolithic sites (Nice-Giribaldi and La Rouvière) South-West of the Alps had been investigated. These sites date to between the end of the 6th millennium and the 2nd millennium cal. BCE, and published data indicate the use of pure birch bark tar (Binder et al., 1990; Perthuison et al., 2019; Rageot et al., 2019b; Regert et al., 2000).

Given the significant gaps in our knowledge regarding adhesive use in the North-West Mediterranean, our goal is to gain a more comprehensive and diachronic understanding of the exploitation of adhesive and hydrophobic materials in the region. Thus far, only a small number of publications have addressed adhesive management, with most of these focusing on procurement strategies of bitumen (Buckley et al., 2004; Connan, 1999; Nardella et al., 2019) and birch bark tar (Rageot et al., 2016, 2019b; Urem-Kotsou et al., 2018). One study also deals with decisive steps in the chaîne opératoire of tar production in archaeological contexts (Rageot et al., 2019b).

In this study, organic residues were analysed from 16 archaeological sites (23 archaeological layers) located between North-Eastern Iberia and Abruzzo and occupied between the Early and the Late Neolithic (6000-2500 cal. BCE), with a particular focus on Middle and Late Neolithic contexts from Southern France as these have yielded a particularly large quantity of adhesive materials. An integrated approach employing biomolecular archaeology, spatial analysis, experimental archaeology and botany was developed to (i) characterise the organic substances, (ii) investigate procurement strategies and systems of production of adhesive and hydrophobic materials, and (iii) determine the spheres of activity areas in which adhesives were used. Specific practices and mobility patterns linked to the exploitation and circulation of these biomaterials are also examined yielding new insights into technical and territorial systems of the Neolithic.

Section snippets

Archaeological sites and samples investigated in the North-Western Mediterranean Neolithic

A total of 85 visible organic residues adhering to ceramic vessels, lithic or bone tools or recovered as free lumps from 16 sites were chemically analysed (for a detailed list of the sites and sampling contexts, see Table S2). The investigation was focused on organic residues from sites in southern France (76 samples). A large inventory of archaeological materials from Provence was studied including, free lumps recovered directly from the sediment or following flotation (together with

Results

Extractable organic residues were detected in 64 of the 85 samples tested. At least six different organic substances were identified based on their molecular composition. They were detected pure or as mixtures, sometimes at different stages of transformation or degradation: birch bark tar, fat/oil, beeswax, bitumen and two different profiles of Pinaceae resin. Most of the samples from which organic could not be extracted were carbonised residues from the cave of Pertus II (17/21). Their

Discussion

With this study, the number of samples and of archaeological contexts associated with adhesive materials from the Mediterranean Neolithic have both substantially increased (from 135 to 198 and from 17 to 32, respectively) (Table S3 and Table S4). Maps of Fig. 6, Fig. 7, Fig. 8, Fig. 9 combine the data based on molecular analyses obtained in this work with those already published. Although this study is not exhaustive, the expanded body of data nevertheless enables discussion of the evolution of

Conclusion

This work provides the most extensive view to date of the exploitation of adhesive and hydrophobic materials in the North-West Mediterranean Neolithic. Despite the continuous use of birch bark tar throughout this period, current results indicate that substances used for their adhesive and hydrophobic properties became more diversified from the 4th millennium BCE onwards (Fig. S4). Overall, pure Pinaceae exudates were only identified as waterproofing agents of ceramic vessels, while bitumen and

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

The authors thank the French National Research Agency (ANR) for the funding of the project Exsudarch (2010-2014, M. Regert dir.) which allowed extensive diachronic interdisciplinary investigations on plant exudates and tars as well as researching the biogeography of plant raw materials. We are also grateful to the Academy 5 of the IDEXJEDI from UCA (Université Côte d’Azur), to the MSHS sud-est, to the CNRS-INEE and to the CEPAM for funding the research project ARCHEOPLANTES (2018-2020, M.

References (121)

  • J.S. Mills

    Diterpenes of larix oleoresins

    Phytochemistry

    (1973)
  • V. Andrieu-Ponel et al.

    Towards the reconstruction of the Holocene vegetation history of Lower Provence: two new pollen profiles from Marais des Baux

    Veg. Hist. Archaeobotany

    (2000)
  • L. Angeli et al.

    2019. La produzione ceramica di Colle Santo Stefano (Ortucchio, L'Aquila) nel quadro del Neolitico antico medio-adriatico

    Rivista di Sci. Preistoriche

    (2018)
  • E.M. Aveling et al.

    Identification of birch bark tar at the mesolithic site of star carr

    Anc. Biomol.

    (1998)
  • E.M. Aveling et al.

    Neolithic glue from the Sweet Track, somerset

    England NewsWARP

    (1998)
  • E.M. Aveling et al.

    Chewing tar in the early Holocene: an archaeological an etnographic evaluation

    Antiquity

    (1999)
  • M. Barbero

    55/61. Tignes-Larche

  • J. Battentier et al.

    La grotte de Pertus II (Méailles, Alpes-de-Haute-Provence) : exploitation du couvert forestier au Chasséen récent (3850-3650 cal. BC)

  • J. Battentier et al.

    L’abri Pendimoun (Castellar, Alpes-Maritimes) : évolution du couvert forestier et exploitation du milieu au Néolithique (5800-2000 cal. BCE)

    Quaternaire

    (2015)
  • J. Battentier et al.

