The article presents the results of a technical and technological study of organic and inorganic microstates on the surface of stone artefacts lying in the Early Mesolithic layer of the Dvoinaya Cave (North-West Caucasus). Based on microchemical and IR spectroscopic analyses, organic substances of plant and animal origin, as well as mineral components, were determined. The presence of organic residues on the tool blades is consistent with the functional determinations obtained using the tracological analysis performed earlier.

Keywords: Mesolithic, Northwest Caucasus, stone tools, organic remains, microchemical analysis, IR spectroscopy, tracology.

Introduction

The Dvoinaya Cave is located in the Guba Gorge in the Northwestern Caucasus and has been studied since 2007 under the guidance of E. V. Leonova (Leonova and Alexandrova, 2012; Leonova, 2014). To date, three cultural layers with their own structural features and differences in stone inventory have been identified on the monument (Leonova et al., 2013). Materials from the Early Mesolithic cultural layer of the Dvoyaya Cave (lithological layer 6) were used for the study. At the moment, the museum's collection includes more than 3,700 stone products.

In the course of tracological study, a significant amount of residues of substances of different morphology and color was found on the surface of the tools. Such remains (20 % of the number of artefacts studied by the trace method) were recorded on 153 stone objects (Alexandrova, 2014). Their organic origin has been suggested*.

The work was carried out within the framework of the Program of the Presidium of the Russian Academy of Sciences "Traditions and Innovations" and the RFBR project N 12 - 06 - 00202-a.

*All the finds were washed in water with a soft brush during on-site processing. Immediately before performing the analysis under a microscope, the surface of stone tools was treated with alcohol.

By shape, color, and location, the remains are divided into four groups. Group 1 includes residues that are long, smoothly curved, rarely branching bands of gray, porous, and fibrous matter at the microlevel. Their width is approx. 1 mm (in some cases 2-3 mm) and a thickness of approx. 0.5 - 2.0 mm. Similar structures were recorded on the surface of 111 studied objects (69 % of the number of finds with remains), both on morphologically expressed tools, nuclei, and debitages. The appearance of these formations on the surface of stone tools is probably associated with post-depositional processes. The same group includes subcircular and oblong, but shorter spots of gray-brown matter, the structure of which is also fibrous at the microlevel. The fibrous structure of Group 1 residues can be a carbonized imprint of plant fibers that have adhered to the surface of tools after they have already entered the cultural layer. Wood fibers (presumably pine) were found in the host rock of the Early Mesolithic layer (Leonova, 2013, p. 68).

Group 2 includes residues in the form of spots of a resin-like substance of different colors: from translucent light yellow to opaque dark brown and reddish, which do not have a clear structure. The spots are more voluminous than those described above, varying in size (from 1.5 cm to several millimeters across and from fractions of a millimeter to 2-3 mm in height). In rare cases, resin-like residues form colored (brown, brown, dark gray shades) stripes with a width of no more than 2 mm and a thickness of no more than 1 mm. The remains of this group are recorded on 38 stone objects (24 % of the number of finds with remains), which, according to the results of trace analysis, are tools. These spots are located on the accommodation parts of tools - the edges of scrapers, incisors, petioles of tips, etc. The traces under consideration were presumably interpreted as the remains of resin or adhesive masses containing resin, with which the stone tool was attached to the handle.

Group 3 includes residues on the blades of tools in the form of strips of substance, the direction of which coincides with the direction of wear marks. As part of a group of 12 items (7 % of the number of finds with leftovers): scraper, notched tools, plates with traces of retouching, segments. On the blade of the end scraper for processing hides/leather at the macro level, strips of light red-brown substance were found, which completely coincide with linear micro-traces in the direction. Similar combinations of macrostatches presumably of organic origin with micro traces of wear are noted on the plow for wood processing. Similar bands of reddish matter are traced on the blades of two segments, which, according to the complex of macro-injuries, were used as oblique arrowheads [Alexandrova, in print].

Group 4 includes remnants in the form of spots and stripes of red, brown, black, and whitish shades presumably of mineral origin. As a rule, the regularity in their arrangement on stone tools is not traced; most likely, these remains are of natural origin. Ocher spots of various shades are visually detected on some of the items in this group. Several objects were found, the surface of which was almost completely covered with ochre, which suggested the presence of a binder in the composition of the "paint".

The problem of preservation of organic substances on the surface of Stone Age artifacts has been actively developed in the last decade. Organic remains were found on stone products from Holocene deposits in Emu Cave and Ruf Fol Canopy in Australia. The presence of organic components in the form of animal residues (collagen, muscle, fat and bone tissue, blood (including protein and red blood cells), hair, wool), as well as vegetable (fragments of amorphous cellulose, plant tissue, resin and phytoliths) and mineral components (ochre, vivianite) was established [Robertson, 2011; Eales et al., 1999]. Several studies based on a wide range of materials from the Pacific Islands and Alaska have been devoted to specialized analysis of organic residues [Gerlach, Newman, and Knell, 1996; Allen et al., 1995].

