Conventional petroleum-based adhesives present environmental challenges due to their toxicity, limited recyclability, and reliance on finite resources. Because ancient technology may serve as an inspiration for future solutions, the BiDebA (BioBased Debondable Adhesives) Interreg NWE project, systematically evaluated three archaeo-inspired bio-based adhesives –birch tar, rosin-beeswax blends and hide glue. The aim is to generate performance data relevant for future sustainable adhesive development. Natural additives used historically and in contemporary bio-based formulation research, including hematite and biochar, were incorporated to assess their influence on mechanical and thermal behaviour. A multi-analytical approach combining single lap-shear testing, thermal and rheological characterisation, and structural analysis was performed. The adhesives exhibited average lap shear strengths between 1.5 and 3.5 MPa, consistent with other light-duty bio-based systems. Birch tar showed the broadest substrate compatibility, including effective bonding to plywood and carbon-fibre composites, while rosin-beeswax blends and hide glue demonstrated material-specific strengths and limitations. Among the fillers tested, hematite provided the most consistent enhancements, improving mechanical strength and thermal stability while lowering debonding temperatures, particularly in birch tar and rosin-based systems. This identifies hematite as a dual-function additive capable of tuning performance while maintaining reversibility, supporting the development of repairable and recyclable bio-based adhesive systems. These findings highlight the value of archaeological adhesive technologies as informative material models rather than direct formulations. The dataset produced here also provides a scientific foundation for tailoring the mechanical and thermal behaviour of natural adhesives and supports ongoing efforts toward sustainable innovation in adhesive technology.

Adhesives are central to debates on the cognitive and technological capabilities of Neanderthals and modern humans. Spectrometric and chemical analyses suggest that Neanderthals relied primarily on birch bark tar, with some use of bitumen and conifer resin, whereas modern humans employed a broader range of materials, including resins, gums, tars, beeswax, and bitumen, sometimes mixed with inorganic additives. This evidence reveals a complex and varied technological landscape in which adhesive recipes were shaped by raw material availability, functional requirements, and cultural traditions. To explore Palaeolithic adhesive technology, we applied a multi-analytical approach—including optical and scanning electron microscopy, spectrometry, and chemical analyses—to lithic assemblages spanning the entire sequence of Morín Cave, northern Spain. This integrated protocol enabled us to distinguish modern contaminants from residues of probable archaeological origin and to suggest the presence of adhesives on a Châtelperronian and a Gravettian tool. Gas chromatography–mass spectrometry (GC-MS) detected resin or tar from a Cupressaceae plant on the Châtelperronian point, while potential insect wax, plant wax, or bitumen was identified on the Gravettian tool. Together with earlier observations of possible adhesive residues at Morín (Bradtmöller et al., Journal of Archaeological Science, 7:1-13, 2016), these findings increase the number of chemically supported cases to four, making the site one of the few in Europe with potential adhesive evidence spanning multiple Palaeolithic technocomplexes. The residues are consistent with hafting applications, likely linked to projectile technology, though the degree of certainty varies. Although the limited number of identified residues and difficulties in precise characterisation prevent direct comparison of Neanderthal and modern human adhesive traditions at Morín Cave, our results provide insights into Palaeolithic adhesive use. More importantly, they demonstrate the potential of a multi-analytical methodology to disentangle ancient residues from modern contaminants and to advance the systematic study of prehistoric adhesive technologies.

[This corrects the article DOI: 10.1371/journal.pone.0288629.].

Birch bark tar was used extensively throughout human history. While later ceramic-based production technologies are known, prehistoric aceramic techniques leave little to no archaeological evidence. Experimental tar production attempts to fill this gap and suggest potential techniques. However, their archaeological relevance is unclear. Through an in-depth biomolecular analysis using Gas Chromatography-Mass Spectrometry, this study attempts to differentiate tars produced using four experimental aceramic techniques: condensation, ash mound, pit roll, and raised structure. In doing so we publish the largest collection of GC-MS results of aceramic birch tars. The results show that pentacyclic triterpenoids, characteristic of birch bark, vary between the production techniques in relation to heating exposure and perhaps the tar collection method. This allows for a tentative identification of tars produced through the condensation and ash mound techniques, which were formed consistently using short periods of heating and collected systematically by scraping. In contrast, tars produced using the pit roll and raised structure techniques do not have consistent molecular signatures. Despite the partial success of Gas Chromatography-Mass Spectrometry, the archaeological relevance is questioned because this technique is only applicable to samples from optimum lipid preservation conditions when a high number of pentacyclic triterpenoids are preserved. Therefore, using Gas Chromatography-Mass Spectrometry to determine the transformation methods of organics, like birch bark, may not be an appropriate standalone technique to fairly discuss the technological capabilities of past populations.

