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List of molecular constituents identified in the VOCs of experimental birch bark tars

List of molecular constituents identified in the VOCs of experimental birch bark tars

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To develop an analytical methodology, as non-destructive as possible, suitable for the identification of natural substances from archaeological origin, we studied the potentiality of solid-phase microextraction (SPME) for analysing birch bark tar, an adhesive commonly used during ancient times. First of all, birch bark tars were produced by a contr...

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Context 1
... was also necessary to avoid any constituent co-eluted with another one. Seven constituents (numbered 4, 5, 14, 20, 31, 48 and 56 in Table 1, chromatograms and graphs) corresponding to different chemical types with var- ious polarities and molecular weights (an alkane, a sesquiter- penoid, a naphthalene derivative and four phenolic compounds) present these characteristics. Fig. 3 plots the chromatographic peak area counts for each of these compounds against the time of exposure when using the DVB/CAR/PDMS coating. ...
Context 2
... data obtained correspond to exposure time of 15, 30 and 60 min. Numbers between brackets: numbering of individual compounds in Table 1. detected. ...
Context 3
... data obtained correspond to exposure time of 15, 30 and 60 min. Numbers between brackets: numbering of individual compounds in Table 1. slowly after a 60 • C temperature of exposure than at lower tem- perature, probably indicating that equilibrium is almost reached at 80 • C. ...
Context 4
... chromatograms obtained are very complex and provide a great number of individual compounds (Figs. 2, 6 and 8). Because of the similarities of the chromatographic patterns, the results of the identification of the VOCs are presented for the optimised conditions for liquid and solid birch bark tars (Table 1). ...

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Citations

... Overall, compared to other residue types such as starch (Barton et al., 1998;Fullagar, 2006;Haslam, 2004Haslam, , 2006Mercader et al., 2008Mercader et al., , 2018Torrence & Barton, 2006), phytoliths (Anderson, 1980;Kealhofer et al., 1999) and plant-based adhesives (Cnuts et al., 2018a(Cnuts et al., , 2018bCnuts et al., 2018aCnuts et al., , 2018bKozowyk et al., 2020;Perrault et al., 2018;Regert, 2004;Regert et al., 2006), apatite residues have received less attention, and particularly studies devoted to their taphonomy are only beginning to emerge (for a summary of burial experiments, see Monnier & May, 2019). These works have so far demonstrated the relative longevity of functional bone residues through burial of residue-bearing experimental tools (Langejans, 2010;Monnier & May, 2019). ...
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Bone mineral residues derived from stone tool production and use can survive on lithic artefacts for extended periods of time. They thus form a line of evidence for reconstructing Palaeolithic human activities. Despite having been frequently reported on ancient stone tools, the identification of these residues is not without complications, and their diagenesis as well as their potential overlap with residues formed in the burial environment are only beginning to be addressed. We report here environmental and use-related calcium phosphate residues on previously washed and handled Gravettian stone tools from Hohle Fels (Germany) and Abri Pataud (France). The residues were characterised with optical microscopes and SEM–EDS. Our results provide an optimistic note on the preservation of bone mineral residues at sheltered Upper Palaeolithic sites, but also point to multiple and complex origins of apatite deposits on lithic tools. We discuss the characteristics of functional versus taphonomic residues and draw attention to the formation of authigenic hydroxylapatite and its implications for the identification of ancient bone mineral residues from tool use. We argue that this aspect has been largely overlooked by analysts until now. This calls for further refinement of analytical techniques, including continued research into sediment diagenesis and residue taphonomy, as well as the incorporation of production and use-wear evidence to ensure reliable residue interpretations.
... Birch tar is a substance derived from the triterpenes of birch bark (Regert et al., 2006). The earliest examples are known from the European Middle Palaeolithic and are attributed to Neanderthals (Grünberg et al., 1999;Mazza et al., 2006;Niekus et al., 2019). ...
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Birch tar was the first adhesive produced by humans. Its study has consequences for our understanding of human evolution or the development of specialised craftsmanship. One of the better‐documented birch tar making methods is the ‘double‐pot’ technique where two containers are used, one containing bark, the other collecting the tar. Birch tar made with double‐pots has low viscosity and bad adhesive properties. To obtain a usable adhesive, it must be reduced in volume by cooking. We investigate the evolution of tar’s mechanical properties during cooking. We use lap‐shear tests to investigate strength, stiffness and failure behaviour. We found that tar must be cooked for one hour and a half to acquire adhesive properties. When cooked for longer, strength and stiffness increase over a 30 min lasting time span. Cooking for even longer, beyond this 30 min window, produced a substance that could no longer be used as an adhesive. The implications are that tar cooking requires a high level of skill because specific signs indicating the desired properties must be recognised during the process. Tar cooking constitutes a supplementary investment in time and resources and appears to be an activity associated with a certain degree of risk.
