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Composition of a floor from an Upper Paleolithic skeletal grave – A case from Dolni Vestonice (Moravia, Czechia, Central Europe)
Vibrational Spectroscopy 60 (2012) 129–132
Contents lists available at SciVerse ScienceDirect
Vibrational Spectroscopy journal homepage: www.elsevier.com/locate/vibspec
Composition of a floor from an Upper Paleolithic skeletal grave – A case from Dolni Vestonice (Moravia, Czechia, Central Europe) a,∗ b ´ ˛ Aleksandra Wesełucha-Birczynska , Joanna Trabska , Martin Oliva c a
Faculty of Chemistry, Jagiellonian University, Kraków, Poland Institute of Archeology, University of Rzeszów, Rzeszów, Poland c Moravske Zemske Muzeum, Brno, Czech Republic b
a r t i c l e
i n f o
Article history: Received 12 September 2011 Received in revised form 28 November 2011 Accepted 29 November 2011 Available online 8 December 2011 Keywords: Skeletal grave Burial site Raman micro-spectroscopy Hematite
a b s t r a c t Dolní V˘estonice is a complex of sites, with a broad range of information about Early Modern Humans and the Upper Paleolithic (Gravettian), with regard to technology, art, faunal, site and human remains. Dolní V˘estonice is located near the town of Brno in the region of Moravia, Czech Republic. The subject of our interest covers a floor of a grave niche, from the site Dolní V˘estonice I. Raman micro-spectroscopic research pointed at presence of hematite in the several selected randomly from the burial bed samples. Raman spectroscopy seems to be a useful tool for processing analyses of microdimensional archeological objects. © 2011 Elsevier B.V. All rights reserved.
1. Introduction Raman spectroscopy has well been rooted in research of microdimensional objects, including archeological and art ones. Paleolithic pigments, for example, particles themselves as well as after processing phenomena were examined in some recent works; general information on the Raman application in the field is accessible anywhere [1]. Red iron raw materials were extensively used by Paleolithic (in Europe prevailingly by Upper Paleolithic) societies; both in sacral and everyday use. That is why red iron powders, both intentionally produced and by products must have appeared on the archeological sites and now they are common within archeological context. They may bear information on their raw material provenance [2] as well as processing and should be concerned as a rightful archeological source of data [3,4]. Raman spectroscopy for the first time, as to our knowledge, has been applied to resolve some question in the area. Our interest focused at microparticles dispersed within a floor of an Upper Paleolithic, Gravettian female burial from the Dolní Vˇestonice I archeological site (Moravia, Czech Republic). Dolní Vˇestonice is a south Moravian area famous for a couple of Gravettian settlements, where, among others, a Venus figurine, fired clay figurines, imprinted in clay woven patterns as well as skeletal burials were discovered [5]. Dolní Vˇestonice I site
∗ Corresponding author. Tel.: +48 12 663 2067; fax: +48 12 634 0515. ´ E-mail address: [email protected] (A. Wesełucha-Birczynska). 0924-2031/$ – see front matter © 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.vibspec.2011.11.013
was excavated from 1924 by Karel Absolon, later on by Bohuslav Klíma. The grave of a woman about 40 years old was found in 1949. The skeleton laid in a crouched position, the face was dissymmetric as a consequence of a blow which broke the condyle of mandible in the youth. As has shown the preparation of the postcranial, some long bones are so close one to another so that the possibility of a secondary burial cannot be ruled out [6]. Skeleton was sprinkled with red ochre. The coloration was the most intensive on the skull and on the upper part of the body. Also the surrounding rock bears traces of it [7]. The body was probably bedaubt with a clay containing the red ochre, because the same reddish sediments as above is also under the skeleton, mainly on the skull. Only after the decomposition of the body, the ochre penetrated into the bones [8]. Samples from the burial bed are collected in the Moravské Zemské Muzeum – Anthropos Institute in Brno. 2. Experimental 2.1. Sampling Several samples selected randomly from volumed, unlabeled (no exact in situ position of the samples is known) material, represent 2–3 cm dimension pieces of gray, compact, earthy material with irregularly dispersed red and cherry powders and lumps, from ca. 1 to 7 mm as well as thin crusts of dark red substance. They are accompanied by white, earthy powders of ca. 1–5 mm as well as by black powders of similar size. It has been assumed that, along with
130
A. Wesełucha-Birczy´ nska et al. / Vibrational Spectroscopy 60 (2012) 129–132
Fig. 1. Oval shaped red powder grain, compact, harder than marly matrix. White grains within the powder is bone. Magn. 15×, parallel nicols. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of the article.)
