Raman microscopy and IR spectroscopy of prehistoric paintings from Los Murciélagos cave (Zuheros, Córdoba, Spain)

Hernanz, A.; Mas, Martí; Gavilán, Beatriz; Hernández, Belén

doi:10.1002/jrs.1422

Cited by 47 publications

(46 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The characterisation of the composition of the pigments, binders, substrata and accretions, as well as their microstratigraphy and chemical alterations, are the main objectives of this investigation. This information is fundamental to consider potential radiocarbon absolute dating, [14 -19] to investigate degradation processes [9,10,13] and to undertake the appropriate conservation action of the paintings. In the present work, we study the painted panel 3, Fig.…”

Section: Introductionmentioning

confidence: 99%

Raman microscopy of prehistoric rock paintings from the Hoz de Vicente, Minglanilla, Cuenca, Spain

Hernanz

Ruìz

Gavira-Vallejo

et al. 2010

J Raman Spectroscopy

Self Cite

View full text Add to dashboard Cite

The third painted panel of the Hoz de Vicente rock shelter (Minglanilla, Cuenca, Spain) contains a series of prehistoric pictographs which were studied by Raman microscopy. Scanning electron microscopy (SEM), energy dispersive X-ray microanalysis (EDX) and petrographic polarised light microscopy were used as auxiliary techniques. The results obtained indicate that well-crystallised haematite (α-Fe 2 O 3 ) of grain size less than 1 µm was used as red pigment. However, amorphous carbon, probably vegetable charcoal or soot, was used as the black pigment. A patina of whewellite and weddellite covers the areas of the painting panel with pictographs. The microstratigraphic study of a schematic figure revealed that the layer of pigment is sandwiched between layers of these hydrated forms of calcium oxalate produced by the activity of fungi and lichens. These products have also been detected in the layer of pigment. These findings will enable obtaining limiting radiocarbon 14 C accelerator mass spectrometry (AMS) dates for the corresponding pictorial events. On the other hand, crystallisation of gypsum in the external layers of the panel is related to the deterioration observed in the flaking areas. Gypsum and clayish minerals appear as the main components of an ochre-coloured accretion covering several parts of the panel.

show abstract

Section: Introductionmentioning

confidence: 99%

Raman microscopy of prehistoric rock paintings from the Hoz de Vicente, Minglanilla, Cuenca, Spain

Hernanz

Ruìz

Gavira-Vallejo

et al. 2010

J Raman Spectroscopy

Self Cite

View full text Add to dashboard Cite

show abstract

“…Laboratory and synchrotron-based FT-IR spectroscopic instruments have been used successfully to analyse sampled rock art pigments (Hernanz et al, 2006;Prinsloo et al, 2008;Prinsloo et al, 2013;Prinsloo et al, 2014 ;Goodall et al, 2009). In these studies, the pigment samples were either powdered and mixed with KBr and pressed into pellets for transmission measurements, or directly analysed using an ATR (attenuated total reflection) cell inside the instrument or attached to a microscope.…”

Section: Ft-ir Spectroscopymentioning

confidence: 99%

Characterising pigments on 30 000-year-old portable art from Apollo 11 Cave, Karas Region, southern Namibia

Rifkin

Prinsloo

Dayet³

et al. 2016

Journal of Archaeological Science: Reports

View full text Add to dashboard Cite

As an unambiguous indication of complex cognitive capacity, representational art presents explicit evidence for modern and symbolic human behaviour. The only examples of African figurative art dating to the Late Pleistocene comprise seven stone plaques recovered from Apollo 11 Cave in the Huns Mountains, southern Namibia. The plaques derive from a single anthropogenic layer dated by radiocarbon ( 14 C) accelerator mass spectrometry (AMS) and optically simulated luminescence (OSL) methods to c. 30 000 years ago. We present the results of digital (CIE) L*a*b* colourimetric and portable energy dispersive X-ray fluorescence (ED-XRF), Raman spectroscopic and Fourier transform infrared reflectance (FT-IR) analyses of the pigments present on the plaques. These results provide the earliest direct evidence, in Africa, for the preparation of pigment-based paint-like mixtures and their application to create prehistoric art. Our research shows that in the creation of the depictions on the plaques, the artists used black pigments derived from manganese and charcoal, red pigments likely derived from ocherous shale and white pigments possibly derived from ostrich eggshell. Additionally, these plaques provide unique evidence for the combined use of mineral-and carbon-based pigment 'crayons' during the African Middle Stone Age.

show abstract

“…Rock art has been a topic of study in many parts of the world over a long period of time and vibrational spectroscopy (Raman and FTIR) has played an important role in identifying pigments, substrata and deterioration products (Bonneau et al, 2012;Edwards et al, 1998Edwards et al, , 1999Edwards et al, , 2000Hernanz et al, 2006Hernanz et al, , 2008Hernanz et al, , 2010Hernanz et al, , 2012Goodall et al, 2009;Lufromento et al, 2012;Prinsloo et al, 2008;Smith et al, 1999;Zoppi et al, 2002). The advent of portable instruments has added the extra bonus of performing analyses on-site, making it possible to study paintings of choice in their original setting, with a non-destructive and non-invasive technique (Lahlil et al, 2012;Olivares et al, 2012;Ravindran et al, 2013;Tournié et al, 2010).…”

Section: Introductionmentioning

confidence: 99%

In search of the optimum Raman/IR signatures of potential ingredients used in San/Bushman rock art paint

Prinsloo

Tournié

Colomban

et al. 2013

Journal of Archaeological Science

View full text Add to dashboard Cite

Vibrational spectroscopy (Raman and FTIR) has played an important role in identifying pigments, substrata and deterioration products in rock art studies worldwide: in the laboratory and on-site. However, the detection of organic binders and carrying agents has so far been scarce and the quality of many spectra recorded on-site inadequate. In this study, possible pigments (charcoal, ochre, raptor faeces, thermally treated ostrich egg shell, etc.), binders (fat, egg, blood) and carrying agents (saliva, gall, egg, water) were selected based on artistic considerations and analysed with FTIR and Raman (514.6 and 785nm excitation, both available in mobile instruments) spectroscopy in order to determine usable marker bands for each ingredient. The resultant marker bands were then used to analyse five San replica paints. It was found that FTIR spectroscopy is very efficient to identify organic compounds as there is no fluorescence but the broadness of the bands inhibits the exact assignment of many ingredients. A high fluorescence background experienced for many natural products prevented the recording of Raman spectra for all ingredients, in many instances though the sharp peaks usually associated with Raman spectra make identification easier than with FTIR spectroscopy. Most of the ingredients in the paints could be identified, but it is clear that better results are obtained when more that one technique is used.

show abstract

Raman microscopy and IR spectroscopy of prehistoric paintings from Los Murciélagos cave (Zuheros, Córdoba, Spain)

Cited by 47 publications

References 19 publications

Raman microscopy of prehistoric rock paintings from the Hoz de Vicente, Minglanilla, Cuenca, Spain

Raman microscopy of prehistoric rock paintings from the Hoz de Vicente, Minglanilla, Cuenca, Spain

Characterising pigments on 30 000-year-old portable art from Apollo 11 Cave, Karas Region, southern Namibia

In search of the optimum Raman/IR signatures of potential ingredients used in San/Bushman rock art paint

Contact Info

Product

Resources

About