... In the development of previous studies, the solubility and purity of extractive substances from the outer bark of birch in petroleum ether at its boiling point were investigated [87]; subsequent works [88,89] showed that the use of fractional crystallization during extraction in a specially designed apparatus for intensive mass transfer can be a promising, inexpensive and simple method of simultaneous concentration of lupeol in the mother liquor and purification of betulin from mixtures of triterpenes (Scheme 1). A relatively simple and cheap method of separating betulin from birch bark and purifying it to a very high purity (>99%) was proposed in [23]. ...
... In the development of previous studies, the solubility and purity of extractive substances from the outer bark of birch in petroleum ether at its boiling point were investigated [87]; subsequent works [88,89] showed that the use of fractional crystallization during extraction in a specially designed apparatus for intensive mass transfer can be a promising, inexpensive and simple method of simultaneous concentration of lupeol in the mother liquor and purification of betulin from mixtures of triterpenes (Scheme 1). Scheme 1. Technological scheme of betulin production in works [87][88][89]. ...
... In the development of previous studies, the solubility and purity of extractive substances from the outer bark of birch in petroleum ether at its boiling point were investigated [87]; subsequent works [88,89] showed that the use of fractional crystallization during extraction in a specially designed apparatus for intensive mass transfer can be a promising, inexpensive and simple method of simultaneous concentration of lupeol in the mother liquor and purification of betulin from mixtures of triterpenes (Scheme 1). Scheme 1. Technological scheme of betulin production in works [87][88][89]. ...
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Betulin is the most popular of the known triterpenoids of the lupan series. It has valuable pharmacological properties. It exhibits antibacterial, antiviral, antitumor, hypolipidemic and other types of activity. The prospects of using betulin in medicine, pharmacology, and veterinary medicine require the development of effective methods for obtaining it from waste from the woodworking industry. Therefore, the question arises of the need to develop a technology for isolating and purifying triterpenoids from birch bark in large quantities. This review contains a variety of methods for the isolation of betulin. The advantages and disadvantages of the proposed methods are described. The following methods are considered: vacuum sublimation after preliminary alkaline; vacuum pyrolysis; supercritical extraction with carbon dioxide or mixtures of carbon dioxide with various solvents; extraction with organic solvents. Also, the method of microwave is described, it is activation on the example of the Kyrgyz birch (Betula kirghisorum), this is an endemic species that has not been studied before, growing on the territory of the Republic of Kazakhstan.
... Gas chromatography-mass spectrometry (GC-MS) has been the most widely employed technique for analyzing different resinous materials (Aveling & Heron, 1998;Bailly et al., 2016;Degano et al., 2019;Egenberg et al., 2002;Lucquin et al., 2007;Morandi et al., 2018;Orsini et al., 2015;Regert et al., 2006). Although efficient and a well-proven approach providing detailed molecular information (esp. ...
... The terpenoid compounds identified in samples were assigned to biomarkers of wood tars from betulaceae and pinaceae. The triterpenoids with lupane skeleton were detected in significant amounts in all samples but one (Stanovoye 4 (90)): biomarkers of birch bark tar, such as, lupeol, lupenone, betulin, betulin aldehyde, oleanic acid, lanostane, and their derivatives (Perthuison et al., 2020;Regert et al., 2006). Thus we can conclude that in most of the cases we have clear tendency toward the dominance of birch bark tar biomarkers (betulin derivatives), with sometimes additional small inclusions of coniferous tree resin in the samples analyzed with GC-MS. ...
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Attenuated total reflection‐Fourier transform‐infrared spectroscopy (ATR‐FT‐IR) analysis of 100 adhesive samples from different prehistoric composite artefacts, pottery and amorphous lumps across Eastern Europe and Urals were conducted with the aim to establish a fast analytical screening method for adhesive assignment. The ATR‐FT‐IR analysis allowed the identification of major chemical components of the adhesive samples which were assigned to three main groups: birch bark tar without major additives, birch bark tar with additives and minor/non‐birch bark tar samples. ATR‐FT‐IR spectra were further analyzed using principal component analysis (PCA)‐based discriminant analysis (DA) that allowed additional refinement of adhesive classifications. The ATR‐FT‐IR results and the DA classification were confirmed by analyzing a selection of samples with gas chromatography‐mass spectrometry (GC‐MS). Results demonstrate that ATR‐FT‐IR coupled with DA classification allows fast and reliable preliminary identification of the major components in archaeological adhesives and their further classification. As such it is a considerable and faster alternative to more laborious GC‐MS analysis, especially in the case of very small samples.