well discernible, some millimeters lumps and crusts, true powders, of microscopic size (below 1 mm) should be dispersed within the gray matrix. The research focuses at features of the latter: their shape, compactness and composition. Resins patterns were also tested: Epothin produced by Bühler, used to manufacture thin sections and fresh pine resin. 2.2. Methods 2.2.1. Plane polarized light microscopy Plane polarized light microscopy (PLM) was applied with Olympus BX 51 apparatus, photographs were taken also with the camera Olympus DP 25 attached to the microscope. Thin sections were performed of pieces of burial floor and observed at transmitted polarized light. 2.2.2. Raman micro-spectroscopy Thin sections were used to analyze selected objects (red particles) with Raman micro-spectroscopy, Renishaw inVia instrument working in confocal mode. The Raman light was dispersed by a diffraction grating with 2400 l/mm and 1200 l/mm for Ar+ ion laser, 514.5 and HP NIR diode 785 nm lines, respectively. The laser radiation was focused on the sample by 100× microscope objective (Leica, NA = 0.80). The laser power (ca. 1–3 mW) was kept well below level that results damage to the sample. Spectra were collected on a compact variety of powders on two various thin sections, arbitrarily labeled by us 15 and 16 (we do not know their in situ space arrangement).
Fig. 2. Lower part of the image: semi-compact, red powder with “cloudy” edges. White, rectangular pieces above: bone at various degree of heating. A black, cracked area: a piece of an organic material. Magn. 15×, parallel nicols. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of the article.)
should be noted that all observed powdered substances (red iron ones, bones and of organic origin) are spatially very close. 3.2. Raman spectroscopy observations Raman research pointed at presence of hematite of similar spectrum shape for both samples (Figs. 3 and 4). The spectra have been collected in Table 1, data from [9,15] were quoted but it should be pointed that the data of other authors may differ by some or some tens cm−1 , the difference appears also in the [9,10] for pure and experimental compounds. Bands of high wavenumber range were collected within the red powder in the sample 15; they point at an organic substance (Fig. 5). There also come into sight bands at: 2930 for CH2 asymmetric stretching 2870 cm−1 for CH3 symmetric stretching as well as 3066 and 2908 cm−1 for CH stretching (Fig. 5A) [11]. Corresponding
3. Results 3.1. Transmitted light observations Gray fine crystalline matrix is marl (fine grained calcareous-clay rock) with microfossils. Red particles are prevailingly oval shaped, in the examined samples not exceeding 1 mm size, compact and hard (compared to surrounding micritic marl). Bone splinters are present within grains of red powder (Fig. 1). Some powders are of opposite features; though macroscopically well discernible, under microscope they appear to have looser structure and “cloudy” edges. Heated bone powder of a more or less uniform size but of various shape as well as opaque, uniform but cracked, rectangular shape powders, also up to 1 mm size were detected (Fig. 2). The latter are undoubtedly fragments of an organic substance, for the moment now – unknown. It
Fig. 3. Photomicrograph of sample 16 (reflected light, objective 20 and 100×). Raman spectrum (excitation 785 nm, objective 100×); region 800–120 cm−1 .
