The authors identify natural bitumen on stone implements dating to 70 000 BP. Ir u proposed that this represents residue from hafting, taking the practice back a further 30 000 years from the date previously noted and published in Nature. The bitumen was tracked to a source 40km away, using gas chromatography-mass spectrometry and carbon isotopes.
Keywords: Near East, Djebel Bichri, Mousterian, bitumen, micro-traces, hafting, microscopic techniques, geochemical analysis, stable isotope, absolute dating, gas chromatography-mass spectrometry
In 1992 bitumen was discovered on convergent sidescrapers and Levallois flakes in Mousterian leveis dating to 40 000 BP ar Umm el Tlel (el Kowm Basin, Central Syria, Figure 1) (Borda & Muhesen 1993; Borda et al. 1996; 1998). This led to a reconsideration of the commonly accepted idea that bitumen on artefacts appeared in the Near East (near the Dead Sea at Netiv Hagdud) only in the eighth millennium BC. Since the year 2000, eight archaeological levels in Mousterian complex VI 3 at Umm el Tlel have been excavated over an area of 50[m.sup.2], yielding an impressive amount of lithic and faunal material (between 150 and 300 objects per [m.sup.2]). There is considerable uniformity between the assemblages from these levels, showing successive occupations by human groups sharing the same knowledge (Boeda et al. 2002). Seven burnt flints from layers VI 3c and d were dated by thermoluminescence (Aitken 1985), and yielded statistically compatible results anda weighted mean of 71 [+ or -] 4ka, which places the deposition of these two layers (Martinson et al. 1987) at the transition between MIS 4 and 3 (Table 1).
[FIGURE 1 OMITTED]
Among more than 1000 artefacts from the eight layers in complex VI 3, 200 lithic artefacts carried a black residue. Some of them had impregnated the underlying sediment with a very clear and well-preserved imprint. These black macro-residues are logically located, always corresponding to those parts of the tool which were grasped or handled as shown by two of the artefacts presented in this paper: a flake (no. 1780, Figure 2) anda Levallois point (no. 2023, Figure 3). While it is impossible to know the precise use of such material, we infer that it could have been used as adhesive to attach a handle composed of animal or vegetal material or as a sleeve to provide protection for the user's hand. It is also probable that the treatment or preparation of this material, as well as the amount applied to the surface of tools, would vary depending on its ultimate purpose.
Geochemical analysis of bitumen: identification of source
Geochemical analyses were carried out on samples of macro-residues of bitumen taken from the artefact surface or from imprints of three Levallois artefacts (nos. 1780, 1781 and 2023, Table 2), a fragment of black pebble (no. 1782, Table 2), and bitumen samples collected from Bichri tar sands (nos. 170 and 430, Table 2).
A crust of black organic matter, located on both faces of the Levallois artefacts (Figures 2 and 3), was scraped from the surface. Initial Rock-Eval pyrolysis (Espitalie & Bordenave 1993) was fully consistent with archaeological bituminous mixtures previously excavated from various sites from the Near East and the Gulf (Connan & Deschesne 1996; Connan et al. 1998). Samples extracted with dichloromethane exhibited a gross composition (Table 2) of archaeological bitumen, i.e. crude oil which has been severely altered by weathering (photo-oxidation, biodegradation, oxidation, water washing, evaporation, etc.).
The source of the bitumen was tracked using the carbon 13 isotope, since it has been shown that the [delta][sup.13]C values of asphaltenes can correlate archaeological bitumen to parent oil seeps (e.g. Connan et al. 2006; Connan & Carter 2007; Stern et al. 2007). In the present study, [delta][sup.13]C values of the three Umm el Tlel artefact samples (nos. 1780, 1781 and 1782, Table 2) agree with values recorded in 24 samples of tar sands from various locations in the Djebel Bichri (Figures 1 and 4). These values are significantly different from those recorded in samples of the other famous source of bitumen in the area, namely Hit (Connan & Nishiaki 2003).
