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