A. Wesełucha-Birczy´ nska et al. / Vibrational Spectroscopy 60 (2012) 129–132
131
Table 1 Raman spectra bands interpretation and assignments, according to [9,15], pure oxides. Sample DV 15 [cm−1 ]
Sample DV 16 [cm−1 ]
Haematite [cm−1 ]
Goethite [cm−1 ]
227 293 410
226 294 414 529
225; A1g 293; Eg 412; Eg
229
602
787
400 550
Maghemite [cm−1 ]
390; T2g 507; T2g
613; Eg 711 773
665; A1g 721; A1g
to natural admixture in raw material or weathering processes or both. Spectra were compared with the ones widely reported in sources and data bases, e.g. [10,13]. Sharp and intense bands in low wavenumbers suggest that the material was not heated, at least not in a high temperature, i.e. ca. 900 ◦ C [14]. A question remains when 530 and 688 cm−1 lines are considered as they resemble the ones of maghemite [9,10] that is a product of weathering (also in low temperature heating, [14]) – but magnetite, not hematite. Magnetite was not detected in loose, red, ca. 2 cm lumps from the site, suspected to have been a raw material for powders but ˛ stilbite (zeolite group) was (Trabska et al. in preparation [14]): it can be assumed that: (a) magnetite may have been present in XRD undetectable concentration, (b) stilbit may have appeared either as a product of heating marl in the presence of vapor, or (c) the mineral is an primary component of a raw material. Further research is expected to cast light on the problem.
Fig. 4. Photomicrograph of sample 15 (reflected light, objective 100×). Raman spectrum (excitation 785 nm, objective 100×); region 800–120 cm−1 .
to these bands, respective peaks appear in the bending vibration region, 1200–1600 cm−1 (Fig. 5B), for example 1453 cm−1 . The band observed at 1606 cm−1 may indicate C C stretching vibrations characteristic for ring aromatics. Raman spectra of pine and Epothin resins were compared with the organic compound spectrum (Fig. 5): it is a synthetic resin that is responsible for the sample spectrum shape [12]. 4. Discussion and conclusions We are unable to reconstruct in situ space arrangement of red powders of the examined pieces as no detailed planigraphy, referring to red powders, could have been performed in 1949. In this work a stress has been put on examination of powders dispersed within gray marl matrix, accompanying larger red lumps and cherry crusts. Powder color and other features are poorly accessible for naked eye observations and comparisons with larger pieces. Spectra shape are similar in the two randomly selected samples, labeled by us as 15 and 16, and we claim that the raw material is of the same origin. Collected spectra reveal presence of hematite and low concentration of goethite, a common phenomenon due
Fig. 5. Raman spectrum of: (1) sample 15 (excitation 514.5 nm, objective 100×); (2) epothin resin (Bühler) and (3) fresh pine resin; region: (A) 3200–2600 cm−1 ; (B) 1600–300 cm−1 .
132
A. Wesełucha-Birczy´ nska et al. / Vibrational Spectroscopy 60 (2012) 129–132
An organic substance bands, reported by us in Raman spectrum point at presence of contemporary, synthetic resin applied to perform thin sections (Fig. 5). Further research of resinous substances from the site, of correctly documented context may help in finding solution. It should be noted that the ancient (ca. 30 000 years) old resin and the contemporary one (collected in summer 2011) are completely different. The reason for it may be twofold: either no pine resin was documented or a pine but well ordered after the time span. It must be taken into account that during or just after excavations samples may have been impregnated with an organics (e.g. bone glue) and the fact may have not been reported, though macroscopic appearance does not suggest the event. Additionally the resin spectrum was collected only in a one grain of powder, not in another context. Raman spectroscopy seems to be a useful tool for processing of archeological powders, especially heating (due to hematite crystallinity destruction) analyses. Obviously, it may reveal a lot on neighboring substances and admixtures: their phase composition and heating degree. Further examinations of the problems as well as recognition of other red raw materials are planned to be performed.
