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Characterizing the pigments and paints of prehistoric artists

Characterizing the pigments and paints of prehistoric artists This paper offers a broad and critical overview of current discussions on the potential uses and the characterization of pigments in prehistory, with a special focus on prehistoric rock art. Today, analytical approaches to pigments and paints allow us to go beyond the identic fi ation of the elemental and molecular composition of these archaeological remains, to explore also raw material procurement, transformation and use strategies of interest to investigate the technological and socio-cultural practices of prehistoric artists and their change over space and time. The paper also summarizes the palette of prehistoric artists, as well as the techniques and analytical strate- gies used to date to characterize prehistoric pigments and paints (colours, raw materials, binders and recipes) used in prehistoric rock art. Keywords Prehistoric art · Analytical chemistry · Pigments · Paints · Binders Premise et al. 2021).The second group of contributions is focused on pigments, starting from a philological essay on terminology This Topical Collection (TC) covers several topics in the (Becker 2021). Three archaeological reviews on prehistoric field of study, in which ancient architecture, art history, (this paper), Roman (Salvadori and Sbrolli 2021) and Medi- archaeology and material analyses intersect. The chosen per- aeval (Murat 2021) wall paintings clarify the archaeological spective is that of a multidisciplinary scenario, capable of and historical/cultural framework. A series of archaeometric combining, integrating and solving the research issues raised reviews illustrate the state of the art of the studies carried out by the study of mortars, plasters and pigments (Gliozzo et al. on Fe-based red, yellow and brown ochres (Mastrotheodoros 2021). The first group of contributions explains how mortars et al. forthcoming); Cu-based greens and blues (Švarcová have been made and used through the ages (Arizzi and Cul- et al. 2021); As-based yellows and reds (Gliozzo and Burgio trone 2021; Ergenç et al. 2021; Lancaster 2021; Vitti 2021). 2021); Pb-based whites, reds, yellows and oranges (Gliozzo An insight into their production, transport and on-site organ- and Ionescu 2021); Hg-based red and white (Gliozzo 2021) ization is further provided by DeLaine (2021). Furthermore, and organic pigments (Aceto 2021). An overview of the use several issues concerning the degradation and conservation of inks, pigments and dyes in manuscripts; their scientific of mortars and plasters are addressed from practical and examination and analysis protocol (Burgio 2021) and an technical standpoints (La Russa and Ruffolo 2021; Caroselli overview of glass-based pigments (Cavallo and Riccardi forthcoming) are also presented. Furthermore, two papers on cosmetic (Pérez Arantegui 2021) and bioactive (antibac- This article is part of the Topical Collection on Mortars, plasters terial) pigments (Knapp et al. 2021) provide insights into the and pigments: Research questions and answers variety and different uses of these materials. * Inés Domingo ines.domingo@ub.edu Annalisa Chieli Introduction annalisachieli@ub.edu Archaeological research has provided evidence of human Departament d’Història i Arqueologia, ICREA/Universitat de Barcelona/SERP, Montealegre, 6-8, 08001 Barcelona, use of natural minerals and earths with colouring proper- Spain ties (iron and manganese oxides and hydroxides including Departament d’Història i Arqueologia, Universitat de haematite, goethite, maghemite, siderite and other miner- Barcelona//LArcHer, Montealegre, 6-8, 08001 Barcelona, als such as kaolinite, huntite, white chalk and others), with Spain Vol.:(0123456789) 1 3 196 Page 2 of 20 Archaeol Anthropol Sci (2021) 13:196 some examples dating back thousands of years (Watts et al. The many uses of pigments in prehistoric 2016; Wolf et al. 2018). The presence of pieces of pigment times of various sizes, pigment powders and residues and even drops of paint in archaeological deposits, contexts or materi- We know today that the presence of pigments in archaeo- als (shells, stone and bone tools, grinding stones, different logical deposits is not only related to the artistic production sorts of containers and so forth) is well attested, even before since many of these raw materials have other preservative, the appearance of rock art or the global dispersal of anatomi- antiseptic, abrasive, repellent, protective or even medical cal modern humans. properties (Velo, 1984; Hovers et al. 2003; García-Borja The identification of ochre processing workshops (includ- et al. 2004; Soressi and d’Errico, 2007; Roebroeks et al. ing raw materials, processing tools and/or storage contain- 2012; Rifkin et al. 2015, among many others), which were ers) in different chronologies and places—e.g. Blombos very probably known in prehistoric times. cave in South Africa 100,000 years ago (Henshilwood et al. As early as the 1980s, Couraud (1988) proposed already 2011), Qafzeh Cave in Israel around 92,000 years ago (Hov- three different uses of colouring raw materials during the ers et al. 2003), Porc-Epic Cave in Ethiopia ca. 40 ka cal BP European Palaeolithic, which could be also extended to other (Rosso et al. 2014), Santa Maira in Spain between 15 and regions and periods: 6 ka cal BP (Tortosa et al. 2020), Cova de l’Or in Spain in early Neolithic deposits (Domingo et al. 2012), the Early- – The production of different forms of artistic expression Middle Holocene site of Takarkori, in Lybia (di Lernia et al. – Domestic and functional uses 2016), among many others—reveals that the use of colour- – Funerary practices ing raw materials was not accidental but a well-planned activity since prehistoric times, demanding an important The archaeological literature has often related the use investment of time and effort to source and process these of these materials to different sorts of artistic, aesthetic or materials. symbolic practices. These include different sorts of deliber - In the last few decades, the combination of multi-tech- ate marks, drawings and paintings produced on rock walls nical (different non-invasive and invasive analytical tech- both within caves and rock shelters as well as in the open air niques, use-wear analysis, experimental archaeology, etc.) and on different sorts of portable objects. For a long time, and multidisciplinary approaches (chemistry, archaeology, this kind of artistic production seemed to be mainly related geology, traceology, ethnography and so forth) is providing to anatomical modern humans, with the earliest examples a more comprehensive view of these raw materials beyond including several fragmented ochreous pebbles and cray- the identification of their nature and composition, as we will ons with intentional incisions located at different South discuss along with this paper. With the new approaches, we African sites (Blombos cave, Klasies River, Pinnacle Point are now able to explore also potential sources, processing 13B, Klein Kliphuis) and dating back between 100,000 and practices and uses informing on ancient pigment sourcing, 85,000 years ago (Henshilwood et al. 2009; D’Errico et al. procurement (whether autonomous or obtained through 2012); 73,000-year-old red crosshatch marks identified exchange networks) and transformation strategies and tech- on a rock fragment at Blombos Cave (Henshilwood et al. nologies, and their changes over time. We can also explore if 2018); 77,000-year-old shell beads decorated with ochre the raw materials were used directly on soft or hard surfaces at Blombos Cave, Sibudu and Border Cave (Henshilwood (e.g. as crayons) or transformed into powder through grind- et al. 2004) and other African sites or the earliest examples ing and scraping and if any additives or binders were added of figurative and non-figurative painted rock art produced to produce a paste or a paint. by anatomical modern humans (AMH) in Spain (Pike et al. Our aim with this paper is to oe ff r a broad overview of the 2012; Hoffman et al. 2018a) and Indonesia (Aubert et al. techniques and analytical strategies used so far to character- 2014, 2018; Brum et al. 2021) dating back at least 40 and ize prehistoric pigments and the raw materials, binders and 45,000 years respectively. From then on, the tradition of recipes identified to date in rock art. A full review of the using colouring raw materials to produce different sorts of global literature dealing with pigment analysis of prehistoric art on different media (stone, bone, antler, pottery and so rock art is beyond the scope of this paper since in the last forth) spread around the world at different points in time. couple of decades the number of papers addressing this topic Today, a central debate in research on archaeological has considerably increased across the world. Thus, while pigments and human evolution is if their use to produce we reference global literature when offering examples, we different sorts of visual arts and marks on different media specially selected those from Western and Mediterranean was exclusive to us (AMH) or there are any precedents in European prehistory and rock art to illustrate our discus- the human lineage. In the last decade, several red rock art sions, as it is our main study area. marks and paintings located at different Spanish sites (some 1 3 Archaeol Anthropol Sci (2021) 13:196 Page 3 of 20 196 mouth or airbrush blown red paint located over a stalagmitic sorts of containers and tools (offerings?), as well as in the dome at Ardales site, Málaga, a hand stencil at Maltravieso, form of body or clothing decorations (e.g. Schotsmans et al. Cáceres, and a scalariform sign at La Pasiega, Cantabria) 2020), or even covering human skeletal remains. Couraud have been dated as early as, at least, 64 to 66,000 years ago suggested that some of these funerary practices could aim (Hoffman et al. 2018a, Zilhão 2020). At that time, AMH had at facilitating the preservation of the human remains since not yet arrived in the Iberian Peninsula, thus suggesting that ochre helps slow down decomposition (Couraud 1988). these depictions were produced by Eurasian Neanderthals. A similar interpretation is provided by other researchers Neanderthals’ use of personal ornaments with red colour- (Delibes 2000; Blas 2003; Martín-Gil et al. 2004) when ing residues as well as the use of colouring materials has the mineral used in these funerary contexts was cinnabar. been also reported by several researchers. For example, at Other authors, though, see a more symbolic explanation Cueva de los Aviones (Murcia, Spain) Zilhão et al. (2010) when ochre is recorded in relation to human skeletal remains interpreted a mixture of charcoal, dolomite, haematite and (Hovers et al. 2003). Interestingly, ethnographic accounts pyrite as well as yellow natrojarosite associated with marine suggest that the boundaries between symbolic and practical shells dating back 115,000 years (Hoffman et al. 2018b), as domains are often blurred and both can coexist in the same potentially used for cosmetic purposes, since according to object, tradition or practice (Rosso 2017; Domingo et al. them, the only known archaeological use of natrojarosite is 2020). Nevertheless, symbolic uses are usually culturally in cosmetics. Along the same lines, Soressi and d’Errico constructed and archaeologically invisible since they leave (2007) suggest that the manganese dioxide from the French behind no empirical evidence, and thus, they are hard to Mousterian sites of Pech de l’Azé I and Pech de l’Azé IV demonstrate. Based on the different uses identified in funer - may have been used for body painting (Soressi and d’Errico ary contexts of Çatalhöyük, Schotsmans et al. (2020) sug- 2007). Drops of a haematite-rich liquid of unknown use gest that pigments were probably used to build identities as were also identified on the sediment at Maastricht-Belvédère well as for social differentiation. For example, in funerary deposits in the Netherlands pushing back in time the use of contexts, most of the inhabitants of this site did not receive this mineral by early Neanderthals to at least 200–250 ka pigment treatment, and the very few who did point to differ - (Roebroeks et al. 2012). Thus, long before the arrival of ent treatment depending on their sex (cinnabar for male and AMH to Eurasia, Neanderthals were already using mineral blue and green pigments for female). colouring materials for different purposes. Whether this use In the last few decades, interdisciplinary approaches to of different pigments was symbolic or practical is difficult to the archaeology of colour have been also applied to the know since (as already discussed) many of these colouring characterization of pigments used for rock art production raw materials had many properties and as such, they were in prehistoric times, which are the focus of our research well suited for other daily activities like hide tanning, tool (Domingo et  al. 2021). This particular topic faces more hafting, tool polishing and so forth (Hovers et al. 2003). challenges than the study of other archaeological pigments The use of different colouring raw materials for practical since rock art sampling entails compromising the integrity