[FIGURE 2 OMITTED]
To further substantiate this correlation, the molecular spectra of [C.sub.15]+alkanes and [C.sub.15]+aromatics was undertaken on the data acquired from gas chromatographymass spectrometry (GCMS analysis). Sterane and terpane distribution patterns confirmed the fossil character of the black organic matter and its origin from the Djebel Bichri tar sands. Two of the 24 samples (nos. 430 and 170), show almost identical patterns (Figure 5). Well-preserved triaromatic steroids (Riolo et al. 1986; Lemoine 1996) also show similar GCMS results (Figure 6) from Umm el Tlel samples and Bichri tar sands.
Detecting micro-residues of bitumen
The detection of micro-residues required a different analytical approach as there was insufficient sample material for geochemical analysis by GCMS. The problem was approached experimentally: bitumen from the same Djebel Bichri tar deposits was prepared and applied as an adhesive, and then compared under the microscope to the traces on the Levallois artefacts. Bitumen from the quarry site was mixed with quartz and gypsum to render it malleable, and then applied in large quantities onto five pieces to obtain sleeves, and in lesser amount on five other flakes to serve as adhesive between the flint and wooden handles.
[FIGURE 3 OMITTED]
These experimentally produced layers were then compared microscopically to bitumen identified geochemically on three Levallois artefacts (nos. 1780, 1781 and 2023, Table 2) and on other Levallois artefacts from layer VI 3d for which black micro-residues could not be analysed by geochemical techniques. These comparisons showed strong similarity and all are therefore very likely bitumen traces. The presence of the same microscopic traits on the 200 artefacts analysed clearly attests to a generalised use of bitumen.
[FIGURE 4 OMITTED]
These new analyses confirm the use of bitumen during the Middle Palaeolithic at Umm el Tlel at the beginning of MIS 4, as well as its importance in the lithic technological system. Far from being a tare occurrence, it appears rather to be ah omnipresent element on Levallois artefacts. The raw material likely came from a source more than 40km east in the Bichri Mountains.
Nevertheless, this use cannot be generally applied to ali 60 Mousterian layers currently known at Umm el Tlel. It is currently absent in 15 layers dated between 71 000 and 42 000 BP, a hiatus with no obvious explanation. The only pertinent element is that, based on typological, technological and use-wear analyses, these 15 archaeological layers are all culturally different from each other. By contrast the four layers showing bitumen use at 40 000 BP are culturally identical, as are the eight layers of complex VI 3 dated to 71 000 BP. This suggests two periods at least in which stable populations were established with a wide control of territorial resources, including bitumen.
Very recent discoveries from the underlying Mousterian complex Vil seem to attest to ah even older use of bitumen. All of these data confirm that bitumen was ah integral part of the Near Eastern Mousterian technological world from irs earliest phase. More generally, taking into account the data available for this period, we see that hafting and use of other tars, such as birch-bark pitch in Europe (Grunberg 2002; Mazza et aL 2006; Modugno et al. 2006) were commonly known in different Neanderthal populations and perhaps anatomically modern humans ones. This use simply reflects a level of technological development in certain Mousterian populations that is too often underestimated.
[FIGURE 5 OMITTED]
[FIGURE 6 OMITTED]
A fuller version of this investigation, together with a more comprehensive dataset will appear in Paleorient by kind permission of Antiquity's editor.