References [1] H.G.M. Edwards, S.E.J. Villar, A.R. David, D.L.A. de Faria, Anal. Chim. Acta 503 (2004) 223. ˛ [2] J. Trabska, A. Gaweł, Archaeological Reports, 59, PAN, 2007, Krakow, pp. 41–48 (in English). [3] F. D’Errico, H. Salomon, C. Vignaud, C. Stringer, J. Archaeol. Sci. 37 (2010) 117. [4] J. Watts, J. Hum. Evol. 59 (2010) 392. [5] J. Svoboda, Dolní Vˇestonice – Pavlov, Ed. Museum Mikulov, 2010 (in English). [6] E. Trinkaus, J. Jelínek, J. Hum. Evol. 33 (1997) 33. [7] B. Klima,. Études et recherches archéologiques de l’Université de Liège, The Dolni V˘estonice Studies, vol. 3, 1995. ´ [8] B. Klima, Dolni Vestonice Vyzkum táboˇriˇstˇe lovcu˚ mamutu˚ v letech 1947–1952, Academia, Praha, 1963. [9] M.A. Legodi, D. de Waal, Dyes Pigments 74 (2007) 161. [10] D.L.A. de Faria, S.V. Silva, M.T. de Oliveira, J. Raman Spectrosc. 28 (1997) 873. [11] N.B. Colthup, L.H. Daly, S.E. Wiberley, Introduction to Infrared and Raman Spectroscopy, Academic Press, New York, 1964. [12] P. Vandenabeele, B. Wehling, L. Moens, H. Edwards, M. De Reu, G. Van Hooydonk, Anal. Chim. Acta 407 (2000) 261. [13] R.T. Downs, M. Hall-Wallace, The American Mineralogist Crystal Structure Database, Am. Mineral. 88 (2003) 247. ˛ ´ [14] J. Trabska, A. Wesełucha-Birczynska, B. Trybalska, M. Przybyła, 6th International Congress on the Application of Raman Spectroscopy in Art and Archaeology (RAA 2011), Parma, 2011. [15] D.L.A. de Faria, F.N. Lopes, Vib. Spectrosc. 45 (2007) 117.
Contents lists available at SciVerse ScienceDirect
Vibrational Spectroscopy journal homepage: www.elsevier.com/locate/vibspec
Composition of a floor from an Upper Paleolithic skeletal grave – A case from Dolni Vestonice (Moravia, Czechia, Central Europe) a,∗ b ´ ˛ Aleksandra Wesełucha-Birczynska , Joanna Trabska , Martin Oliva c a
Faculty of Chemistry, Jagiellonian University, Kraków, Poland Institute of Archeology, University of Rzeszów, Rzeszów, Poland c Moravske Zemske Muzeum, Brno, Czech Republic b
a r t i c l e
i n f o
Article history: Received 12 September 2011 Received in revised form 28 November 2011 Accepted 29 November 2011 Available online 8 December 2011 Keywords: Skeletal grave Burial site Raman micro-spectroscopy Hematite
a b s t r a c t Dolní V˘estonice is a complex of sites, with a broad range of information about Early Modern Humans and the Upper Paleolithic (Gravettian), with regard to technology, art, faunal, site and human remains. Dolní V˘estonice is located near the town of Brno in the region of Moravia, Czech Republic. The subject of our interest covers a floor of a grave niche, from the site Dolní V˘estonice I. Raman micro-spectroscopic research pointed at presence of hematite in the several selected randomly from the burial bed samples. Raman spectroscopy seems to be a useful tool for processing analyses of microdimensional archeological objects. © 2011 Elsevier B.V. All rights reserved.