of purposes in prehistoric times has been also deduced based on ancient works of art often protected and listed in the different a mixture of archaeological, ethnographic and experimental National Heritage acts (e.g. in Spain rock art is protected observations. Some practical applications proposed so far with the highest level of legal protection—Asset of Cultural include their use as additives mixed with natural glues to Interest—according to the 1985 Spanish Heritage Act, and be used as a fixative for hafting tools (Beyries and Inizan as such, it cannot be destroyed or removed). Some are even 1982; Allain and Rigaud 1989; Wadley 2005; Lombard 2007; listed in the UNESCO World Heritage list (Fig. 1). So even Helwig et al. 2014), as natural abrasives for fine polishing of if today we are talking about microsamples, rock art is con- bone tools and ornaments (Goñi et al. 1999; García Borja sidered an irreplaceable asset and it entails (as it should be) et al. 2004), as a natural antiseptic for tanning hides to reverse more restrictions when it comes to invasive sampling. the decay process (Audion and Plisson 1982; Adams 1988; In this part of the world, prehistoric art appears from Nor- Rifkin 2011), to dry tendons for different purposes (such us way to Spain and covers more than 60,000 years (Hoffman bow strings or for attaching stone tools to the shafts), etc. et al. 2018a), spanning from the Middle Palaeolithic to the (Domingo et al. 2012). Bronze Age. It includes several forms of non-figurative and Colouring materials have been also reported in funerary figurative art produced on different media (stone, bone, ant- contexts from the Middle Palaeolithic to the Neolithic and ler, ivory, animal teeth and maybe some perishable materials beyond (for example, Formicota 1986; Molleson et al. 1992; such as wood) and using a variety of techniques (paintings, Cacho et al. 1996; Stringer and Gamble 1996; Bar-Yosef engravings, carvings). In such a vast territory, different tra- 1997; Goren et al. 2001; d’Errico and Backwell 2016). In ditions developed over time, including among others Pal- these contexts, they appeared as lumps of different sizes or aeolithic, Levantine and Schematic art. Palaeolithic art is powder remains identified in the deposits or within different an art of naturalistic animals and signs with singular sites 1 3 196 Page 4 of 20 Archaeol Anthropol Sci (2021) 13:196 in Iberia and France like Altamira, Chauvet, Lascaux, Foz worldwide to create the first masterpieces of the history of Côa, to name a few) dating between 40,000 and 11,700 cal. art (Salomon et al. 2008; Menu 2009; de Balbín Behrmann BP. Levantine rock art is an art of naturalistic humans and and Alcolea González 2009; Aubert et al. 2014; Chalmin animals illustrating narratives of hunting, war and vio- and Huntley 2017; Stuart and Thomas 2017; Domingo lence, maternity and death. This art is specific to Mediter - et al. 2021; Gallinaro and Zerboni 2021; Sepúlveda 2021). ranean Iberia, with outstanding sites like Cova dels Cav- The identification of the archaeological pigments and their alls, Remigía, la Sarga or Cogul. It dates sometime around sources (e.g. Pitarch et al. 2014 and 2019; Defrasne et al. 7500 years ago (no reliable numerical dates are known yet) 2019), the examination of the manufacturing techniques and (Ochoa et al. 2021). Schematic art is an art of schematic pictorial recipes (e.g. Brunet et al., 1982; Menu and Walter humans, animals and geometric shapes, with different tradi- 1992, 1996; Baffier et al. 1999; Salomon et al. 2008; Menu tions across Europe dating between the Early Neolithic and 2009) or understanding the mechanisms causing paint and the Bronze Age (for a global overview of European prehis- bedrock degradation (Hernanz et al. 2007; Aramendia et al. toric art, see Sauvet et al. 2014). 2020) are some of the common archaeological questions that can be effectively unravelled through physicochemical anal- yses. Beyond the more traditional dating purposes (Steelman Characterizing prehistoric pigments and Rowe 2012; Ochoa et al. 2021), analytically studying rock paintings, we can gain information about the technolog- Over the last three decades, archaeometric approaches have ical and socio-cultural practices and backgrounds of prehis- highly increased our knowledge of prehistoric pigments toric artists and, at the same time, acquire knowledge about used both in caves and in open-air rock shelters and boulders the conservation of these particular artistic expressions often Fig. 1 Map with rock art sites and concentrations of sites included (Algeria). 20. Tadrart Acacus (Libya). 21. Ennedi Massif natural in the UNESCO World Heritage list. 1. Writing-on-Stone Áisinai’pi and cultural landscape (Chad). 22. Ecosystem and Relict Cultural (Canada). 2. Mesa Verde National Park (United States). 3. Sierra Landscape of Lopé-Okanda (Gabon). 23. Kondoa (Tanzania). 24. de San Francisco (Mexico). 4. Chiribiquete National Park (Colom- Twyfelfontein o/Ui-//aes (Namibia). 25. Tsodilo (Botswana). 26. bia). 5. Nasca and Palpa (Perú). 6. Serra da Capivara (Brasil). 7. Chongoni (Malawi). 27. Matobo Hill (Zimbabwe). 28. Maloti Drak- Ischigualasto/Talampaya Natural Park (Argentina). 8. Cueva de las ensberg (South Africa). 29. Wadi rum Protected area (Jordan). 30. Manos (Argentina). 9. Risco Caído and the Sacred Mountains of Hail Region (Saudi Arabia). 31. Gobustan (Azerbaijan). 32. Tamgaly Gran Canaria Cultural Ladscape (Spain). 10. Valle do Côa (Portugal) (Kazakhstan). 33. Sulaiman-Too Sacred Mountains (Kyrgyzstan). 34. and Siega Verde (Spain). 11. Bend of Boyne (Ireland). 12. Altamira Bhimbetka (India). 35. Mongolian Altai (Mongolia). 36. Zuojiang and Palaeolithic cave art of Northern Spain. 13. Rock art of the Medi- Huashan rock art (China). 37. Rock Islands Southern Lagoon (Repub- terranean Basin on the Iberian Peninsula. 14. Vézère Valley (France). lic of Palau). 38. Kakadu National Park (Australia). 39. Uluru-Kata 15. Grotte Chauvet-Pont d’Arc (France). 16. Valcamonica (Italy). 17. Tjuta (Australia) Tanum (Sweden). 18. Rock Art of Alta (Norway). 19. Tassili n’Ajjer 1 3 Archaeol Anthropol Sci (2021) 13:196 Page 5 of 20 196 located in changing environments. Indeed, accurate diag- any scientific research (Pollard et al. 2007; Madariaga 2015; nostic analysis of rock art productions can provide insight Hernanz and Gavira-Vallejo 2021). As such, the analysis of into pigments’ raw materials and their provenance, offering rock art pigments requires a combination of several ana- precious information on the geographic practices and the lytical methods to provide a complete characterization of social networks of prehistoric artists and their counterparts the materials within their environment in terms of physical, (Chalmin et al. 2006; Iriarte et al. 2009; Jezequel et al. 2011; chemical, optical, structural, geological and morphological Mas et al. 2013; Pitarch et al. 2014), as well as into paint- properties. The integration of data from different analyti- ers’ manufacturing methods for pigment processing, such as cal techniques represents the best strategy to overcome the grinding, heating, sieving and settling, and pigment appli- intrinsic limitation of every single method when applied to cation techniques (Menu and Walter 1992; Salomon et al. the study of heterogeneous matrices, such as those usually 2008; Bonneau et al. 2012; Salomon et al. 2015, Hernanz found in rock art, often multilayered and complex due to et al. 2008; López et al. 2017; Cuenca-Solana et al. 2016; overlapping of pictorial layers, patinas, crusts and bedrock d’Errico et a. 2016; Gay et al. 2020). Through these sorts media characterized by different materials. Moreover, con- of approaches, we obtain information to reconstruct the dif- sidering the enormous value of these heritage assets, usually ferent steps of the chaîne operatoire (operative sequence) appearing in remote locations, portable non-invasive analyti- required to produce an artwork, the behaviours, acts and cal methods and non-destructive techniques when analyz- skills of ancient artists and their changes over space and ing micro-samples are usually required for the examination time, of interest to identify cultural differences, similarities of these valuable artworks. According to the literature and and interactions (Jezequiel et al. 2011; Bonneau et al. 2012; our own experience, pigment analyses of rock art are gener- Pitarch et al. 2014; Velliky et al. 2020; Tortosa et al. 2020). ally performed in progressive smaller scales, from macro-, Moreover, the physicochemical analyses of the rock paint- micro- to nano-size (Fig. 2). Their chemical characterization ings are also important to characterize any alteration mecha- is usually made by elemental and molecular spectroscopic nisms threatening the preservation of the paintings, due to techniques such as X-ray fluorescence spectroscopy (XRF) natural aging and weathering or to anthropic direct or indi- and Raman spectroscopy. In addition, to determine their rect interventions. Such an approach is necessary to develop morphology and crystalline structure, other techniques like the best conservation strategies and practices adapted to the optical microscopy (OM), transmission electron microscopy particular features of the artworks and the environmental (TEM), scanning electron microscopy (SEM), typically com- specificities of their contexts. Distinguishing between picto- bined with energy-dispersive X-ray spectroscopy to perform rial layers, the rock supports and any interstratified/external elemental micro-analyses (SEM–EDX) and X-ray diffraction patinas and crusts is decisive for understanding weather- (XRD) have been also used. A similar analytical approach ing processes and the preservation of the rock art paints can be also applied to the study of prehistoric portable art. A (Doehnne and Price 2010; Dorn et al. 2008). complete description of the commonest laboratory and port- Overall, multidisciplinary research based on analytical able analytical methods used in archaeological and cultural approaches applied to the study of prehistoric rock art has heritage research can be found in Pollard et al. (2008), Nigra changed the way we understand the materials, tools and pro- et al. (2015), Madariagara (2015), Vandenabeele and Donais cedures involved in rock paintings production. In the past (2016), Bersani and Lottici (2016), Brunetti et al. (2016), few decades, we have moved from the more purely stylistic while their specific application to the characterization of and descriptive studies of the art to the objective examina- prehistoric rock art pigments worldwide can be obtained in tion of the chemical and physical properties of the materi- Vignaud et al. (2006), Menu (2009), Aubert et al. (2014), als constituting the pictograms. In this way, the universal Chalmin and Huntley (2017), Stuart and Thomas (2017), language of science, integrated with aesthetical evaluations, Sepúlveda (2021), Gallinaro and Zerboni (2021), Domingo is now a better integral means to distinguish, analyze, under- et al. (2021), Hernanz and Gavira-Vallejo (2021), to name stand, compare and describe prehistoric rock paintings. It is a few. It is worth mentioning that the analytical approaches worth mentioning that scientific examinations alone are not and the scientific methods used in the study of rock art pig- enough to offer complete answers to archaeological research ments have changed over the last 30 years, following and questions, but they need to be opportunely included in a adapting to the contemporary technological advances that larger archaeological research context using a multidiscipli- occurred in the field of portable spectroscopic analyti- nary and collaborative approach among the different disci- cal instruments. In fact, the first extensive and systematic plines. A crucial aspect related to the study of rock art pig- physicochemical studies of rock art pigments started at the ments and paintings, and more in general to the examination beginning of the 1990s and they were performed exclusively of a wide range of cultural heritage objects, is the increas- on micro-samples, as occurred in the substantial research ing awareness that there is not known technique that—by regarding European Palaeolithic cave art. Several min- itself—could answer all of the research questions raised by ute samples coming from important French and northern 1 3 196 Page 6 of 20 Archaeol Anthropol Sci (2021) 13:196 Spanish painted caves such as Altamira, Niaux, Lascaux, Ekain and La Garma were analytically studied at the labora- tories of Centre de Recherche et de Restauration des Musées de France, C2RMF, in Paris (Clottes et al. 1990; Menu 1990; Menu and Walter, 1992; Clottes 1997; Chalmin et al. 2003; Vignaud et al. 2006; Chalmin et al. 2017). These precious research works shed light on the nature of the pigments employed by Palaeolithic artists and they brought to light elaborated pictorial recipes and manufacturing methods, dis- playing remarkable technical skills of the prehistoric paint- ers. Afterwards, in the last few years, several technological efforts have been spent in the miniaturization of optical and electronic components of portable spectroscopic instruments trying to balance their performance with that of their respec- tive bench top laboratory setups. These