A comprehensive analysis of Middle Paleolithic stone materials from two Rose Cottage and Sibudu cave sites in South Africa allowed us to determine that the arrowheads and geometric microliths under study served as arrowheads, as well as to identify accommodation zones and reconstruct how they were fixed on the shaft. Remains of tar, blood, bone matter, and ochre were found on the tips (Lombard and Wadley, 2007, 2009).

Based on biomolecular analysis, an interpretation of the genesis of organic remains on Upper Paleolithic stone tools from the cultural layers of the Naves Kastrishcha site in Greece was proposed. The appearance of these formations on the surface of stone tools is explained by contact with organic and inorganic components of the cultural layer already in the post-positional period (Galanidou, 2006).

Considerable work related to the determination of the degree of preservation of organic remains depending on the conditions of storage and processing of collections of stone objects was carried out by a team of American and German specialists on the materials of

from Aurignacian layers of cave sites in Germany (Hardy, Bolus, and Conard, 2008; Hardy, 2009). According to their conclusion, organic remains on the surface of Stone Age tools can be preserved, even if the latter were subjected to cameral cleaning.

Archaeological materials

To find out the origin of the described substances on the surface of stone tools from the Mesolithic layer in the Dvaya Cave and to study their composition, nine artefacts were selected from all groups, with 12 micro-samples taken from the surface (see table):

N 5086-plate fragment (lost proximal part), sample N 1;

N 4866-plate fragment (distal end lost) with traces of fire exposure, no traces of disposal, sample N 2;

N 4647 - low plate segment, weakly symmetric, one end broken off, sample N 3;

N 4295-high segment from the plate, asymmetric, sample N 4;

N 6069-low segment from the plate, symmetrical, sample N 5;

N 5520-excavated tool made of plate flake, samples N 6.1, 6.2;

N 4231-podo round scraper made of flakes, sample N 7;

N 927 - plate with traces of disposal, samples N8. 1-8.3;

N 719 - plate fragment (medial part) covered with red ochre (?), sample N 9.

Research methodology

The technical and technological study of organic and inorganic residues on the surface of flint artifacts was carried out using microchemical analysis and IR spectroscopy methods.-

Results of technical and technological research of organic and inorganic materials

They were studied by X-ray fluorescence and crystal-optical methods. The following equipment was used: microscopes MBS-10, Micromed MS-1. Mikmed-2; POLAM L-213M and POLAM R-312 polarization microscopes; Varian 610-IR IR microscope with Varian 660-IR IR spectrophotometer; METOREX X-MET 3000T X-ray fluorescence analyzer; SKIMITAR Series Fourier transform IR spectrophotometer with GladiATR diamond attachment. Trace analysis was performed using an Olympus metallographic microscope with a magnification of 50-500x, as well as a Canon EOS HOOD SLR camera.

Results of microchemical and IR spectroscopic analyses and their interpretation Based on the data of a comprehensive analysis of substance residues on the surface of flint products from the Early Mesolithic layer in the Dvoyaya Cave, organic components of various origins were identified (see table). In the studied micro-samples, signs of carbonation of organic material and the presence of mineral components in its composition were recorded. Micro-samples N 1 and 2 obtained from samples of substances belonging to Group 1 according to our classification have the following composition: coniferous exudate (oleoresin), as well as mineral components (coarse-grained calcite and red-brown clay minerals) (Fig. 1). The presence of oleoresin is indicated by the following absorption bands in the graph (Fig. 2): a doublet at ~2,850 and ~2,950 cm^-1, a triplet in the region of 1 698 - 1 740 cm^-1; the remaining characteristic absorption bands of natural resins are poorly expressed due to carbonation and the antiquity of the samples. Thus, confirms the assumption that the studied residues are the negatives of carbonized vegetable fibers, and the randomness of their location on the surface of stone artifacts evidence Slu-

origin on the surface of flint tools from the Early Mesolithic layer in the Dvoyaya Cave

1. Plate with organic residues, sample N 1, N 5086, a -surface, Olympus MPlan FLN-10x, * 100; b - sample in transmitted light, *250; c-sample in polarized light, *x250. Here and further, the arrow indicates the place of sampling.

2. IR spectroscopy of samples N 1, N 5086.

tea origin, probably after getting into the cultural layer.