1. Introduction Raman spectroscopy has well been rooted in research of microdimensional objects, including archeological and art ones. Paleolithic pigments, for example, particles themselves as well as after processing phenomena were examined in some recent works; general information on the Raman application in the field is accessible anywhere [1]. Red iron raw materials were extensively used by Paleolithic (in Europe prevailingly by Upper Paleolithic) societies; both in sacral and everyday use. That is why red iron powders, both intentionally produced and by products must have appeared on the archeological sites and now they are common within archeological context. They may bear information on their raw material provenance [2] as well as processing and should be concerned as a rightful archeological source of data [3,4]. Raman spectroscopy for the first time, as to our knowledge, has been applied to resolve some question in the area. Our interest focused at microparticles dispersed within a floor of an Upper Paleolithic, Gravettian female burial from the Dolní Vˇestonice I archeological site (Moravia, Czech Republic). Dolní Vˇestonice is a south Moravian area famous for a couple of Gravettian settlements, where, among others, a Venus figurine, fired clay figurines, imprinted in clay woven patterns as well as skeletal burials were discovered [5]. Dolní Vˇestonice I site
∗ Corresponding author. Tel.: +48 12 663 2067; fax: +48 12 634 0515. ´ E-mail address: [email protected] (A. Wesełucha-Birczynska). 0924-2031/$ – see front matter © 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.vibspec.2011.11.013
was excavated from 1924 by Karel Absolon, later on by Bohuslav Klíma. The grave of a woman about 40 years old was found in 1949. The skeleton laid in a crouched position, the face was dissymmetric as a consequence of a blow which broke the condyle of mandible in the youth. As has shown the preparation of the postcranial, some long bones are so close one to another so that the possibility of a secondary burial cannot be ruled out [6]. Skeleton was sprinkled with red ochre. The coloration was the most intensive on the skull and on the upper part of the body. Also the surrounding rock bears traces of it [7]. The body was probably bedaubt with a clay containing the red ochre, because the same reddish sediments as above is also under the skeleton, mainly on the skull. Only after the decomposition of the body, the ochre penetrated into the bones [8]. Samples from the burial bed are collected in the Moravské Zemské Muzeum – Anthropos Institute in Brno. 2. Experimental 2.1. Sampling Several samples selected randomly from volumed, unlabeled (no exact in situ position of the samples is known) material, represent 2–3 cm dimension pieces of gray, compact, earthy material with irregularly dispersed red and cherry powders and lumps, from ca. 1 to 7 mm as well as thin crusts of dark red substance. They are accompanied by white, earthy powders of ca. 1–5 mm as well as by black powders of similar size. It has been assumed that, along with
130
A. Wesełucha-Birczy´ nska et al. / Vibrational Spectroscopy 60 (2012) 129–132
Fig. 1. Oval shaped red powder grain, compact, harder than marly matrix. White grains within the powder is bone. Magn. 15×, parallel nicols. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of the article.)
well discernible, some millimeters lumps and crusts, true powders, of microscopic size (below 1 mm) should be dispersed within the gray matrix. The research focuses at features of the latter: their shape, compactness and composition. Resins patterns were also tested: Epothin produced by Bühler, used to manufacture thin sections and fresh pine resin. 2.2. Methods 2.2.1. Plane polarized light microscopy Plane polarized light microscopy (PLM) was applied with Olympus BX 51 apparatus, photographs were taken also with the camera Olympus DP 25 attached to the microscope. Thin sections were performed of pieces of burial floor and observed at transmitted polarized light. 2.2.2. Raman micro-spectroscopy Thin sections were used to analyze selected objects (red particles) with Raman micro-spectroscopy, Renishaw inVia instrument working in confocal mode. The Raman light was dispersed by a diffraction grating with 2400 l/mm and 1200 l/mm for Ar+ ion laser, 514.5 and HP NIR diode 785 nm lines, respectively. The laser radiation was focused on the sample by 100× microscope objective (Leica, NA = 0.80). The laser power (ca. 1–3 mW) was kept well below level that results damage to the sample. Spectra were collected on a compact variety of powders on two various thin sections, arbitrarily labeled by us 15 and 16 (we do not know their in situ space arrangement).