advances have led to the creation of more and more compact, light and smart spectroscopic devices with high performance for in situ non- invasive spectroscopic investigations, especially suited for the analyses of cultural heritage objects (Vandenabeele and Donais 2016; Brunetti et al. 2016). Such progresses in the improvement of portable and handheld systems for in-field non-invasive analysis has facilitated the access to valuable and immovable artworks non-suitable for in-lab analysis, like prehistoric rock art, thus enabling a growing number of studies to be conducted in situ, contributing to preserving the integrity of the artworks (e.g. Roldán et al. 2010; Lahlil et al. 2012; Beck et al. 2014; Olivares et al. 2013; Gay et al. 2015, 2016, 2020; Pitarch et al. 2014). A preliminary non-invasive diagnostic analytical cam- paign represents the roots on which to base further analyses in terms of (i) identic fi ation of the constituting materials, (ii) selection of points or areas to be sampled at a later stage, (iii) evaluation of the state of conservation of the paint- ings within their environment, and their monitoring over time, and (iv) planning of any conservation and/or restora- tion intervention (Fig. 2A). Sampling is still an essential step to advance knowledge on the study of rock art, as it is required to conduct microstratigraphic studies, dating, etc. (Fig. 2B-C). However, if prior to sampling, we conduct in situ non-invasive analyses, we will minimize impacts and obtain information to guide future sampling. Unlike sam- pling, non-invasive approaches allow the potential examina- tion of the whole painting, offering a more global view of Fig. 2 A Portable energy-dispersive X-ray fluorescence (EDXRF) the art under study. Thus, non-invasive analyses are essen- spectrometer designed by ICMUV employed for non-invasive on- tial to design ethically targeted sampling strategies aimed site analyses of Schematic and Levantine paintings at el Carche at analyzing those areas with the potential to provide the site (Jalance, Spain). B Schematic red animal from el Carche site (Jalance, Spain) indicating the sampled area. To minimize visual most interesting results (Beck et al. 2013). On the contrary, impact, the sample was taken next to an area with painting loss. C a micro-sample can be representative only of the site or the Optical microscope image of a micro-fragment sampled from a red sampled figure. Considering the fragility and the values of Schematic painted figure showed in B. Three different layers can be the rock paintings, the number of micro-samples should be recognized, from bottom to top: the bedrock, the red painting layer, and the orangey external patinas reduced to a minimum, to answer questions that can only be answered by sampling. It is now generally accepted that a proper research protocol in the study of an artwork, rock 1 3 Archaeol Anthropol Sci (2021) 13:196 Page 7 of 20 196 art included, involves as a first step, when feasible, the use artists. Very broadly speaking, the palette of prehistoric art- of non-invasive analytical approaches and the synergistic ists is generally composed of two main hues, namely red use of multi-technical and multi-scale analyses. When talk- and black. Other colours such as yellow and white were less ing about rock art, it is important to note that the logistical frequently used (Fig.  3). In addition, the use of charcoal organization of a non-invasive research campaign is not a from the organic origin (wood charcoal and burnt bone) has trivial matter: the geographical location of the rock shel- been also broadly detected. In the following lines, a general ters could represent a real challenge in terms of physical description of the most common pigments used in the pro- access, energy source and portability of the instruments. duction of prehistoric rock art will be outlined, describing These logistical challenges could force us to prioritize direct their chemical nature and characteristics, and drawing atten- sampling, assisted only by small portable digital micros- tion to some selected examples. copy and/or digital cameras when choosing the area to be sampled, rather than being guided by preliminary scientific Red pigments analyses that could have helped us formulate new research questions. This may unnecessarily increase the number of Iron-based oxides and hydroxides compose red pigments, samples needed, resulting in more invasive interventions among which haematite (α-Fe O ) is the most frequently 2 3 and hence causing a more negative impact on this fragile identified in the Palaeolithic and post-Palaeolithic rock art heritage. Thus, a non-invasive spectroscopic analytical cam- record all over the world (Chalmin et al. 2003; Vignaud et al. paign should be always prioritized, when feasibly. Among 2006; Salomon et al. 2008; Menu 2009; de Balbín Behr- the portable non-invasive spectroscopic methods available, mann and Alcolea González 2009; Chalmin and Huntley portable energy-dispersive X-ray fluorescence (Fig.  2A) and 2017; Aubert et al. 2014; Stuart and Thomas 2017; Gallinaro Raman spectroscopies have been extensively used in rock and Zerboni 2021; Domingo et al. 2021; Sepúlveda 2021, art research for elemental and molecular in situ analyses, among others). Haematite is a Fe (III) oxide highly wide- respectively (e.g. Roldan et al. 2010; Hernanz 2015; Gay spread in rocks and soils (Fig. 4), which colour depends on et al. 2016). However, more complex portable devices have its crystal size and shape: the tones range from yellowish/ been brought to the field, as the portable system combin- red for nanoparticles to purple for micrometer sized ones ing X-ray fluorescence and diffraction techniques used for or even black for larger crystals, like specularite (Cornell the first time to analyze the pigments at Rouffignac Cave and Schwertmann, 2003). The mineral haematite is also the (Dordogne, France). This was the first XRF-XRD experi- principal colouring matter constituting red ochres. Focus- ment ever undertaken in an underground and archaeological ing a bit on some definitions, ochres are naturally occurring environment to study prehistoric rock art (Beck et al. 2014). deposits characterized by a variable amount of clayey min- These types of portable instruments are usually employed erals (such as kaolinite, illite), iron oxides/hydroxides and to analyze artworks located in indoor environments, like a other minerals/impurities (like quartz, calcium carbonates, museum, since they are too large and bulky to be brought etc.), showing different colours from brown to red through into the field (Vandenabeele and Donais 2016). Vis–NIR yellows and violets, depending on the specific nature of Fe hyperspectral imaging technology, a novel method in the oxides/hydroxides present (Siddal 2018) (Fig.  5). Thus, field of rock art studies so far, has been employed for the ochres comprise a wide range of raw materials from geo- first time in the analyses of rock art materials and pigments logical formations bearing iron oxides/hydroxides including from the Palaeolithic Cave of El Castillo (Puente Viesgo, shales, mudstones, siltstones, earthy sandstones and other Cantabria, Spain) (Bayarri et al. 2019). This technique is types of ferruginous deposits (e.g. ferricrete and limonite a powerful 2D spectroscopic diagnostic technology for the ores). Their specific red or yellow hues, and their consequent non-invasive analyses of polychromatic surfaces of artworks definition as red/yellow ochres, are due to the presence of highly employed in the study of easel paintings (Cucci et al. haematite (α-Fe O ) and goethite (α-FeOOH), respectively, 2 3 2016). This imaging method provides a non-invasive way as main chromophores among the other ochres’ constitutive to identify colour materials and maps them on the surface, components. Ochres belong to the wider group of earth pig- representing a promising research tool also to study, preserve ments, defined as natural deposits rich in clay minerals, iron and manage this valuable cultural heritage. oxides, manganese oxides and other minerals that produce a coloured fine powder with high tinting strength (Eastaugh et  al. 2008). As a pictorial pigment, thanks to its natural The palette of prehistoric artists abundance and chemical stability, haematite-based materials have been widely used in art from Pleistocene times—with Despite different chronological periods, artistic traditions, world-renowned sites like the western European Palaeolithic cultures and geographic locations, inorganic pigments from sites of Lascaux (Dordogne, France) or Altamira (Spain)— mineral origins usually characterize the palette of prehistoric to the present by all cultures of the world (Eastaugh et al. 1 3 196 Page 8 of 20 Archaeol Anthropol Sci (2021) 13:196 Fig. 3 Colours used in Spanish Levantine rock art. A Red. B Black. C Red infill and white outline. D White 2008). Focusing on Western and Mediterranean European the dehydration of goethite can synthesize it (Cornell and studies, haematite and red ochres have been the main com- Schwertmann, 2003; González et al. 2000). Specifically to ponents of all prehistoric red pictograms, from Palaeolithic the heating procedures, yellow goethite, or high goethite con- rock art, known for the richness of pictorial recipes (Clottes tent materials like yellow ochre, turns its yellowish colour to et  al. 1990; Chalmin et al. 2003, 2004a; de Balbín Behr- red shades upon heating at temperatures above 250–300 °C, mann and Alcolea González 2009; Iriarte et al. 2009; Menu forming disordered haematite whose complete crystallization 2009; Hernanz et. al 2011; Jezequiel et al. 2011; Olivares happens at higher temperatures (> 850 °C), due to a topo- et al. 2013) to the subsequent post-Palaeolithic traditions tactic transformation that involves the loss of water by the such as Levantine rock art (specific to Mediterranean Spain) and the more recent Schematic rock art (Rosina et al. 2018; Domingo et al. 2021). Although haematite and haematite-rich earths occur naturally, heat treatment or mechanical processes inducing Fig. 5 Optical microscope image of an ochre powder sampled from the soil of Coves Llongues site (Castellón, Spain). The image shows the heterogeneous composition and texture of the powder character- ized by crystals of different colours and sizes. From micro-Raman analyses (data not shown), this ochre is mainly composed of calcite, Fig. 4 Fragment of red pigment (haematite and calcite) gypsum, haematite and magnetite 1 3 Archaeol Anthropol Sci (2021) 13:196 Page 9 of 20 196 iron (III) hydroxide. For archaeologists, understanding the (Salomon et al. 2012), at Solutrean levels at Les Maîtreaux pigment production methods is an indirect way to assess the (Bossay-sur-Claise, Indre-et-Loire, France) and the Mid- level of technological and cognitive development of prehis- dle Magdalenian levels of Blanchard cave (Saint-Marcel, toric communities. In this sense, and in the field of archaeol- Indre, France) (Salomon et al. 2015), at Troubat (French ogy, several research efforts initiated by Marie Pierre Pomies Pyrenees), dated to 10 ky BP (Pomiès et al. 1999), at the and coworkers have been successfully performed over the Italians Late Epigravettian site of Riparo Dalmeri (Trento, years to analytically distinguish haematite synthesized by Italy) (Gialanella et al. 2011) and the (Proto) Aurignacian heating from natural haematite (Pomiès et al. 1998 and 1999; levels of Fumane Cave (Verona, Italy) and in the Late Epi- Gialannella et al. 2011; Salomon et al. 2012, 2015; Cavallo gravettian sequence at Tagliente rock shelter (Verona, Italy) et al. 2018). In particular, thanks to the complementary use (Cavallo et al. 2018). So, while the technologies to obtain red of X-ray dir ff action (XRD) and transmission electron micros - pigments from yellow raw materials were already known in copy (TEM) microanalyses, integrated with other comple- the Palaeolithic, it seems prehistoric artists did not resort to mentary analytical methods, and the study of non/archaeo- this technique to produce their art, neither in the Palaeolithic logical samples, nonuniform broadening of diffraction peaks nor in later periods. Or at least, it has not yet been proven. and residual dehydration pores of single crystals can be con- Cinnabar (HgS), the bright red form of mercury (II) sidered as main indicators of previous heating. Moreover, sulphide that represents the most common ore of oxidized when the archaeological and geological contexts are well mercury found in nature, is another mineral with colour- known, this research protocol can also distinguish between ing properties sourced since more recent prehistoric times a deliberate, and perhaps perfectly mastered, heating and an (Fig. 6). While it has been identified as early as in the Pre- accidental one (Salomon et al. 2012, 2015). This knowledge Pottery Neolithic and the early Neolithic funerary and occu- is extremely important for the study and understanding of pation deposits from the Middle East and Spain (Mellaart prehistoric pigments, including those used to create rock art. 1967; Molleson et al. 1992; Martín-Gil et al. 1995; Martínez In fact, for many years, heating has been assumed the motive et al. 1999; Goren et al. 2001; García-Borja 2004; Hunt et al. for the high frequencies of red rocks