Archaeological findings prove the appearance and use of birch bark tar since the Middle Palaeolithic. The production and use of birch bark tar and pine wood tar has overlapped since at least the late Neolithic, but probably for much longer. The reliable chemical identification of such archaeological tar residues can offer valuable insights into, for example, ancient technical complexity, trade and culture. In this context, the scarcity of these mainly organic residue findings in the archaeological record bears the need for non-destructive analytical tools. However, there is currently no systematic proposed way for this purpose. We aim here to verify the organic nature and test the reliability of the identification of archaeological pine wood tar and birch bark tar with a combination of SEM-EDS, FTIR microspectroscopy in reflectance mode and XRD. We examined a set of experimental adhesive replicas of pine tar and birch tar in pristine form, but also after a three-year-long weathering experiment. Additionally, we studied a set of archaeological samples, consisting of Mesolithic bone/antler points with adhering hafting residues, form the Dutch North Sea. This research shows that degradation negatively influences the reliable verification and identification of the organic residue constituents significantly. SEM-EDS as a starting point of analysis verifies the residue's organic nature, but it cannot be used to identify birch or pine tar. XRD can identify crystalline additives in the adhesive mixture, like ochre and wax, as well as phases related to the artefact's environment of burial and provenance. Micro-FTIR is also capable of verifying the organic matter of the residue constituents. The differentiation of birch and pine tars is hindered by vibrational modes occurring in neighbouring wavenumbers for both tars, and by the limited research on degradation markers indicative of thermal treatment to prove tar production. Until reference collections also account for degradation and include a wide variety of adhesives, results of FTIR collected in reflectance mode are best treated with some caution.

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Evidence of different compound resin-based adhesives is present in South Africa from at least 77000 years ago. Ancient glue production is considered one of the oldest known highly complex technologies, requiring advanced technological and mental abilities. However, our current knowledge of adhesive materials, recipes, and uses in South Africa is limited by the lack of in-depth analysis and molecular characterization of residues. To deepen our knowledge of past adhesive technology, we performed a detailed multi-analytical analysis (use-wear, XRD, μ-CT, IR spectroscopy, GC-MS) of 30 Later Stone Age tools with adhesive remains from Steenbokfontein Cave, South Africa. At the site, tools made of various rocks were hafted with compound adhesives, and we identified three recipes: 1) resin/tar of Widdringtonia or Podocarpus species combined with hematite; 2) resin/tar of Widdringtonia or Podocarpus species mixed with hematite and another plant exudate; 3) resin/tar without hematite. The studied scrapers were used in hide-working activities, and the studied cutting tools were used to work animal and soft plant matters. All scrapers display evidence of intense resharpening and were discarded when no longer useable. The combination of different methods for residue analysis reveals the flexibility of adhesive technology at Steenbokfontein. Despite the consistent use of conifer resin/tar throughout the sequence, we observed that other ingredients were added or excluded independently of the tools’ raw materials and functions. Our results highlight the long-lasting tradition of using adhesive material from conifer species but also the adaptability and flexibility of adhesive traditions. The systematic application of this multi-analytical approach to Pleistocene adhesives will be useful to better characterise adhesive traditions and enhance the debate on the technological, cognitive, and behavioural implications of this technology.@en