Fig. 2. Lower part of the image: semi-compact, red powder with “cloudy” edges. White, rectangular pieces above: bone at various degree of heating. A black, cracked area: a piece of an organic material. Magn. 15×, parallel nicols. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of the article.)
should be noted that all observed powdered substances (red iron ones, bones and of organic origin) are spatially very close. 3.2. Raman spectroscopy observations Raman research pointed at presence of hematite of similar spectrum shape for both samples (Figs. 3 and 4). The spectra have been collected in Table 1, data from [9,15] were quoted but it should be pointed that the data of other authors may differ by some or some tens cm−1 , the difference appears also in the [9,10] for pure and experimental compounds. Bands of high wavenumber range were collected within the red powder in the sample 15; they point at an organic substance (Fig. 5). There also come into sight bands at: 2930 for CH2 asymmetric stretching 2870 cm−1 for CH3 symmetric stretching as well as 3066 and 2908 cm−1 for CH stretching (Fig. 5A) [11]. Corresponding
3. Results 3.1. Transmitted light observations Gray fine crystalline matrix is marl (fine grained calcareous-clay rock) with microfossils. Red particles are prevailingly oval shaped, in the examined samples not exceeding 1 mm size, compact and hard (compared to surrounding micritic marl). Bone splinters are present within grains of red powder (Fig. 1). Some powders are of opposite features; though macroscopically well discernible, under microscope they appear to have looser structure and “cloudy” edges. Heated bone powder of a more or less uniform size but of various shape as well as opaque, uniform but cracked, rectangular shape powders, also up to 1 mm size were detected (Fig. 2). The latter are undoubtedly fragments of an organic substance, for the moment now – unknown. It
Fig. 3. Photomicrograph of sample 16 (reflected light, objective 20 and 100×). Raman spectrum (excitation 785 nm, objective 100×); region 800–120 cm−1 .
A. Wesełucha-Birczy´ nska et al. / Vibrational Spectroscopy 60 (2012) 129–132
131
Table 1 Raman spectra bands interpretation and assignments, according to [9,15], pure oxides. Sample DV 15 [cm−1 ]
Sample DV 16 [cm−1 ]
Haematite [cm−1 ]
Goethite [cm−1 ]
227 293 410
226 294 414 529
225; A1g 293; Eg 412; Eg
229
602
787
400 550
Maghemite [cm−1 ]
390; T2g 507; T2g
613; Eg 711 773
665; A1g 721; A1g
to natural admixture in raw material or weathering processes or both. Spectra were compared with the ones widely reported in sources and data bases, e.g. [10,13]. Sharp and intense bands in low wavenumbers suggest that the material was not heated, at least not in a high temperature, i.e. ca. 900 ◦ C [14]. A question remains when 530 and 688 cm−1 lines are considered as they resemble the ones of maghemite [9,10] that is a product of weathering (also in low temperature heating, [14]) – but magnetite, not hematite. Magnetite was not detected in loose, red, ca. 2 cm lumps from the site, suspected to have been a raw material for powders but ˛ stilbite (zeolite group) was (Trabska et al. in preparation [14]): it can be assumed that: (a) magnetite may have been present in XRD undetectable concentration, (b) stilbit may have appeared either as a product of heating marl in the presence of vapor, or (c) the mineral is an primary component of a raw material. Further research is expected to cast light on the problem.
Fig. 4. Photomicrograph of sample 15 (reflected light, objective 100×). Raman spectrum (excitation 785 nm, objective 100×); region 800–120 cm−1 .