used in archaeological 2011; Domingo et al. 2012), examples of cinnabar use in campsites and the red pigments in rock art paintings from prehistoric rock art are unknown. However, at the famous Western Europe (Salomon et al. 2015). Thus, this research Neolithic site of Çatalhöyük (Turkey), this particular pig- protocol has been effectively adopted to examine prehistoric ment was used both alone or mixed with red ochre to pro- pigments from different sites, contexts and archaeological duce wall paintings. The mixed use of this mineral has been levels. As an example, and contrary to what it was previously interpreted as intentional, to achieve a brighter red colour thought, several studies showed that no heat treatment had and/or related to the potential symbolic meaning of this been applied to the red pigments sampled from wall figures more rare and harder to source raw material (Çamurcuoğlu and cave deposits at Lascaux (Dordogne, France) cave, iden- 2015). tifying four different types of natural haematite (hexagonal lamellar, trapezoidal lamellar, fibrous and almost amorphous Black pigments haematite). This implies that the large variety of red hues used during the Solutrean and Magdalenian periods char- Black prehistoric paintings have been produced with two acterizing the majestic paintings from Lascaux were natural different classes of natural pigments. Organic blacks, char - and the Palaeolithic artists knew where to find them (Chalmin acterized by carbon-based pigments, mainly in the form of et al. 2004a; Vignaud et al. 2006; de Balbín Behrmann and charcoal or soot, and mineral blacks, based on manganese Alcolea González 2009; Menu 2009). Similarly, in Arcy-sur- oxides/hydroxides, are the principal components identified Cure (Yonne, France), where the prehistoric living area also has rock art and where the red pigment found on the ground Fig. 6 Red powder (cinnabar has been interpreted as a workshop to prepare the paints, the and quartz) preserved inside experimental protocol showed that such haematite was not a shell at the Neolithic site of the result of dehydration of goethite present in the neighbour- Cova de l’Or (Beniarrès, Ala- ing cave of Saint Moré (Chalmin et al. 2003; Salomon 2008). cant, Spain) Overall, no direct cases of heating have been documented in pigments used to produce rock paintings during the European Palaeolithic period so far (Menu 2009; Salomon 2008; Salo- mon et al. 2015). If we move beyond the art and focus on pig- ments identified in archaeological deposits, the use of heated yellow ochre pigments has been reported at Mousterian lev- els of Es-Skhul (Mount Carmel, Israel) dated to 100 ky BP 1 3 196 Page 10 of 20 Archaeol Anthropol Sci (2021) 13:196 in black pictographs worldwide (Chalmin et al. 2003; Vig- Behrmann and Alcolea González 2009). In Gargas (Hautes- naud et al. 2006; Salomon et al. 2008; de Balbín Behrmann Pyrénées, France), famous for preserving more than 250 and Alcolea González 2009; Menu 2009; Chalmin and Hunt- “negative hands” (or hand stencils) painted in red and black ley 2017; Stuart and Thomas 2017; Gallinaro and Zerboni and only one in white, several black negative hands were 2021; Domingo et  al. 2021; Sepúlveda 2021). In nature, made with charcoal (“Hand Sanctuary”), and the others with carbonaceous matter can be found as geological deposits of manganese oxides (“Entrance Gallery”), in which manganite graphite, coal, etc., but disordered and heterogeneous amor- in association with other Mn-based oxides like pirolusite and phous carbonaceous matters like charcoal or soot can be criptomelano has been identified (Chalmin et al. 2006). made by firing organic substances including wood or bone If we move to post-Palaeolithic art, and more specifically (Coccato et  al. 2015). Manganese oxides/hydroxides are to Spanish Levantine rock art, amorphous carbon from veg- naturally occurring minerals present in soil and sediments. etal origin occurred more frequently than manganese-based They are frequently found as coatings on rocks and nodules. pigments (Fig. 7) (Domingo et al. 2021). While the num- According to the chemical composition, valence states of ber of sites with black pigments analyzed is still low, this the manganese metal (II, III, IV or mixed) and crystalline preliminary finding could suggest a better access to vegetal structure, more than 20 different mineralogical varieties can organic matters to be charred and employed as pictorial be distinguished among them. They can be divided into two material, than to manganese sources (Domingo et al. 2021). main families based on the presence or absence of additional Something similar happens with black pigments in Latin foreign cation (Chalmin et al. 2008). Manganite MnOOH, America where charcoal has been detected randomly in all pyrolusite MnO , bixbyite Mn O , hausmannite Mn O and, prehistoric cultures (Sepúlveda 2021). This does not mean 2 2 3 3 4 on the other hand, romanechite Ba Mn O ‧xH O, hollandite that the prehistoric Levantine painters were not ingenious in 2 5 10 2 BaMn O ‧xH O represent some of the most recurring min- finding their raw materials. For example, at the Los Chapar - 8 16 2 erals taking part of such two categories, respectively. They ros site (Albalate del Arzobispo, Spain), pigment analysis can be found in a large variety of natural settings, also in the revealed the use of manganese oxides/hydroxides, whose mixture, and in the form of wads, a general term to describe precise mineral nature was not exactly characterized due to dark brown to black coloured earth pigments and materi- the low crystallinity of the analyzed compounds, as black als in which manganese oxide/hydroxide are contained ca. pigment. Similarities between the analyses of the Levantine 50% (Siddal 2018). In Western European Palaeolithic rock pigment and a dendrite mineralization located close to the art, the use of both types of black pigments is equable in rock art site suggest local procurement strategies (Pitarch both French and Spanish sites. In fact, there is no system- et al. 2014). atic prevalence of the use of the organic black with respect Driven by the same motivations that led archaeologists to the inorganic one, even the former was used mainly for and scientists to deeply study the goethite-haematite thermal drawing outlines. In some sites, both are present (Menu and transformation system, also manganese oxides/hydroxides Walter 1992; Chalmin et al. 2003, 2006; Vignaud et al. 2006; have been highly examined under heat treatment to compre- Menu 2009; de Balbín Behrmann and Alcolea González hend their transformation mechanisms and to gain insights 2009; Gay et al. 2020). For instance, in Ekain Cave (Basque into black pigment processing technologies during the Pal- Country, Spain), dating to the Magdalenian culture, black is aeolithic. In fact, some analytical studies and archaeological the dominant colour and charcoal is the primary black pig- findings suggested to archaeologists a possible use of heated ment used to create the famous horses (Chalmin et al. 2003). black pigments by prehistoric artists (Smith et  al. 1999; Only two uncommon figures, one horse and two bears, have Guineau et al. 2001; Chalmin et al. 2008). Thus, despite the been painted with manganese oxide. This uncommon use, absence of any colour change in the black pigments, it was compared to the other paintings, suggested to archaeologists supposed that the calcination could potentially induce modi- that this pigment was precious or symbolic. On the contrary, fications of the microstructural features, such as dehydra- in Lascaux (Dordogne, France), only manganese black pig- tion, a loss in the cohesion of the matter, facilitating grind- ments with different mineral nature have been identified in ing (Guineau et al. 2001; Chalmin et al. 2008). To verify the black figures. Their mineral composition is similar to that these assumptions, Emily Chalmin and coworkers studied of several black crayons found next to the cave walls (Chal- the thermal transformation of manganese oxides/hydroxides min et al. 2003, 2004a, b). Similarly, in the Great Ceiling at systems both in artificial and several archaeological sam- Rouffignac Cave (Dordogne, France), at least three different ples. They found an analytical protocol to follow in order to types of barium-bearing manganese oxides (that could be recognize the application of heat treatment to this kind of assimilated to different black raw colouring materials) were black pigments using scanning electron microscopy com- used. Meanwhile, only charcoal has been detected in the bined with energy-dispersive X-ray analysis (SEM–EDX), black samples belonging to Grande Grotte of Arcy-sur-Cure X-ray diffraction (XRD), transmission electron microscopy (Yonne, France) or Altamira (Cantabria, Pain) (de Balbín (TEM) and X-ray absorption near edge structure (XANES) 1 3 Archaeol Anthropol Sci (2021) 13:196 Page 11 of 20 196 to minimize damaging the paintings, in Western European Palaeolithic caves, both French and Spanish researchers have focused on determining the age of spectacular rock paintings by dating charcoal pigments, obtaining more than a hundred dates so far (Steelman and Rowe 2012; Ochoa et al. 2021). Standard procedures have been adopted for dating archaeo- logical charcoal, using acid to remove carbonates and com- bustion to collect carbon for AMS C dating. Most dates obtained on pictographs worldwide have been on charcoal pigmented paintings. There are about 150 publications on dating charcoal pigment in rock art that involve at least six laboratories (Rowe 2012), providing variable and sometimes contested results (Ochoa et al. 2021). A balance between the need to date the art and the impact of such actions should be found since while sampling large paintings like the ones found in Palaeolithic art may cause only small scars to the charcoal drawings, dating much smaller Levantine paintings may result in the destruction of a large part of the motifs to obtain enough matter for dating. Fig. 7 Black Levantine deer from coves de la Saltadora IX (Cas- tellón, Spain) painted with manganese-based pigment Yellow pigments (Chalmin et al. 2003, 2004a, b, 2006, 2008). In particular, The prehistoric yellow pigments are usually characterized manganese oxides/hydroxides can undergo a series of suc- by yellow ochres (see Red pigments for the definition of cessive phase transformations involving oxidation/dehydra- ochres and earth pigments) whose brownish-yellow typi- tion/reduction reactions depending on the heating tempera- cal colour is due to the presence of goethite (α-FeOOH), ture and on the specific nature of the original mineral. As an iron (III) oxide-hydroxide natural occurring mineral, an example, at 360 °C, the monoclinic manganite (MnOOH) as the main chromophore. Similar to what happens for the phase is transformed into tetragonal pyrolusite (MnO ) by use of haematite and red ochres, the use of goethite and oxidation and dehydration. At 560  °C, this pyrolusite is goethite-rich materials is common to all prehistoric tradi- reduced as well into cubic bixbyite (Mn O ); at the end, tions worldwide to create yellow paintings. However, they 2 3 bixbyite is transformed into tetragonal hausmannite (Mn O ) are uncommon in works of art prior to the Late Neolithic 3 4 at 950 °C and so on (Chalmin et al. 2004a, b, 2008). Two (Siddal 2018). Regarding Western European Palaeolithic different protocols have been defined depending on the rock art, according to Menu (2009), about 1% of the paint- presence or not of foreign cations in the manganese-based ings were completed with yellow or brown colour, some of mineral, based on the evaluation of specific morphological, which are displayed on the Lascaux site. In this case, they chemical and structural criteria to be followed during the are based on yellow ochre (Chalmin et al. 2006; Vignaud changes induced by heating. The complete description of et al. 2006; Menu 2009; de Balbín Behrmann and Alcolea all heating patterns that could occur to manganese oxides/ González 2009). Moreover, in some works from the end hydroxides when calcined is well summarized in Chalmin of the Magdalenian, jarosite, a basic hydrous sulphate of et al. (2008). From their results, they concluded that not potassium and iron KFe (SO ) (OH) , has been also found 3 4 2 6 heating treatment had been applied to any of the various sporadically. Jarosite is a beautiful yellow mineral, quite black Mn-based pigments they studied from the paintings rare, available in Ariège near caves (Menu 2009). Jarosite of various prehistoric sites such as Lascaux, Ekain, Gargas, has been also detected in several prehistoric yellow figures Labastide, Combe Sauniere and Roucador (Chalmin et al. from Latin America (Sepúlveda 2021). Furthermore, while 2003, 2004a,b, 2006, 2008). it is not specifically rock art, it is important to mention the Finally, to rock art research, the identification of carbon- unique collection of Palaeolithic painted portable art coming based organic pigments is of special interest since it opens from Parpalló Cave, (Gandía, Spain), one of the most impor- the way for radiocarbon dating. Dating rock art is one of the tant Palaeolithic sites in the Spanish Mediterranean region. major challenges faced by archaeologists, and it is absolutely With over 5600 decorated plaquettes, this