Received: 21 May 2007; Revised: 9 April 2008; Accepted: 17 June 2008
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Eric Borda (1), Stephanie Bonilauri (1), Jacques Connan (2), Dan Jarvie (3), Norbert Mercier (4), Mark Tobey (5), Helene Valladas (6), Heba al Sakhel (7) & Sultan Muhesen (8)
(1) Department d'Ethnologie et de Prehhtoire, CNRS, UMR 7041, ArScAn, equipe An TET, Maison de l'Archeologie et de l'Ethnologie, Universite de Paris X- Nanterre, 21 allee de l'Universite, 92023 Nanterre, France (Email: email@example.com; firstname.lastname@example.org)
(2) Laboratoire de Biogeochimie Moleculaire, CNRS, UMR 7177, Universite Louis Pasteur, 25 rue Becquerel, 67200-Strasbourg, France (Email: email@example.com)
(3) Worldwide Geochemistry, LLC, P.O. Box 789, Humble, Texas 77347, USA (Email: firstname.lastname@example.org)
(4) Institut de Recherche sur les Archeomateriaux, CNRS, UMR 5060, Centre de Recherche en Physique Appliquee a l'Archeologie (CRP2A), Maison de l'Archeologie, Universite de Bordeaux, 33607-Pessac Cedex, Erance (Email: Norbert.Mercier@u-bordeaux3.fr)
(5) Encana Oil & Gas, USA Inc., 370 17th St., Suite 1700, Denver, CO 80303, USA (Email: Mark.Tobey@ encana.com)
(7) Labomtoire des Sciences du Climat et de l'Environnement, LSCE/IPS, UMR CEA-CNRS-UVSQ, Centre des faibles Radioactivites, Laboratoire mixte CNRS-CEA, avenue de la Terrasse, 91198-Gif-sur-Yvette Cedex, France (Email: email@example.com) Musee National de Damas, Ministere de la Culture, Direction generale des Antiquites et des Musees, Shoukry al-Qouwatly St., Damas, Syrie (Email: firstname.lastname@example.org)
(8) Departement d'Archeologie, Universite de Damas, Damas, Syrie (Email: email@example.com)
Table 1. Each flint specimen was treated according to the procedure described by Valladas (1992) and Valladas et al (1994). The U-238, Th-232, and K-40 contents of the dated specimens (columns 2 to 4) were measured by neutron activation analysis Joron 1974). For each radioisotopic measurement, a combined statistical and systematic error of [+ or -] 10% is essentially caused by uncertainties in the reference standard. The alpha sensitivity (column 5) was determined by comparing the TL-[alpha] and TL-[beta] signals induced by [alpha] and [beta] particles from Pu-238 and Y/Sr-90 sources, respectively (Valladas & Valladas 1982). The internal dose-rate (column 8) of each flint was computed from its contents U, Th and K and from the specific dose-rates given by Adiamec and Aitken (1998). The external dose-rates (column 12) were deduced from measurements taken in the field by [SO.sub.4]Ca:Dy dosimeters. The gamma dose-rate (column 10) has been corrected to take into account the absorption of the gamma rays passing through the sample. The cosmic dose-rate (column 11) was estimated after taking into account the thickness of the sediment fill (Prescott & Hutton 1994). The ED values (column 16) were measured with an automatic apparatus by the additive method; they include the supralinearity correction. This latter was measured from the TL growth curve regenerated after the natural powder was reheated for 1.5 hrs. at 350[degrees]C (Mercier et al. 1992). Following Aitken's (1985) recommendations, the statistical and systematic errors were calculated separately for each flint. Each of the tabulated overall errors represents the mean square