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... Dans ce contexte, les études réalisées jusqu'à présent sur des échantillons organiques archéologiques en vue d'identifier les substances naturelles utilisées pour leur préparation ont porté principalement sur la caractérisation de composés de bas poids moléculaire (Regert, 2004 ;Lucquin et al., 2007 ;Burger et al., 2010 ;Sarret et al., 2017 ;Courel et al., 2018). Ces composés présentent l'avantage d'être facilement analysables par les méthodes analytiques conventionnellement employées pour l'analyse moléculaire de mélanges complexes, comme la GC-MS (Charters et al., 1993 ;Modugno et al., 2006b ;Regert et al., 2006 ;Burger et al., 2009Burger et al., , 2010Courel et al., 2018), la HPLC-MS ( Van der Doelen et al., 1998a ;Charrié-Duhaut et al., 2007), ou encore la Py-GC-MS (Pyrolysechromatographie en phase gazeusespectrométrie de masse), et la TD-GC-MS (Thermodésorption -Chromatographie en phase gazeusespectrométrie de masse) (Buckley et al., 1999(Buckley et al., , 2004Languri, 2004 ;Hao et al., 2019). ...
... Ces composés, en combinaison avec les dérivés de type allobétulane T59-T62 également identifiés grâce à leur mode de fragmentation et aux spectres de masse disponibles dans la littérature (Budzikiewicz et al., 1963 ;Schmidt and Huneck, 1979 ;Li et al., 1989 ;Aveling et Heron, 1998 ;Rageot, 2015 ;Courel, 2016 ;Courel et al., 2018), sont connus pour être des marqueurs d'altération issus de la pyrolyse des triterpènes natifs de l'écorce de bouleau. De ce fait, ils sont utilisés comme des biomarqueurs importants pour l'identification de brais de bouleau, substance qui semble donc constituer notre échantillon archéologique (Bosquet et al., 2001 ;Modugno et al., 2006b ;Regert et al., 2006 ;Courel et al., 2018 ;Rageot et al., 2019). Ainsi, les Δ 2 -triterpènes T56-T57 sont formés respectivement par élimination de la fonction alcool en C-3 du lupéol T25 et de la bétuline T54 (Fig. 4.6). ...
... d) Mode de préparation du brai de bouleau archéologique L'analyse par GC-MS de la substance organique provenant de la céramique I15 a permis de révéler une majorité de biomarqueurs de la série du lupane comprenant à la fois des composés naturellement présents dans l'écorce de bouleau, mais aussi, et surtout, des produits de dégradation thermique de ceux-ci, menant donc à son identification comme étant du brai de bouleau. Celui-ci ayant été trouvé le long d'une ancienne fissure de la céramique, il a très probablement été utilisé pour la réparer (Charters et al., 1993 ;Connan et al., 2000 ;Bosquet et al., 2001 ;Urem-Kotsou et al., 2002 ;Rageot et al., 2016 (Dudd et Evershed, 1999), peut-être fournie par les phénols provenant de la pyrolyse de la lignine (Faix et al. 1990 ;Reunanen et al. 1996 ;Regert et al., 2006 ;Colombini et al., 2009b ;Orsini et al., 2015). ...
Thesis
Cette thèse a été consacrée à la problématique de l’altération de substances organiques en contexte archéologique, avec pour objectifs de donner des clés analytiques et expérimentales pour étudier les processus mis en jeu, d’identifier de nouveaux outils moléculaires indicateurs des processus subis par les matériaux organiques archéologiques et d’interpréter l’impact de ces processus sur les signatures moléculaires de ces matériaux. Après la mise au point d’un protocole expérimental de vieillissement en laboratoire reproduisant les processus « naturels » de vieillissement de substances organiques archéologiques, nous avons déterminé que les réactions croisées entre ingrédients (esters d’acides gras, terpènes) conduit à la formation de composés oligo-/polymériques intéressants à étudier à l’aide de réactions de dégradation chimique. L’étude moléculaire de matériaux organiques archéologiques a aussi été abordée. Ainsi, de la résine de diptérocarpacées provenant de deux épaves asiatiques du XIIème siècle et du brai de bouleau utilisé pour réparer des céramiques néolithiques ont été identifiés. De nouveaux biomarqueurs triterpéniques d’altération issus de la dégradation anaérobie en milieu sédimentaire de triterpènes précurseurs (résine), et des biomarqueurs de traitement thermique intense (brai) ont été caractérisés.
... The use of wood as a fuel is illustrated by several compounds both in extracts and in bulk OM. Most of them are related to benzoic derivatives, phenol derivatives and more generally derivatives related to lignin degradation (Simoneit et al., 1993;Quénéa et al., 2004;Simoneit, 2005;Regert et al., 2006;Shadkami and Helleur, 2010;Lejay et al., 2016). As they are absent from the Control, they can be attributed to the fuel used in the present study. ...