unique site has necessary to place the art in the cultural context (Steelman provided a reference collection for the study of the Palaeo- and Rowe 2012; Ochoa et al. 2021). Not without techni- lithic art in Europe since it covers the entire archaeological cal difficulties and strict protocols to be followed in order sequence from the Gravettian to the Magdalenian periods 1 3 196 Page 12 of 20 Archaeol Anthropol Sci (2021) 13:196 (32–14,000 cal. BP). The plaquettes are characterized by compounds used for the creation of white paintings (Stuart zoomorphic and sign depictions and, in addition to the pre- and Thomas 2017; Chalmin and Huntley 2017; Gallinaro and dictable use of red and black pigments, a large amount of Zerboni 2021; Sepúlveda 2021). Interesting is also the use of those are painted with yellow materials, identified as yellow calcined bones in Argentina (Wainaright et al. 2002). ochres (Roldan et al. 2016). White pigments Prehistoric paints (binders, recipes and application techniques) The occurring of white colour in Western and Mediterra- nean European prehistoric rock art is not frequent. Prehis- In prehistoric times, the production of the artworks required toric European artists did not commonly employ white pig- significant advanced planning to collect the raw materials ments or at least they have not been as well preserved as used to prepare the sourcing, processing and application red and black paintings. Both ethnography and archaeology tools, the crayons and the paints necessary to create paint- have emphasized the problematic conservation of white pig- ings. The complexities of this process and the amount of ments, which may be providing a wrong picture of the col- time invested by prehistoric artists demonstrate that they our preferences of prehistoric artists (e.g. Chaloupka 1993; were not based on improvisation (Fiore 2007). The range of Chippindale and Taçon 1998; Domingo 2005; Domingo et al. mineral and organic pigments described above were used in 2018). During the Palaeolithic, white paintings have been prehistoric times either for dry use (as crayons) to produce only found once on a negative hand in the Gargas Cave, in drawings (with astonishing examples in places like the sites the Pyrenees, consisting of talc (Mg Si O (OH) ) and clay of Chauvet or Ekain, to name a few) or as the bases to pro- 3 4 10 2 (Menu 2009). Later on, during the post-Palaeolithic, and duce paint for their monochromatic and polychromatic crea- more specifically within the Levantine rock art context, a few tions (like the famous polychrome bisons of Altamira Cave). examples demonstrate a minor use of white pigment to pro- In this case, the raw pigments were finely ground, sometimes duce both monochrome and bichrome paintings (Domingo even sieved and finally mixed with a liquid medium (vehicle) et al. 2021). Hernanz et al. (2008) analyzed a bicolour bull and other additives and natural binding substances (animal composed of red and white brushstrokes in the Marmalo IV fat or plant extracts) to facilitate adherence. Different granu- shelter of Sierra de las Cuerdas (Cuenca). Compounds like lometries reflect the quality of the grinding and/or sieving α-quartz (α-SiO ), anatase (T iO ), apatite (Ca (PO ) ), mus- process and the skills of the artists (Hernanz et al. 2008). 2 2 5 4 3 covite (KAl (Si Al)O (OH,F) ), gypsum (CaSO ·2H O) While little archaeological information on binders is 2 3 10 2 4 2 and illite ((K,H O)(Al,Mg,Fe) (Si,Al) O [(OH) ,(H O) available, ethnoarchaeology demonstrates that the use of 3 2 4 10 2 2 ]) were detected in the white lines of the painted figure. In binding agents such as honey, plant resin, natural wax, ani- particular, the white traces in the composition of the painted mal fat, blood and others (Ravenscroft 1985) is necessary animal seem to enhance the perception of the muscles of the for the art to survive, especially in the open air, since paint- red bull. Microstratigraphic studies revealed that the white ings produced without binders disappear in a few years or layer was superimposed to the red one. A similar use of the decades depending on their exposure (Domingo et al. 2018). white pigment for highlighting and emphasizing details of Today, the problematic identification of these substances painted figures had been found in other rock art sites of the is most likely related to the low residual amount of their Valltorta-Gasulla complex (Civil and Centelles sites), again constituent organic macromolecules (carbohydrates, lipids, employed to underline details and adornments in human fig- proteins as main classes and their residuals) in the pictorial ures (Domingo 2005; Domingo et al. 2021). Furthermore, paints due to their chemical transformations caused by their another example of white painting found in the Iberia pen- aging and degradation as well as to the intrinsic limits and insula is located at the rock-art shelter Abrigo del Águila technical constrains of the experimental techniques used (Badajoz), belonging to Iberian Schematic rock art tradition so far for identification purposes (Domingo et al. 2021 ). (Rosina et al. 2018). The micro-Raman analyses pointed out Moreover, the potential carbohydrates, lipids and proteins the presence of anatase and the authors assumed that the that could have been used as binders in prehistoric times white figures could have been made using minerals from the are also some of the nutrients used by microorganism (like illite-kaolinite group. Moving from European borders, white fungi, bacteria, lichens and so on) for growth and they could pigments are most frequently found in prehistoric rock art be fixed as calcium oxalates at the end of the feeding actions coming from other parts of the world, like in Australian, Afri- (Rampazzi 2019; Domingo et al. 2021). Thus, should any can and American rock art creations. In particular, kaolinite residual amounts be left, the detection would be challenging (Al Si O (OH) ), huntite (CaMg (CO ) ), quartz (α-SiO ), (Spades and Russ 2005). 2 2 5 4 3 3 4 2 gypsum (CaSO ·2H O), calcite (CaC O ), and calcium The use of lipid binders was detected at various Palaeo- 4 2 3 oxalates (CaC O ·(H O) ) are some of the most detected lithic sites, such as Fontanet, Enlène and Les Trois Frères, 2 2 2 x 1 3 Archaeol Anthropol Sci (2021) 13:196 Page 13 of 20 196 (Pepe et al. 1991). At some sites of different chronologies, the dangers of making direct assumptions such as this since the these organic binders were interpreted as consistent with ani- use of milk as a binder has been also detected among hunter- mal fats, including for example the Palaeolithic sites of Tito gatherer communities living in South Africa 49,000 years ago Bustillo (Navarro and Gómez 2003), some Levantine paintings (Vila et 2015). Moreover, as the authors of la Saltadora study of la Saltadora site (Roldan et al. 2018) or the more recent art say (Roldán et al. 2018), there is still no direct evidence that of the dolmen of Dombate, where the use of milk fat and but- the detected casein is not a ubiquitous contemporary contami- ter was suggested (Bello and Carrera 1997). Further examples nant since it has been identified both in un/pigmented areas so have been also reported in other regions around the world (e.g. more scientific efforts have to be spent to resolve this question. Boschín et al. 2002; Prinsloo et al. 2008; Moya et al. 2016; Among other uses, milk and casein have been also documented Brook et al. 2018). Nevertheless, attention should be paid in cultural heritage studies as a fixative or stabilizing agent to whether organic molecules identified today are really of in different kinds of more recent painted and stone artworks prehistoric origin. For example, fatty acids, among the main (Chamberly et al. 2009; Snethlage and Sterflinger 2011). constituent of lipids, have been identified equally both in the The use of blood as an agent has not been detected in any paint and in natural rock coating, composed mainly by calcium European site, and it is rare in other regions, with only a few oxalate and to a lesser extent by gypsum and clays, in micro- references from Australian (Loy et al. 1990) and African samples from the Lower Pecos Region of southwestern Texas sites (Lewis-Williams 1994: 281; Williamson 2000). Fibres (Spades and Russ, 2005). The authors attributed such con- and plant extracts have been also suggested as potential tents to microbial activity on the rock surfaces due to lichens, binders in Australia (Watchman and Cole 1993) and South bacteria and others that naturally live on the rock surface and America (Boschín et al. 2002). they indicated that fats or oils were either not used to prepare Other inorganic additives intentionally added to pre- the paints or that if such binders were used, they had already historic paintings include clays (e.g. Baffier et  al. 1999; degraded when analyzed by gas chromatography–mass spec- Hernanz et  al. 2008; Hamenau et  al. 1995); quartz (like trometry (GC–MS). Thus, the presence of this kind of accre- in Lascaux, Clottes 1997); quartz and amber in Altamira tions commonly correlated to the paints and often fossilized on (Groenen, 2000); K-feldspar at La Vache, Salón Noir de them could create misleading interpretations when investigat- Niaux and de Fontane (Clottes, 1997); quartz and K-feldspar ing organic molecules. Not only patinas, but also the analyses in Arenaza (Garate et al. 2004); talc in some Schematic art of raw ochres collected close to several rock art sites in Aus- sites (Hameau et al. 2001) and mixed with biotite in Niaux tralia showed a high amount of organic matter in the pigments (Clottes, 1997), burned bones in Western European Palaeo- themselves, such as lichens and bacteria (Ridges et al. 2000). lithic (de Balbín Behrmann and Alcolea González 2009), Thus, the identification of biological molecules such as lipids Levantine (Hernanz et  al. 2008) and Schematic art (e.g. and proteins, on the rock art pictographs, has to be carefully Hameau et al. 2001). This variety of additives, often used considered since they could also belong to the microorganisms to obtain different colour hues or textures, has been used to living on rock surfaces, coatings and pigments, like lichens talk about the preparation of different paint recipes in Pal- (García et al. 2001), bacteria (Roldan et al. 2018), fungi and aeolithic times (Menu and Walter, 1996; Baffier et al. 1999; algae. Thus, they cannot be immediately attributed to origi- Hameau et al. 2001; Chalmin et al. 2003; Garate et al. 2004, nal binders used to produce prehistoric paint (Hernanz 2015). among others), reflecting elaborated technologies and dif- This issue has to be also taken into account when considering ferent cultural choices in paint preparation. The degree of radiocarbon dating rock painting samples (Bednarik 2002) paint homogeneity of the rock art panels or sites may pro- since organic matter from the natural occurring environment vide information for discussing the completion times of the is undistinguishable from that coming from organic materials artworks. For instance, Garate et al. (2004) deduce that the used as part of the prehistoric paints or binders. Another exam- paintings of Arenaza result from a single intervention based ple regarding proteinaceous binders is found at la Saltadora site on the consistency of the paints used, while Groenen (2000) in Spain, where the presence of casein peptides of animal ori- suggests that the production of the hand stencils from Gargas gin has been identified on both pigmented and non-pigmented stretched over a period of time considering the variety of areas by proteomic approaches, as described by Roldán et al. recipes detected. (2018). The presence of casein in Levantine pigments suggests Once the pictorial mixture was ready and depending on the authors the use of milk as binding media. If finally proven, the period and region, the paint was applied using a variety these results would be highly interesting from the archaeologi- of techniques. For example, European Palaeolithic artists cal point of view, and more specifically for the chrono-cultural used different types of brushes and pads, hands and fingers debates surrounding the authorship of Levantine paintings, and the blow painting techniques (i.e. blowing the paint since the use of milk could be interpreted as a conr fi mation directly from the mouth or through hollow tubes), while that it was created by farming communities and not by the last Levantine artists only used a variety of brushes, as deduced hunter-gatherers. Nonetheless, another recent finding warns of from the fine strokes characteristic of this tradition (Menu 1 3 196 Page 14 of 20 Archaeol Anthropol Sci (2021) 13:196 2009; D’Errico et al. 2016). The nature of the brushes is of production seems to be strongly influenced by cultural unknown, though, since they are not preserved in the archae- decisions and choices, traditions and probably even beliefs. ological record (Domingo 2020). Physico-chemical analyses have also potential as a tool to identify whether pigment remains located on the walls of caves and rock shelters are natural formations or inten- Conclusions tionally produced by humans, and also as an authentication tool to confirm whether any new finds are truly prehistoric The systematic application of scientific analyses from differ - (Garate et al. 2004), even though subject to certain limits ent disciplines (physics, chemistry, mineralogy, petrography, (García et al. 2001). geology and biology) to the study of prehistoric pigments Furthermore, physico-chemical approaches are also and paints have improved the way prehistoric art and colours important to advance knowledge on pigment conservation, are analyzed and understood today, allowing the discovery of interest to understand how the art has survived, predict the of multiple uses of different raw materials with colouring long-term behaviour of pigments and bedrocks and identify properties in prehistoric times and expanding the frontiers potential risks. They are also crucial to develop best conser- of archaeological knowledge on one of the most fascinating vation practices and protocols, giving careful consideration legacies of the past: rock art. to the fact that any materials introduced (modern pigments As discussed in this paper, building a systematic knowl- used to tone areas of bedrock loss, materials for consolida- edge about the raw materials and their potential sources, tion and so forth) or removed (crusts) in any conservation the techniques, instruments and processes involved in the interventions could impact archaeological approaches to past production of prehistoric art and exploring their patterns pigments, paints, technologies and practices. of change over space and time are questions of interest to Today the range of portable non-invasive spectroscopic archaeological research to gain information on the palette, techniques available to archaeologists has been a push for the the technologies and the socio-cultural practices of ancient scientific analysis of prehistoric art and pigments, minimizing artists as well as on aspects of social dynamics and produc- impacts on this unique and fragile heritage. They have opened tive processes. Such an approach is showing that while the up new opportunities for direct on-site analysis, enabling the amount of minerals and colours used in prehistoric art is application of new analytical research approaches to the study limited, the patterns of production of different regions or of rock art and providing guidance to avoid or at least mini- periods are different, demonstrating that the exploration of mize the need to resort to sampling and the use of invasive the non-visual aspects of the art offers new avenues to track analytical methods (whether non-destructive or destructive). past social identities (see for example Vergara and Troncoso, While sampling is still necessary, portable non-invasive meth- 2015). As Gosselain (1992) states, the visual aspects of the ods allow us to perform more targeted sampling, which should artefacts (in rock art, variations in form and subject matter) only be performed as a last resort when no other non-invasive can be easily replicated, while non-visual aspects (or those techniques can answer our research questions. This sampling that we will have to explore through archaeometry, such as strategy reduces potential impacts on the art. the nature of the raw materials used and the transformation What is clear from this review is the importance of mul- practices, pigments recipes and so forth) are more difficult titechnical and multistep multidisciplinary approaches in to copy, thus providing more opportunities to explore the studying prehistoric pigments and paints to gain a more more stables aspects of social identities (Domingo and Fiore, comprehensive understanding of the many uses of these 2014). particular archaeological remains and the many aspects of As debated along this paper, and broadly speaking, while past cultures they can shed new light on. We are confident prehistoric humans were constraint by a limited number of that in the next few years, continued technological advances raw materials available in nature (mainly 4 colours—red, in analytical techniques will improve our approaches to rock black, yellow and white—were used all around the globe), art, opening new avenues of research now still unthinkable. analytical approaches are demonstrating certain variability in different steps of paint production (raw materials used, Author contributions Both authors contributed equally to this work. grain sizes, recipes, etc.) and application between different traditions. These variations do not simply result from envi- Funding This research has been supported by several research grants ronmental constraints, such as the availability of certain raw directed by Inés Domingo: HAR2016-80693-P funded by the Spanish materials and no others since the absence of local supplies Ministry of Science, Innovation and Universities and the ERC-CoG LArcHer project, funded by the European Research Council (ERC) was solved through different strategies, such as long-distance under the European Union’s Horizon 2020 research and innovation procurement or the development of exchange networks. Thus, programme (grant agreement No 819404). the variability observed in the different steps of the process 1 3 Archaeol Anthropol Sci (2021) 13:196 Page 15 of 20 196 Data availability Not applicable. Beck L, Genty D, Lahlil S, Lebon M, Tereygeol F, Vignaud C, Reiche I, Lambert E, Valladas H, Kaltnecker E, Plassard F, Menu M, Paillet P (2013) Non-destructive portable analytical techniques Code availability Not applicable. for carbon in situ screening before sampling for dating prehistoric rock paintings. Radiocarbon 55(2–3):436–444 Declaration Beck L, Rousselière H, Castaing J, Duran A, Lebon M, Moignard B, Plassard F (2014) First use of portable system coupling X-ray dif- Competing interests The authors declare no competing interests. fraction and X-ray fluorescence for in-situ analysis of prehistoric rock art. Talanta 129:459–464 Open Access This article is licensed under a Creative Commons Attri- Becker H (2021) Pigment nomenclature in the ancient Near East, bution 4.0 International License, which permits use, sharing, adapta- Greece, and Rome. Archaeol Anthropol Sci. https:// doi. org/ 10. tion, distribution and reproduction in any medium or format, as long 1007/ s12520- 021- 01394-1 as you give appropriate credit to the original author(s) and the source, Bednarik R G (2002) The Dating of Rock Art: a Critique. J Archaeol provide a link to the Creative Commons licence, and indicate if changes Sci 29:1213–1233Bello J Mª, Carrera F (1997) Las pinturas were made. The images or other third party material in this article are del monumento megalítico de Dombate: estilo, técnica y com- included in the article's Creative Commons licence, unless indicated posición. In: Rodríguez A (ed.) O neolítico atlántico e as orixes otherwise in a credit line to the material. If material is not included in do megalitismo: Actas do Coloquio Internacional (Santiago de the article's Creative Commons licence and your intended use is not Compostela, 1–6 de Abril de 1996). 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Characterizing the pigments and paints of prehistoric artists

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Abstract

This paper offers a broad and critical overview of current discussions on the potential uses and the characterization of pigments in prehistory, with a special focus on prehistoric rock art. Today, analytical approaches to pigments and paints allow us to go beyond the identic fi ation of the elemental and molecular composition of these archaeological remains, to explore also raw material procurement, transformation and use strategies of interest to investigate the technological and socio-cultural practices of prehistoric artists and their change over space and time. The paper also summarizes the palette of prehistoric artists, as well as the techniques and analytical strate- gies used to date to characterize prehistoric pigments and paints (colours, raw materials, binders and recipes) used in prehistoric rock art. Keywords Prehistoric art · Analytical chemistry · Pigments · Paints · Binders Premise et al. 2021).The second group of contributions is focused on pigments, starting from a philological essay on terminology This Topical Collection (TC) covers several topics in the (Becker 2021). Three archaeological reviews on prehistoric field of study, in which ancient architecture, art history, (this paper), Roman (Salvadori and Sbrolli 2021) and Medi- archaeology and material analyses intersect. The chosen per- aeval (Murat 2021) wall paintings clarify the archaeological spective is that of a multidisciplinary scenario, capable of and historical/cultural framework. A series of archaeometric combining, integrating and solving the research issues raised reviews illustrate the state of the art of the studies carried out by the study of mortars, plasters and pigments (Gliozzo et al. on Fe-based red, yellow and brown ochres (Mastrotheodoros 2021). The first group of contributions explains how mortars et al. forthcoming); Cu-based greens and blues (Švarcová have been made and used through the ages (Arizzi and Cul- et al. 2021); As-based yellows and reds (Gliozzo and Burgio trone 2021; Ergenç et al. 2021; Lancaster 2021; Vitti 2021). 2021); Pb-based whites, reds, yellows and oranges (Gliozzo An insight into their production, transport and on-site organ- and Ionescu 2021); Hg-based red and white (Gliozzo 2021) ization is further provided by DeLaine (2021). Furthermore, and organic pigments (Aceto 2021). An overview of the use several issues concerning the degradation and conservation of inks, pigments and dyes in manuscripts; their scientific of mortars and plasters are addressed from practical and examination and analysis protocol (Burgio 2021) and an technical standpoints (La Russa and Ruffolo 2021; Caroselli overview of glass-based pigments (Cavallo and Riccardi forthcoming) are also presented. Furthermore, two papers on cosmetic (Pérez Arantegui 2021) and bioactive (antibac- This article is part of the Topical Collection on Mortars, plasters terial) pigments (Knapp et al. 2021) provide insights into the and pigments: Research questions and answers variety and different uses of these materials. * Inés Domingo ines.domingo@ub.edu Annalisa Chieli Introduction annalisachieli@ub.edu Archaeological research has provided evidence of human Departament d’Història i Arqueologia, ICREA/Universitat de Barcelona/SERP, Montealegre, 6-8, 08001 Barcelona, use of natural minerals and earths with colouring proper- Spain ties (iron and manganese oxides and hydroxides including Departament d’Història i Arqueologia, Universitat de haematite, goethite, maghemite, siderite and other miner- Barcelona//LArcHer, Montealegre, 6-8, 08001 Barcelona, als such as kaolinite, huntite, white chalk and others), with Spain Vol.:(0123456789) 1 3 196 Page 2 of 20 Archaeol Anthropol Sci (2021) 13:196 some examples dating back thousands of years (Watts et al. The many uses of pigments in prehistoric 2016; Wolf et al. 2018). The presence of pieces of pigment times of various sizes, pigment powders and residues and even drops of paint in archaeological deposits, contexts or materi- We know today that the presence of pigments in archaeo- als (shells, stone and bone tools, grinding stones, different logical deposits is not only related to the artistic production sorts of containers and so forth) is well attested, even before since many of these raw materials have other preservative, the appearance of rock art or the global dispersal of anatomi- antiseptic, abrasive, repellent, protective or even medical cal modern humans. properties (Velo, 1984; Hovers et al. 2003; García-Borja The identification of ochre processing workshops (includ- et al. 2004; Soressi and d’Errico, 2007; Roebroeks et al. ing raw materials, processing tools and/or storage contain- 2012; Rifkin et al. 2015, among many others), which were ers) in different chronologies and places—e.g. Blombos very probably known in prehistoric times. cave in South Africa 100,000 years ago (Henshilwood et al. As early as the 1980s, Couraud (1988) proposed already 2011), Qafzeh Cave in Israel around 92,000 years ago (Hov- three different uses of colouring raw materials during the ers et al. 2003), Porc-Epic Cave in Ethiopia ca. 40 ka cal BP European Palaeolithic, which could be also extended to other (Rosso et al. 2014), Santa Maira in Spain between 15 and regions and periods: 6 ka cal BP (Tortosa et al. 2020), Cova de l’Or in Spain in early Neolithic deposits (Domingo et al. 2012), the Early- – The production of different forms of artistic expression Middle Holocene site of Takarkori, in Lybia (di Lernia et al. – Domestic and functional uses 2016), among many others—reveals that the use of colour- – Funerary practices ing raw materials was not accidental but a well-planned activity since prehistoric times, demanding an important The archaeological literature has often related the use investment of time and effort to source and process these of these materials to different sorts of artistic, aesthetic or materials. symbolic practices. These include different sorts of deliber - In the last few decades, the combination of multi-tech- ate marks, drawings and paintings produced on rock walls nical (different non-invasive and invasive analytical tech- both within caves and rock shelters as well as in the open air niques, use-wear analysis, experimental archaeology, etc.) and on different sorts of