average of the two (column 19).sector sector U Th K [alpha]-sens. (PPM) (PPM) (%) [mu]G[gamma]/a/ 1000 [alpha] V 0.93 0.24 0.06 23.20 V 0.73 0.22 0.07 19 VI 0.81 0.27 0.07 18.70 VI 1.45 0.20 0.07 14.60 VI 1.54 0.18 0.08 21.60 VI 1.43 0.15 0.08 22.80 VI 1.02 0.22 0.01 20.50 VI 0.86 0.19 0.19 14.80 VI 1.32 0.17 0.02 22.50 Total dose [mu]G[gama]/a alpha beta internal [+ or -] V 386 192 584 44 V 251 167 423 31 VI 274 180 462 29 VI 366 273 653 48 VI 570 291 870 68 VI 558 272 841 62 VI 368 165 538 42 VI 227 281 519 29 VI 511 211 732 57 Total dose [mu]G[gama]/a gamma Cosmic External [+ or -] V 606 160 766 60 V 635 160 795 60 VI 295 160 455 51 VI 294 160 454 50 VI 302 160 462 52 VI 299 160 459 51 VI 302 160 462 52 VI 294 160 454 50 VI 297 160 457 51 Total dose [mu] G[gama]/a Total Ed dose [+ or -] (Gy) [+ or -] V 1350 75 88.9 4.7 V 1218 67 85.5 7 VI 918 58 68.6 3 VI 1107 70 87.4 2.4 VI 1331 86 84.1 4.8 VI 1300 81 75 15 VI 1000 66 80.6 5.9 VI 972 58 67 2.7 VI 1189 76 90 3.5 Age (ka) [+ or -] V 65.9 5.5 V 70.2 6.8 VI 74.8 6.6 VI 79 7.1 VI 63.2 6.3 VI 57.7 8.4 VI 80.6 8.1 VI 68.9 6 VI 75.7 7 Table 2. References and geochemical data on the three Umm el Tlel samples and on the two related Bichri tar sands. Significance of abbreviations: TOC = Total Organic Carbon (in % by weight/sample), HI = Hydrogen Index, HC = hydrocarbons formed by cracking between 300 and 600 [degrees]C, OI = Oxygen Index, [CO.sub.2] = [CO.sub.2] formed and released below 400 [degrees]C, Tmax = temperature of the maximum of S2 pyrolysis peak, Total extract = Total extractable organic matter isolated by dicholomethane, saturates = [C.sub.15] + saturated hydrocarbons, aromatics = [C.sub.15] + aromatic hydrocarbon, [[delta].sup.13] Casp = [[delta].sup.13] C of asphaltenes (in [per thousand] / (DB), Ts = 18[alpha]-22, 29, 30-trisnorneohopane, Tm = 17 [alpha]-22, 29, 30-trisnorhopane, GCR = Gammacerane, 30[alpha][beta] H = 17[alpha], 21[beta]=hopane. Umm el Tlel Lab Field Sample campaign no. reference Sample type decription UM.01 1780 AL 157 no. black material Black grains with 60--VI on a Levallois excavation earth 3d' point and quartz grains (Bichri Sand?) UM.01 1781 AJ 158 no. black material Two black lumps 5--VI on a Levallois 3d' flake UM.01 1782 AL 159 no. small fragments Thin flat crust 518--VI of a black with numerous 3d'1 pebble quartz grains (Bichri tar sand?) UM.04 2023 AJ 154-VI black material Some black grains 3c'--seat on a Levallois in a beige matrix point Bichri 170 samples from Tar sand outcrops surface Bichri 430 BS07 surface of the Tar sand quarry accumulation HI (in OI Umm el TOC mg (in mg Tlel Lab (weight HC/g [C0.sub.2]/ Tmax campaign no. %/ sample TOC) g TOC) ([degrees]C) UM.01 1780 21.3 570 8 430 UM.01 1781 UM.01 1782 10.8 552 15 429 UM.04 2023 Bichri 170 outcrops Bichri 430 quarry Total umm el extract Tlel Lab (weight %/ % % % campaign no. sample) saturates aromatics resins UM.01 1780 24.5 3.2 7.8 17 UM.01 1781 49 8.1 8.1 18.2 UM.01 1782 9 3 7.9 15.2 UM.04 2023 4.3 8.5 36.2 Bichri 170 outcrops Bichri 430 quarry [[delta].sup.13] umm el Ca sp (in GCR/ Tlel Lab % [per thousand]/ 30[alpha] campaign no. asphaltenes PDB) Ts/Tm [beta] H UM.01 1780 64.2 -28.5 0.9 3.8 UM.01 1781 58.6 -28.8 0.9 3.4 UM.01 1782 68.2 -28.5 0.4 5.1 UM.04 2023 51.1 -28.4 0.31 2.6 Bichri 170 -28.4 0.58 2.6 outcrops Bichri 430 -28.7 0.34 2.2 quarry…