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A better understanding of the operation and use of prehistoric fires is fundamental to interpreting the organization of living spaces. Following a previous study that focused on the organic signatures of fireplaces fueled with wood and/or bones, this study targeted the completion of an experimental reference database through the addition of a wood-fueled fireplace dedicated to the cooking of meat. Different sedimentary features of this experimental fireplace were visually identified (e.g. darkening, reddening), sampled, and subjected to geochemical analysis. Corg and N contents were quantified, samples were extracted with organic solvents and analyzed through GC–MS and bulk organic matter was characterized through py(TMAH)-GC–MS. Five different samples were studied and compared with a control sample, representative of the local background. A significant increase of Corg and N contents was measured for the three samples presenting darkened or charred caracteristics. The meat-cooking fireplace seems to be characterized by the strong contribution of nitrogen, which was visible in elementary analyses as well as in the molecular composition of solvent extracts, and bulk organic matter. More specifically, compounds containing nitrile functions, amides, N-heterocyclic and N-aromatic compounds could be detected in solvent extracts. Amines, amides, N-heterocyclic and N-aromatic compounds could be identified in py(TMAH)-GC–MS. Some of these compounds present a relative stability in soils and could therefore aid in our comprehension and functional interpretations of archaeological fireplaces, and may, more particularly, make it possible to highlight the use of fireplaces for the cooking of meat.
... Our aim was (1) to investigate the chemical composition of the first exudation of the tar and (2) to determine the heating parameters (temperature, heating time) that would allow the initiation of bark transformation into tar. Similar laboratory tests performed to date have reported results showing a great variability (Charters et al. 1993;Aveling and Heron 1998;Sauter et al. 2000;Regert et al. 2006). Our experiments in test tubes using fresh supple and smooth barks showed the formation of a volatile yellow liquid at around 300°C, with the exudate becoming yellow-brown at 350°C and a black tar appearing after a further 10 min of constant heating. ...
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Birch bark tar, the oldest adhesive known in Europe, was widely used during Prehistory. This material, produced by the dry distillation of birch bark, has been identified in various spheres of activities and provides valuable information on the know-how and technical and territorial systems of past societies. This biomaterial can also provide evidence on socio-economic networks and mobility. However, very little is known about the production systems of birch bark tar during Prehistory, including the Neolithic period. The lack of findings in the archaeological record necessitates the development of an approach that combines experimental archaeology and biomolecular chemistry. We present here (1) the results of experiments in which different birch bark tar production systems were tested and (2) the molecular signatures of the birch bark tars produced according to different processes based on the use of ceramic vessels. The key role of bark quality is highlighted for the first time. This study also details direct archaeological inference of the experimental results obtained: a total of 23 samples from the site of Nice-Giribaldi (France, second part of the fifth century BCE) was investigated. Different categories of birch bark tars were identified during Neolithic in the south of France, providing evidence for the existence of complex manufacturing systems and procurement networks.
... To the best of our knowledge, there are no published reports of solid-phase microextraction (SPME) applied to archaeological studies of the volatile constituents of canned or other prepared foodstuffs. However, SPME applications in archaeology appear to be increasing [12][13][14], and reports of other analytical/chemical methods applied to archaeological studies of historical foods and food remains dates back to the late 20th century [10,11,[15][16][17][18][19][20]. ...
... To the best of our knowledge, there are no published reports of solid-phase microextraction (SPME) applied to archaeological studies of the volatile constituents of canned or other prepared foodstuffs. However, SPME applications in archaeology appear to be increasing [12][13][14], and reports of other analytical/chemical methods applied to archaeological studies of historical foods and food remains dates back to the late 20th century [10,11,[15][16][17][18][19][20]. ...
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An essential dimension of food tasting (i.e., flavor) is olfactory stimulation by volatile organic compounds (VOCs) emitted therefrom. Here, we developed a novel analytical method based on solid-phase microextraction (SPME) sampling in argon-filled gas sampling bags with direct gas chromatography-mass spectrometry (GC-MS) determination to profile the volatile constituents of 31 homemade preserves prepared in South Dakota (USA) during the period 1950-1953. Volatile profiles varied considerably, but generally decreased in detected compounds, complexity, and intensity over three successive 2-h SPME sampling periods. Volatile profiles were generally predominated by aldehydes, alcohols, esters, ketones, and organic acids, with terpenoids constituting much of the pickled cucumber volatiles. Bisphenol-A (BPA) was also serendipitously detected and then quantified in 29 samples, at levels ranging from 3.4 to 19.2 µg/kg, within the range of levels known to induce endocrine disruption effects. Absence of BPA in two samples was attributed to their lids lacking plastic liners. As the timing of their preparation coincides with the beginning of BPA incorporation into consumer products, these jars may be some of the first BPA-containing products in the USA. To the best of our knowledge, this is the first effort to characterize BPA in and volatile profiles of rare historical foods with SPME.