portable objects. For a long time, and multidisciplinary approaches (chemistry, archaeology, this kind of artistic production seemed to be mainly related geology, traceology, ethnography and so forth) is providing to anatomical modern humans, with the earliest examples a more comprehensive view of these raw materials beyond including several fragmented ochreous pebbles and cray- the identification of their nature and composition, as we will ons with intentional incisions located at different South discuss along with this paper. With the new approaches, we African sites (Blombos cave, Klasies River, Pinnacle Point are now able to explore also potential sources, processing 13B, Klein Kliphuis) and dating back between 100,000 and practices and uses informing on ancient pigment sourcing, 85,000 years ago (Henshilwood et al. 2009; D’Errico et al. procurement (whether autonomous or obtained through 2012); 73,000-year-old red crosshatch marks identified exchange networks) and transformation strategies and tech- on a rock fragment at Blombos Cave (Henshilwood et al. nologies, and their changes over time. We can also explore if 2018); 77,000-year-old shell beads decorated with ochre the raw materials were used directly on soft or hard surfaces at Blombos Cave, Sibudu and Border Cave (Henshilwood (e.g. as crayons) or transformed into powder through grind- et al. 2004) and other African sites or the earliest examples ing and scraping and if any additives or binders were added of figurative and non-figurative painted rock art produced to produce a paste or a paint. by anatomical modern humans (AMH) in Spain (Pike et al. Our aim with this paper is to oe ff r a broad overview of the 2012; Hoffman et al. 2018a) and Indonesia (Aubert et al. techniques and analytical strategies used so far to character- 2014, 2018; Brum et al. 2021) dating back at least 40 and ize prehistoric pigments and the raw materials, binders and 45,000 years respectively. From then on, the tradition of recipes identified to date in rock art. A full review of the using colouring raw materials to produce different sorts of global literature dealing with pigment analysis of prehistoric art on different media (stone, bone, antler, pottery and so rock art is beyond the scope of this paper since in the last forth) spread around the world at different points in time. couple of decades the number of papers addressing this topic Today, a central debate in research on archaeological has considerably increased across the world. Thus, while pigments and human evolution is if their use to produce we reference global literature when offering examples, we different sorts of visual arts and marks on different media specially selected those from Western and Mediterranean was exclusive to us (AMH) or there are any precedents in European prehistory and rock art to illustrate our discus- the human lineage. In the last decade, several red rock art sions, as it is our main study area. marks and paintings located at different Spanish sites (some 1 3 Archaeol Anthropol Sci (2021) 13:196 Page 3 of 20 196 mouth or airbrush blown red paint located over a stalagmitic sorts of containers and tools (offerings?), as well as in the dome at Ardales site, Málaga, a hand stencil at Maltravieso, form of body or clothing decorations (e.g. Schotsmans et al. Cáceres, and a scalariform sign at La Pasiega, Cantabria) 2020), or even covering human skeletal remains. Couraud have been dated as early as, at least, 64 to 66,000 years ago suggested that some of these funerary practices could aim (Hoffman et al. 2018a, Zilhão 2020). At that time, AMH had at facilitating the preservation of the human remains since not yet arrived in the Iberian Peninsula, thus suggesting that ochre helps slow down decomposition (Couraud 1988). these depictions were produced by Eurasian Neanderthals. A similar interpretation is provided by other researchers Neanderthals’ use of personal ornaments with red colour- (Delibes 2000; Blas 2003; Martín-Gil et al. 2004) when ing residues as well as the use of colouring materials has the mineral used in these funerary contexts was cinnabar. been also reported by several researchers. For example, at Other authors, though, see a more symbolic explanation Cueva de los Aviones (Murcia, Spain) Zilhão et al. (2010) when ochre is recorded in relation to human skeletal remains interpreted a mixture of charcoal, dolomite, haematite and (Hovers et al. 2003). Interestingly, ethnographic accounts pyrite as well as yellow natrojarosite associated with marine suggest that the boundaries between symbolic and practical shells dating back 115,000 years (Hoffman et al. 2018b), as domains are often blurred and both can coexist in the same potentially used for cosmetic purposes, since according to object, tradition or practice (Rosso 2017; Domingo et al. them, the only known archaeological use of natrojarosite is 2020). Nevertheless, symbolic uses are usually culturally in cosmetics. Along the same lines, Soressi and d’Errico constructed and archaeologically invisible since they leave (2007) suggest that the manganese dioxide from the French behind no empirical evidence, and thus, they are hard to Mousterian sites of Pech de l’Azé I and Pech de l’Azé IV demonstrate. Based on the different uses identified in funer - may have been used for body painting (Soressi and d’Errico ary contexts of Çatalhöyük, Schotsmans et al. (2020) sug- 2007). Drops of a haematite-rich liquid of unknown use gest that pigments were probably used to build identities as were also identified on the sediment at Maastricht-Belvédère well as for social differentiation. For example, in funerary deposits in the Netherlands pushing back in time the use of contexts, most of the inhabitants of this site did not receive this mineral by early Neanderthals to at least 200–250 ka pigment treatment, and the very few who did point to differ - (Roebroeks et al. 2012). Thus, long before the arrival of ent treatment depending on their sex (cinnabar for male and AMH to Eurasia, Neanderthals were already using mineral blue and green pigments for female). colouring materials for different purposes. Whether this use In the last few decades, interdisciplinary approaches to of different pigments was symbolic or practical is difficult to the archaeology of colour have been also applied to the know since (as already discussed) many of these colouring characterization of pigments used for rock art production raw materials had many properties and as such, they were in prehistoric times, which are the focus of our research well suited for other daily activities like hide tanning, tool (Domingo et  al. 2021). This particular topic faces more hafting, tool polishing and so forth (Hovers et al. 2003). challenges than the study of other archaeological pigments The use of different colouring raw materials for practical since rock art sampling entails compromising the integrity of purposes in prehistoric times has been also deduced based on ancient works of art often protected and listed in the different a mixture of archaeological, ethnographic and experimental National Heritage acts (e.g. in Spain rock art is protected observations. Some practical applications proposed so far with the highest level of legal protection—Asset of Cultural include their use as additives mixed with natural glues to Interest—according to the 1985 Spanish Heritage Act, and be used as a fixative for hafting tools (Beyries and Inizan as such, it cannot be destroyed or removed). Some are even 1982; Allain and Rigaud 1989; Wadley 2005; Lombard 2007; listed in the UNESCO World Heritage list (Fig. 1). So even Helwig et al. 2014), as natural abrasives for fine polishing of if today we are talking about microsamples, rock art is con- bone tools and ornaments (Goñi et al. 1999; García Borja sidered an irreplaceable asset and it entails (as it should be) et al. 2004), as a natural antiseptic for tanning hides to reverse more restrictions when it comes to invasive sampling. the decay process (Audion and Plisson 1982; Adams 1988; In this part of the world, prehistoric art appears from Nor- Rifkin 2011), to dry tendons for different purposes (such us way to Spain and covers more than 60,000 years (Hoffman bow strings or for attaching stone tools to the shafts), etc. et al. 2018a), spanning from the Middle Palaeolithic to the (Domingo et al. 2012). Bronze Age. It includes several forms of non-figurative and Colouring materials have been also reported in funerary figurative art produced on different media (stone, bone, ant- contexts from the Middle Palaeolithic to the Neolithic and ler, ivory, animal teeth and maybe some perishable materials beyond (for example, Formicota 1986; Molleson et al. 1992; such as wood) and using a variety of techniques (paintings, Cacho et al. 1996; Stringer and Gamble 1996; Bar-Yosef engravings, carvings). In such a vast territory, different tra- 1997; Goren et al. 2001; d’Errico and Backwell 2016). In ditions developed over time, including among others Pal- these contexts, they appeared as lumps of different sizes or aeolithic, Levantine and Schematic art. Palaeolithic art is powder remains identified in the deposits or within different an art of naturalistic animals and signs with singular sites 1 3 196 Page 4 of 20 Archaeol Anthropol Sci (2021) 13:196 in Iberia and France like Altamira, Chauvet, Lascaux, Foz worldwide to create the first masterpieces of the history of Côa, to name a few) dating between 40,000 and 11,700 cal. art (Salomon et al. 2008; Menu 2009; de Balbín Behrmann BP. Levantine rock art is an art of naturalistic humans and and Alcolea González 2009; Aubert et al. 2014; Chalmin animals illustrating narratives of hunting, war and vio- and Huntley 2017; Stuart and Thomas 2017; Domingo lence, maternity and death. This art is specific to Mediter - et al. 2021; Gallinaro and Zerboni 2021; Sepúlveda 2021). ranean Iberia, with outstanding sites like Cova dels Cav- The identification of the archaeological pigments and their alls, Remigía, la Sarga or Cogul. It dates sometime around sources (e.g. Pitarch et al. 2014 and 2019; Defrasne et al. 7500 years ago (no reliable numerical dates are known yet) 2019), the examination of the manufacturing techniques and (Ochoa et al. 2021). Schematic art is an art of schematic pictorial recipes (e.g. Brunet et al., 1982; Menu and Walter humans, animals and geometric shapes, with different tradi- 1992, 1996; Baffier et al. 1999; Salomon et al. 2008; Menu tions across Europe dating between the Early Neolithic and 2009) or understanding the mechanisms causing paint and the Bronze Age (for a global overview of European prehis- bedrock degradation (Hernanz et al. 2007; Aramendia et al. toric art, see Sauvet et al. 2014). 2020) are some of the common archaeological questions that can be effectively unravelled through physicochemical anal- yses. Beyond the more traditional dating purposes (Steelman Characterizing prehistoric pigments and Rowe 2012; Ochoa et al. 2021), analytically studying rock paintings, we can gain information about the technolog- Over the last three decades, archaeometric approaches have ical and socio-cultural practices and backgrounds of prehis- highly increased our knowledge of prehistoric pigments toric artists and, at the same time, acquire knowledge about used both in caves and in open-air rock shelters and boulders the conservation of these particular artistic expressions often Fig. 1 Map with rock art sites and concentrations of sites included (Algeria). 20. Tadrart Acacus (Libya). 21. Ennedi Massif natural in the UNESCO World Heritage list. 1. Writing-on-Stone Áisinai’pi and cultural landscape (Chad). 22. Ecosystem and Relict Cultural (Canada). 2. Mesa Verde National Park (United States). 3. Sierra Landscape of Lopé-Okanda (Gabon). 23. Kondoa (Tanzania). 24. de San Francisco (Mexico). 4. Chiribiquete National Park (Colom- Twyfelfontein o/Ui-//aes (Namibia). 25. Tsodilo (Botswana). 26. bia). 5. Nasca and Palpa (Perú). 6. Serra da Capivara (Brasil). 7. Chongoni (Malawi). 27. Matobo Hill (Zimbabwe). 28. Maloti Drak- Ischigualasto/Talampaya Natural Park (Argentina). 8. Cueva de las ensberg (South Africa). 29. Wadi rum Protected area (Jordan). 30. Manos (Argentina). 9. Risco Caído and the Sacred Mountains of Hail Region (Saudi Arabia). 31. Gobustan (Azerbaijan). 32. Tamgaly Gran Canaria Cultural Ladscape (Spain). 10. Valle do Côa (Portugal) (Kazakhstan). 33. Sulaiman-Too Sacred Mountains (Kyrgyzstan). 34. and Siega Verde (Spain). 11. Bend of Boyne (Ireland). 12. Altamira Bhimbetka (India). 35. Mongolian Altai (Mongolia). 36. Zuojiang and Palaeolithic cave art of Northern Spain. 13. Rock art of the Medi- Huashan rock art (China). 37. Rock Islands Southern Lagoon (Repub- terranean Basin on the Iberian Peninsula. 14. Vézère Valley (France). lic of Palau). 38. Kakadu National Park (Australia). 39. Uluru-Kata 15. Grotte Chauvet-Pont d’Arc (France). 16. Valcamonica (Italy). 17. Tjuta (Australia) Tanum (Sweden). 18. Rock Art of Alta (Norway). 