to these bands, respective peaks appear in the bending vibration region, 1200–1600 cm−1 (Fig. 5B), for example 1453 cm−1 . The band observed at 1606 cm−1 may indicate C C stretching vibrations characteristic for ring aromatics. Raman spectra of pine and Epothin resins were compared with the organic compound spectrum (Fig. 5): it is a synthetic resin that is responsible for the sample spectrum shape [12]. 4. Discussion and conclusions We are unable to reconstruct in situ space arrangement of red powders of the examined pieces as no detailed planigraphy, referring to red powders, could have been performed in 1949. In this work a stress has been put on examination of powders dispersed within gray marl matrix, accompanying larger red lumps and cherry crusts. Powder color and other features are poorly accessible for naked eye observations and comparisons with larger pieces. Spectra shape are similar in the two randomly selected samples, labeled by us as 15 and 16, and we claim that the raw material is of the same origin. Collected spectra reveal presence of hematite and low concentration of goethite, a common phenomenon due
Fig. 5. Raman spectrum of: (1) sample 15 (excitation 514.5 nm, objective 100×); (2) epothin resin (Bühler) and (3) fresh pine resin; region: (A) 3200–2600 cm−1 ; (B) 1600–300 cm−1 .
132
A. Wesełucha-Birczy´ nska et al. / Vibrational Spectroscopy 60 (2012) 129–132
An organic substance bands, reported by us in Raman spectrum point at presence of contemporary, synthetic resin applied to perform thin sections (Fig. 5). Further research of resinous substances from the site, of correctly documented context may help in finding solution. It should be noted that the ancient (ca. 30 000 years) old resin and the contemporary one (collected in summer 2011) are completely different. The reason for it may be twofold: either no pine resin was documented or a pine but well ordered after the time span. It must be taken into account that during or just after excavations samples may have been impregnated with an organics (e.g. bone glue) and the fact may have not been reported, though macroscopic appearance does not suggest the event. Additionally the resin spectrum was collected only in a one grain of powder, not in another context. Raman spectroscopy seems to be a useful tool for processing of archeological powders, especially heating (due to hematite crystallinity destruction) analyses. Obviously, it may reveal a lot on neighboring substances and admixtures: their phase composition and heating degree. Further examinations of the problems as well as recognition of other red raw materials are planned to be performed.
References [1] H.G.M. Edwards, S.E.J. Villar, A.R. David, D.L.A. de Faria, Anal. Chim. Acta 503 (2004) 223. ˛ [2] J. Trabska, A. Gaweł, Archaeological Reports, 59, PAN, 2007, Krakow, pp. 41–48 (in English). [3] F. D’Errico, H. Salomon, C. Vignaud, C. Stringer, J. Archaeol. Sci. 37 (2010) 117. [4] J. Watts, J. Hum. Evol. 59 (2010) 392. [5] J. Svoboda, Dolní Vˇestonice – Pavlov, Ed. Museum Mikulov, 2010 (in English). [6] E. Trinkaus, J. Jelínek, J. Hum. Evol. 33 (1997) 33. [7] B. Klima,. Études et recherches archéologiques de l’Université de Liège, The Dolni V˘estonice Studies, vol. 3, 1995. ´ [8] B. Klima, Dolni Vestonice Vyzkum táboˇriˇstˇe lovcu˚ mamutu˚ v letech 1947–1952, Academia, Praha, 1963. [9] M.A. Legodi, D. de Waal, Dyes Pigments 74 (2007) 161. [10] D.L.A. de Faria, S.V. Silva, M.T. de Oliveira, J. Raman Spectrosc. 28 (1997) 873. [11] N.B. Colthup, L.H. Daly, S.E. Wiberley, Introduction to Infrared and Raman Spectroscopy, Academic Press, New York, 1964. [12] P. Vandenabeele, B. Wehling, L. Moens, H. Edwards, M. De Reu, G. Van Hooydonk, Anal. Chim. Acta 407 (2000) 261. [13] R.T. Downs, M. Hall-Wallace, The American Mineralogist Crystal Structure Database, Am. Mineral. 88 (2003) 247. ˛ ´ [14] J. Trabska, A. Wesełucha-Birczynska, B. Trybalska, M. Przybyła, 6th International Congress on the Application of Raman Spectroscopy in Art and Archaeology (RAA 2011), Parma, 2011. [15] D.L.A. de Faria, F.N. Lopes, Vib. Spectrosc. 45 (2007) 117.