Two micro-samples from Group 2 (samples N3, 4) were found to contain organic and mineral components (see Table; Fig. 3). The IR spectrum of sample N3 shows the presence of organic substances in the absorption bands at ~2,850 and ~2,950 cm^-1, oleoresin-triplet in the region of 1,698 - 1,740 cm^-1, animal protein-absorption bands of ~ 1,650 and ~ 1,550 cm^-1, and carbohydrate-containing materials-absorption bands in the region of ~ 1,607 and ~ 1,620 cm^-1 (Fig. 4). No plant fibers were found in the sample; the structuration of the sample is a consequence of their imprint in the soil. resinous substance. The complex composition of these substances and the presence of a fibrous structure suggest that these are the remains of adhesive masses and windings, with which the tool was fixed on the shaft.

From group 3, seven micro-samples were taken from the surface of three guns, N 5-8. The composition of these micro-samples is different. The spectrum of reddish matter on the blade part of the segment (sample N 5) demonstrates the presence of oleoresin and animal protein in the composition. Samples N 6.1 and 6.2 differ in composition (Fig. 5). Thus, sample N6.1 from the blade of the excavated tool includes coniferous exudate (oleoresin), animal protein, and mineral components. The IR spectrum of the sample (Fig. 6 (a)) shows the presence of organic substances in the absorption bands at ~2,850 and ~2,950 cm^-1, and oleoresin-triplet in the region of 1 698 - 1 740 cm^-1, animal protein - absorption bands ~ 1,650 and ~ 1,550 cm^-1. Sample N 6.2 from the accommodation part of the excavated tool contained: carbohydrate-containing materials (probably fruit gum or juice of other carbohydrate-containing plants) and mineral components. On the IR spectrum of the sample (Fig.-

3. Segment with organic residues, sample N 3, N 4647, a -surface, Olympus MPlan FL N-10x, *100; b-surface, Olympus MD Plan 20, x200; c - transmitted light sample, x250; d-polarized light sample, x250.

4. IR spectroscopy of samples N 3, N 4647.

5. Excavated tool with organic remains, N 5520. Sample N 6.1: a-area of the blade with residues, Canon EOS HOOD * 10; b-surface, Olympus MD Plan 5, x50. Sample N 6.2: b - accommodation part with residues, Canon EOS HOOD, *10; d-surface, Olympus MD Plan 5, *50.

6. IR spectroscopy of samples N6.1 (a) and 6.2 (b), N 5520.

absorption bands are obtained that indicate the content of carbohydrate-containing materials: ~3,400 cm^-1. ~2 800 - 3 000 cm^-1, ~1,600 cm^-1, ~ 1 400 - 1 450 cm^-1, ~ 1,100 cm^-1. The presence of tar bands that are identical in direction to the linear traces on the tool surface complements and indirectly confirms the tracology data. Gum stains of fruit plants in the accommodation area can be a sign of the use of this substance for fixing the tool in the handle and/or making the handle from the wood of these plants.

The composition of sample No. 7 indirectly confirms the data of tracological analysis (Fig. 7). The red-brown color of the substance on the scraper blade is due to the organic composition, which includes animal proteins and animal lipids, as well as calcite and coal.

Three samples (N 8.1 - 8.3) taken from the surface of one gun have a complex composition. All samples contained coniferous exudate (oleoresin), one contained animal protein, and the other contained carbohydrate - containing materials (polysaccharides, probably fruit gum or juice of other carbohydrate-containing plants) (Fig. 8). Since all samples were taken from the butt zone of a cutting knife, it can be assumed that traces of gum are the residue of adhesive tape. the mass that was probably used to fix the plate in the handle. The fibrous structure identified in one of the samples may also indicate the presence of a winding made of plant fibers, and the remains of animal protein are associated with the function of the tool.

Investigation of fine-grained powder of brown-red shades (sample No. 9) X-ray fluorescence-

7. IR spectroscopy of samples N 7, N 4231.

8. IR spectroscopy of samples N 8.1 (a) and 8.2 (b), N 927.

9. Ochre-coated plate, N 719, a - surface at the sampling site N 9, Olympus MD Plan 20, *200; b - transmitted light sample, *250; c-polarized light sample, *250.

10. X-ray fluorescence spectrum of samples N 9, N 719.

Using optical and crystal-optical methods, it was shown that the sample consists of native red ochre and calcite (Figs. Thus, the assumption about the presence of an organic component in the dye mass covering the surface of the flint plate was refuted.

Conclusion

The results of our comprehensive analysis of residues of organic and mineral substances on the surface of stone products showed the prospects for further research in this area.

direction. Already at this stage of study, conclusions can be drawn about the methods of fixing flint tools in handles and on shafts, partially reconstruct the compositions of adhesive masses, and also supplement and indirectly confirm the data of tracological analysis.