This study explores traditional adhesives using an ethnobiological approach within a multisocioecological context in Zambia. Through semi-structured interviews, videotaped demonstrations, and herbarium collections, we investigated the traditional adhesives people know and use, the flexibility of production processes, resource usage, and knowledge transmission in adhesive production. Our findings reveal flexibility in adhesive production systems. People use a wide range of organic and inorganic materials in their adhesive recipes. Recipes are flexible, demonstrating the ability to adapt to changes and substitute materials as needed to achieve the desired end product. Additionally, our study reveals a variety of redundant pathways for knowledge transmission typically confined within individual population groups. These include same-sex vertical transmission and distinct learning spaces and processes. Also, we identified material procurement zones showing that people are prepared to travel 70 km for ingredients. We use our findings to review the archaeology and we discuss the identification of archaeological adhesives, the functional roles of adhesive materials, adhesive storage, and the sustained human interaction with species from families such as Euphorbiaceae and Apiade. Our findings underscore the diversity and adaptability of traditional adhesive production and suggest that further research on adhesives would reveal similar diversity within the archaeological record.

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.

We implement a method from computer sciences to address a challenge in Paleolithic archaeology: how to infer cognition differences from material culture. Archaeological material culture is linked to cognition, and more complex ancient technologies are assumed to have required complex cognition. We present an application of Petri net analysis to compare Neanderthal tar production technologies and tie the results to cognitive requirements. We applied three complexity metrics, each relying on their own unique definitions of complexity, to the modeled production processes. Based on the results, we propose that Neanderthal technical cognition may have been analogous to that of contemporary modern humans. This method also enables us to distinguish the high-order cognitive functions combining traits like planning, inhibitory control, and learning that were likely required by different ancient technological processes. The Petri net approach can contribute to our understanding of technology and cognitive evolution as it can be used on different materials and technologies, across time and species.

The intentional production of birch bark tar by European Neanderthals as early as 190,000 years ago plays an important role in discussions about the technological and behavioural complexity of Pleistocene hominins. However, research is hampered because it is currently unknown how Neanderthals were producing birch tar. There are several different techniques that could have been employed, but these differ in their apparent production complexity, time and resource efficiency. Identifying production processes in the archaeological record is therefore paramount for furthering research on the technical behavioural repertoire. Organic biomarkers, identified with Gas Chromatograph–Mass Spectrometry (GC–MS), have been used to identify possible production processes during the Neolithic. Here we test whether these biomarkers can also distinguish Palaeolithic (aceramic) tar production methods. We produced tar using five different methods and analysed their biomolecular composition with GC–MS. Our results show that the biomarkers used to distinguish Neolithic tar production strategies using ceramic technology cannot be reliably used to identify tar production processes using aceramic Palaeolithic techniques. More experimentation is required to produce a larger reference library of different tars for future comparisons. To achieve this, complete GC–MS datasets must also be made publicly available, as we have done with our data.

Technological processes, reconstructed from the archaeological record, are used to study the evolution of behaviour and cognition of Neanderthals and early modern humans. In comparisons, technologies that are more complex infer more complex behaviour and cognition. The manufacture of birch bark tar adhesives is regarded as particularly telling and often features in debates about Neanderthal cognition. One method of tar production, the ‘condensation technique’, demonstrates a pathway for Neanderthals to have discovered birch bark tar. However, to improve on the relatively low yield, and to turn tar into a perennial innovation, this method likely needed to be scaled up. Yet, it is currently unknown how scaling Palaeolithic technological processes influences their complexity. We used Petri net models and the Extended Cyclomatic Metric to measure system complexity of birch tar production with a single and three concurrent condensation assemblies. Our results show that changing the number of concurrent tar production assemblies substantially increases the measured complexity. This has potential implications on the behavioural and cognitive capacities required by Neanderthals, such as an increase in cooperation or inhibition control.

Adhesive production is one of the earliest forms of transformative technology, predating ceramics and metallurgy by over 150,000 years. The study of the adhesives used by Neandertals and early modern humans currently plays a significant role in debates about human technological and cognitive evolution. Depending on the type of adhesive used, different production sequences were required. These can vary in complexity and would have needed different knowledge, expertise, and resources to manufacture. However, our knowledge of this important technological development is severely hampered by poorly understood taphonomic processes, which affects the preservation and identification of adhesive materials and leads to a research bias. Here we present the results from a 3-year field preservation experiment. Flint flakes hafted and non-hafted with replica adhesives were left to weather naturally on and below the surface at two locations with different soils and climatic conditions. Differential preservation was recorded on a variety of natural adhesives by digitally measuring the surface area of each residue before and after the elapsed time. Residues were further assessed and photographed using metallographic optical microscopy. Results show that certain adhesives preserve to a significantly higher degree than others, while some materials may be more easily overlooked or visually misdiagnosed. We must therefore be aware of both taphonomic and identification biases when discussing ancient adhesive technology. This research provides a first look that will help us understand the disparities between which adhesives were used in the past and what we find in the archaeological record today.