    Le paysage végétal des occupations de la plaine de Saint Maximin la Sainte Baume (Var) du Néolithique moyen à l'a^ge du Fer : première synthèse diachronique des résultats anthracologiques des opérations du Clos de Roques

  • D. Binder

    Silex blond et complexité des assemblages lithiques dans le Néolithique liguro-provençal

  • D. Binder

    Approvisionnement et gestion des outillages lithiques au Néolithique: l'exemple de Giribaldi en Provence orientale

  • D. Binder et al.

    Identification de brai de bouleau (betula) dans le néolithique de Giribaldi (Nice, France) par la spectrométrie de masse

    Revue d'Archéométrie

    (1990)
  • D. Binder et al.

    L'abri Pendimoun à Castellar (Alpes-Maritimes). Nouvelles données sur le complexe culturel de la céramique imprimée méditerranéenne dans son contexte stratigraphique

    Gallia préhistoire tome

    (1993)
  • D. Binder et al.

    La circulation de l’obsidienne dans le sud de la France au Néolithique. Rubricatum

    Gavà

    (2012)
  • D. Binder et al.

    Epipaléolithique et Néolithique dans l’arc Liguro-Porvençale

    Bulletin du Musée d’Anthropologie préhistorique de Monaco

    (2008)
  • E. Boëda et al.

    New evidence for significant use of bitumen in middle palaeolitic technical systems at Umm El Tlel (Syria) Around 70,000 BP

    Antiquity

    (2008)
  • E. Boëda et al.

    Bitumen as a hafting material on Middle Palaeolithic artefacts

    Nature

    (1996)
  • K.M. Bonfield et al.

    The Chemical Characterisationof Wood Tars in Prehistoric Europe: a Case Study from Neolithic of Southern Germany

  • F. Borrell et al.

    The Status of Imported Barremian-Bedoulian Flint in North-Eastern Iberia during the Middle Neolithic

    (2019)
  • D. Bosquet et al.

    Identification de brai de bouleau sur quatre vases du siterubané de Fexhe-le-Haut-Clocher "Podrî l'Cortri". Premiers résulrats

    Notae Praehistoricae

    (2001)
  • V. Brisotto

    Quartz hyalin et obsidienne dans les séries néolithiques entre Rhône et Alpes du Nord : poids et signification, Circulations et identités culturelles alpines à la fin de la Préhistoire

    Centre d'Archéologie Préhistorique de Valence, Valence

    (1999)
  • S. Buckley et al.

    Complex organic chemical balms of Pharaonic animal mummies

    Nature

    (2004)
  • S. Burri

    Vivre de l'inculte, vivre dans l'inculte en Basse Provence centrale à la fin du Moyen Âge. Histoire, archéologie et ethnoarchéologie d'un mode de vie itinérant

    Lab. D'archéol. Médiévale Et Moderne En Méditerranée - UMR

    (2012)
  • J. Carles

    Le Puy. Carte de la végétation de la France au 200000e

    (1951)
  • G. Cartoni et al.

    GC-MS characterisation and identification of natural terpenic resins employed in works of art

    Ann. Chim.

    (2004)
  • L. Caruso et al.

    Landscape and forest exploitation at the ancient Neolithic site of La Draga (Banyoles, Spain)

    Holocene

    (2014)
  • S. Charters et al.

    Ifentification of on adhesive used to repair a roman jar

    Archaeometry

    (1993)
  • J. Connan

    Use and trade of bitumen in antiquity and prehistory: molecular archaeology reveals secrets of past civilizations. Philos Trans R Soc Lond B Biol Sci

    (1999)
  • J. Connan et al.

    Archaeological bitumen: identification, origins and uses of an ancient Near easter material

    Mater. Res. Soc. Symp. Proc.

    (1992)
  • J. Connan et al.

    Bitumen in early ceramics art : bitumen-painted ceramics from late Neolithic Tell Sabi Abyad (Syria)

    Archaeometry

    (2004)
  • J. Connan et al.

    De la géochimie pétrolière à l’étude des bitumes anciens : l’archéologie moléculaire

    Comptes Rendus Séances Acad. Inscriptions Belles-Lett. (CRAI)

    (1993)
  • J. Connan et al.

    An overview of bitumen trade in the Near East from the Neolithic (c.8000 BC) to the early Islamic period

    Arabian Archaeol. Epigr.

    (2010)
  • G. Cremonesi

    La Grotta dei Piccioni di Bolognano nel quadro delle culture dal neolitico all'età del bronzo in Abruzzo. Giardini

    Pisa

    (1976)
  • S. Debrand-Passard et al.

    Synthèse géologique du Sud-Est de la France – stratigraphie et paléogéographie

    BRGM Éd.

    (1984)
  • I. Degano et al.

    Hafting of Middle Paleolithic tools in Latium (central Italy): New data from Fossellone and Sant’Agostino caves

    PLOS ONE

    (2019)
  • G. Dupias

    La Corse. Carte de la végétation de la France au 200000e

    (1965)
  • G. Dupias

    Rodez. Carte de la végétation de la France au 200000e

    (1966)
  • G. Dupias

    Avignon. Carte de la végétation de la France au 200000e

    (1973)
  • G. Dupias

    Luz. Carte de la végétation de la France au 200000e

    (1982)
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