The degree of preservation of organic remains of various origins in the Late Upper Paleolithic and Mesolithic layers of Dvoinaya Cave opens up great opportunities for further study of materials using various methods of various fields of science and, probably, for rechecking data obtained by other methods. This will allow us to expand our understanding of primitive communities and create sound scientific reconstructions of individual episodes from their lives.

List of literature

Aleksandrova O. I. Funktsional'nyi analiz kamennykh osudoviy vtorogo mesoliticheskogo sloya caves Dvoinaya na Severo-Zapadnom Kavkaze [Functional analysis of stone tools of the second Mesolithic layer of the Dvoinaya Cave in the North-West Caucasus]. XXVIII Krupnov Readings: proceedings of the International Scientific Conference. Moscow, April 21-25, 2014-Moscow, 2014. - pp. 48-50.

Alexandrova, O. I., Organic remains on flint products from the second Mesolithic layer of the Dvoinaya Cave (according to the tracological analysis), KSIA (in press).

Leonova E. V., Alexandrova O. I. Novye issledovaniya mnogosloynykh pamyatnikov kamennogo veka v Gubskom gorzhele [New studies of Stone Age multilayer monuments in the Guba Gorge]. XXVII Krupnovskie chteniya: mat-ly Mezhdunar. nauchn. conf. April 23 - 28, 2012-Makhachkala, 2012. - pp. 89-92.

Leonova, E. V. monuments of the early Holocene in Gubskaya gorge // problems of ethno-cultural interaction in the Urals-Volga region: history and modernity. Samara: Volga State Social and Humanitarian Academy, 2013, pp. 66-68.

Leonova E. V., Alexandrova O. I., Antipushina Zh. A., Serdyuk N. V., Spiridonova E. A., Tesakov A. S. Complex studies of stone age multilayer monuments in the Guba gorge // Tr. VIII Vseros. the second one. by phone. chetvertich. period "Fundamental problems of the quarter, the results of the study and the main directions of further research". June 10-15, 2013. - Rostov n / A: Southern Scientific Journal. Center of the Russian Academy of Sciences, 2013, pp. 373-375.

Allen J., Newman M., Riford M., Archer G. Blood and Plant Residues on Hawaiian Stone Tools from Two Archaeological Sites in Upland Kane' one, Ko'ola Pogo District, O'ahu Island // Asian Perspectives. - 1995. - Vol. 34, N 2. -P. 283 - 302.

Eales T., Westcott C., Lilley L, Ulm S., Brian D., Clarkson C. Roof Fall Cave, Cania Gorge: Site report // Queensland Archaeol. Research. - 1999. - N 11. - P. 29 - 42.

Galanidou N. Analytical and Ethical Issues Concerning Residues on Stone Tools from Greece // J. of Field Archaeology. - 2006. - Vol. 31, N 4. - P. 351 - 362.

Gerlach S., Newman M., Knell E. Blood Protein Residues on Pithic Artifacts from Two Archaeological Sites in the De Long Mountains, Northwestern Alaska // Arctic. - 1996. -Vol. 49, N 1. - P. 1 - 10.

Hardy B. Understanding Stone Tool Function: Methods and Examples from the Aurignacian Levels at Hohle Fels // Mitteilungen der Gesellschaft fur Urgeschichte. - 2009. -N 18. - P. 109 - 121.

Hardy B., Bolus M., Conard N. Hammer or crescent wrench? Stone-tool form and function in the Aurignacian of southwest Germany // J. of Human Evol. - 2008. - N 54. - P. 648 - 662.

Leonova E.V. Investigation of Mesolithic and Upper Paleolithic multilayer sites in the North-West Caucasus // The Dolni Vestonice Studies. - Vol. 20. - 2014. - P. 45 - 50. - (Mikulov Anthropology Meeting).

Lombard M., Wadley L. The morphological identification of micro-residues on stone tools using light microscopy: progress and difficulties based on blind tests // J. of Archaeol. Science. - 2007. - N 34. - P. 155 - 165.

Lombard M., Wadley L. The impact of micro-residue studies on South African middle stone age research // Archaeological Science Under a Microscope: Studies in Residue and Ancient DNA Analysis in Honour of Thomas H. Loy. Terra Australis. - 2009. - N 30. - P. 11 - 28.

Robertson G. Aboriginal use of backed artifacts at Lapstone Creek rock-shelter, New South Wales: an integrated residue and use-wear analysis // Changing perspectives in Australian archaeology. - Sydney: Australian Museum, 2011. - Pt. VII. -P. 83 - 101. - (Technical reports of the Australian Museum; vol. 23, N 7).

The article was submitted to the Editorial Board on 26.09.14.

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