19. Tassili n’Ajjer 1 3 Archaeol Anthropol Sci (2021) 13:196 Page 5 of 20 196 located in changing environments. Indeed, accurate diag- any scientific research (Pollard et al. 2007; Madariaga 2015; nostic analysis of rock art productions can provide insight Hernanz and Gavira-Vallejo 2021). As such, the analysis of into pigments’ raw materials and their provenance, offering rock art pigments requires a combination of several ana- precious information on the geographic practices and the lytical methods to provide a complete characterization of social networks of prehistoric artists and their counterparts the materials within their environment in terms of physical, (Chalmin et al. 2006; Iriarte et al. 2009; Jezequel et al. 2011; chemical, optical, structural, geological and morphological Mas et al. 2013; Pitarch et al. 2014), as well as into paint- properties. The integration of data from different analyti- ers’ manufacturing methods for pigment processing, such as cal techniques represents the best strategy to overcome the grinding, heating, sieving and settling, and pigment appli- intrinsic limitation of every single method when applied to cation techniques (Menu and Walter 1992; Salomon et al. the study of heterogeneous matrices, such as those usually 2008; Bonneau et al. 2012; Salomon et al. 2015, Hernanz found in rock art, often multilayered and complex due to et al. 2008; López et al. 2017; Cuenca-Solana et al. 2016; overlapping of pictorial layers, patinas, crusts and bedrock d’Errico et a. 2016; Gay et al. 2020). Through these sorts media characterized by different materials. Moreover, con- of approaches, we obtain information to reconstruct the dif- sidering the enormous value of these heritage assets, usually ferent steps of the chaîne operatoire (operative sequence) appearing in remote locations, portable non-invasive analyti- required to produce an artwork, the behaviours, acts and cal methods and non-destructive techniques when analyz- skills of ancient artists and their changes over space and ing micro-samples are usually required for the examination time, of interest to identify cultural differences, similarities of these valuable artworks. According to the literature and and interactions (Jezequiel et al. 2011; Bonneau et al. 2012; our own experience, pigment analyses of rock art are gener- Pitarch et al. 2014; Velliky et al. 2020; Tortosa et al. 2020). ally performed in progressive smaller scales, from macro-, Moreover, the physicochemical analyses of the rock paint- micro- to nano-size (Fig. 2). Their chemical characterization ings are also important to characterize any alteration mecha- is usually made by elemental and molecular spectroscopic nisms threatening the preservation of the paintings, due to techniques such as X-ray fluorescence spectroscopy (XRF) natural aging and weathering or to anthropic direct or indi- and Raman spectroscopy. In addition, to determine their rect interventions. Such an approach is necessary to develop morphology and crystalline structure, other techniques like the best conservation strategies and practices adapted to the optical microscopy (OM), transmission electron microscopy particular features of the artworks and the environmental (TEM), scanning electron microscopy (SEM), typically com- specificities of their contexts. Distinguishing between picto- bined with energy-dispersive X-ray spectroscopy to perform rial layers, the rock supports and any interstratified/external elemental micro-analyses (SEM–EDX) and X-ray diffraction patinas and crusts is decisive for understanding weather- (XRD) have been also used. A similar analytical approach ing processes and the preservation of the rock art paints can be also applied to the study of prehistoric portable art. A (Doehnne and Price 2010; Dorn et al. 2008). complete description of the commonest laboratory and port- Overall, multidisciplinary research based on analytical able analytical methods used in archaeological and cultural approaches applied to the study of prehistoric rock art has heritage research can be found in Pollard et al. (2008), Nigra changed the way we understand the materials, tools and pro- et al. (2015), Madariagara (2015), Vandenabeele and Donais cedures involved in rock paintings production. In the past (2016), Bersani and Lottici (2016), Brunetti et al. (2016), few decades, we have moved from the more purely stylistic while their specific application to the characterization of and descriptive studies of the art to the objective examina- prehistoric rock art pigments worldwide can be obtained in tion of the chemical and physical properties of the materi- Vignaud et al. (2006), Menu (2009), Aubert et al. (2014), als constituting the pictograms. In this way, the universal Chalmin and Huntley (2017), Stuart and Thomas (2017), language of science, integrated with aesthetical evaluations, Sepúlveda (2021), Gallinaro and Zerboni (2021), Domingo is now a better integral means to distinguish, analyze, under- et al. (2021), Hernanz and Gavira-Vallejo (2021), to name stand, compare and describe prehistoric rock paintings. It is a few. It is worth mentioning that the analytical approaches worth mentioning that scientific examinations alone are not and the scientific methods used in the study of rock art pig- enough to offer complete answers to archaeological research ments have changed over the last 30 years, following and questions, but they need to be opportunely included in a adapting to the contemporary technological advances that larger archaeological research context using a multidiscipli- occurred in the field of portable spectroscopic analyti- nary and collaborative approach among the different disci- cal instruments. In fact, the first extensive and systematic plines. A crucial aspect related to the study of rock art pig- physicochemical studies of rock art pigments started at the ments and paintings, and more in general to the examination beginning of the 1990s and they were performed exclusively of a wide range of cultural heritage objects, is the increas- on micro-samples, as occurred in the substantial research ing awareness that there is not known technique that—by regarding European Palaeolithic cave art. Several min- itself—could answer all of the research questions raised by ute samples coming from important French and northern 1 3 196 Page 6 of 20 Archaeol Anthropol Sci (2021) 13:196 Spanish painted caves such as Altamira, Niaux, Lascaux, Ekain and La Garma were analytically studied at the labora- tories of Centre de Recherche et de Restauration des Musées de France, C2RMF, in Paris (Clottes et al. 1990; Menu 1990; Menu and Walter, 1992; Clottes 1997; Chalmin et al. 2003; Vignaud et al. 2006; Chalmin et al. 2017). These precious research works shed light on the nature of the pigments employed by Palaeolithic artists and they brought to light elaborated pictorial recipes and manufacturing methods, dis- playing remarkable technical skills of the prehistoric paint- ers. Afterwards, in the last few years, several technological efforts have been spent in the miniaturization of optical and electronic components of portable spectroscopic instruments trying to balance their performance with that of their respec- tive bench top laboratory setups. These advances have led to the creation of more and more compact, light and smart spectroscopic devices with high performance for in situ non- invasive spectroscopic investigations, especially suited for the analyses of cultural heritage objects (Vandenabeele and Donais 2016; Brunetti et al. 2016). Such progresses in the improvement of portable and handheld systems for in-field non-invasive analysis has facilitated the access to valuable and immovable artworks non-suitable for in-lab analysis, like prehistoric rock art, thus enabling a growing number of studies to be conducted in situ, contributing to preserving the integrity of the artworks (e.g. Roldán et al. 2010; Lahlil et al. 2012; Beck et al. 2014; Olivares et al. 2013; Gay et al. 2015, 2016, 2020; Pitarch et al. 2014). A preliminary non-invasive diagnostic analytical cam- paign represents the roots on which to base further analyses in terms of (i) identic fi ation of the constituting materials, (ii) selection of points or areas to be sampled at a later stage, (iii) evaluation of the state of conservation of the paint- ings within their environment, and their monitoring over time, and (iv) planning of any conservation and/or restora- tion intervention (Fig. 2A). Sampling is still an essential step to advance knowledge on the study of rock art, as it is required to conduct microstratigraphic studies, dating, etc. (Fig. 2B-C). However, if prior to sampling, we conduct in situ non-invasive analyses, we will minimize impacts and obtain information to guide future sampling. Unlike sam- pling, non-invasive approaches allow the potential examina- tion of the whole painting, offering a more global view of Fig. 2 A Portable energy-dispersive X-ray fluorescence (EDXRF) the art under study. Thus, non-invasive analyses are essen- spectrometer designed by ICMUV employed for non-invasive on- tial to design ethically targeted sampling strategies aimed site analyses of Schematic and Levantine paintings at el Carche at analyzing those areas with the potential to provide the site (Jalance, Spain). B Schematic red animal from el Carche site (Jalance, Spain) indicating the sampled area. To minimize visual most interesting results (Beck et al. 2013). On the contrary, impact, the sample was taken next to an area with painting loss. C a micro-sample can be representative only of the site or the Optical microscope image of a micro-fragment sampled from a red sampled figure. Considering the fragility and the values of Schematic painted figure showed in B. Three different layers can be the rock paintings, the number of micro-samples should be recognized, from bottom to top: the bedrock, the red painting layer, and the orangey external patinas reduced to a minimum, to answer questions that can only be answered by sampling. It is now generally accepted that a proper research protocol in the study of an artwork, rock 1 3 Archaeol Anthropol Sci (2021) 13:196 Page 7 of 20 196 art included, involves as a first step, when feasible, the use artists. Very broadly speaking, the palette of prehistoric art- of non-invasive analytical approaches and the synergistic ists is generally composed of two main hues, namely red use of multi-technical and multi-scale analyses. When talk- and black. Other colours such as yellow and white were less ing about rock art, it is important to note that the logistical frequently used (Fig.  3). In addition, the use of charcoal organization of a non-invasive research campaign is not a from the organic origin (wood charcoal and burnt bone) has trivial matter: the geographical location of the rock shel- been also broadly detected. In the following lines, a general ters could represent a real challenge in terms of physical description of the most common pigments used in the pro- access, energy source and portability of the instruments. duction of prehistoric rock art will be outlined, describing These logistical challenges could force us to prioritize direct their chemical nature and characteristics, and drawing atten- sampling, assisted only by small portable digital micros- tion to some selected examples. copy and/or digital cameras when choosing the area to be sampled, rather than being guided by preliminary scientific Red pigments analyses that could have helped us formulate new research questions. This may unnecessarily increase the number of Iron-based oxides and hydroxides compose red pigments, samples needed, resulting in more invasive interventions among which haematite (α-Fe O ) is the most frequently 2 3 and hence causing a more negative impact on this fragile identified in the Palaeolithic and post-Palaeolithic rock art heritage. Thus, a non-invasive spectroscopic analytical cam- record all over the world (Chalmin et al. 2003; Vignaud et al. paign should be always prioritized, when feasibly. Among 2006; Salomon et al. 2008; Menu 2009; de Balbín Behr- the portable non-invasive spectroscopic methods available, mann and Alcolea González 2009; Chalmin and Huntley portable energy-dispersive X-ray fluorescence (Fig.  2A) and 2017; Aubert et al. 2014; Stuart and Thomas 2017; Gallinaro Raman spectroscopies have been extensively used in rock and Zerboni 2021; Domingo et al. 2021; Sepúlveda 2021, art research for elemental and molecular in situ analyses, among others). Haematite is a Fe (III) oxide highly wide- respectively (e.g. Roldan et al. 2010; Hernanz 2015; Gay spread in rocks and soils (Fig. 4), which colour depends on et al. 2016). However, more complex portable devices have its crystal size and shape: the tones range from yellowish/ been brought to the field, as the portable system combin- red for nanoparticles to purple for micrometer sized ones ing X-ray fluorescence and diffraction techniques used for or even black for larger crystals, like specularite (Cornell the first time to analyze the pigments at Rouffignac Cave and Schwertmann, 2003). The mineral haematite is also the (Dordogne, France). This was the first XRF-XRD experi- principal colouring matter constituting red ochres. Focus- ment ever undertaken in an underground and archaeological ing a bit on some definitions, ochres are naturally occurring environment to study prehistoric rock art (Beck et al. 2014). deposits characterized by a variable amount of clayey min- These types of portable instruments are usually employed erals (such as kaolinite, illite), iron oxides/hydroxides and to analyze artworks located in indoor environments, like a other minerals/impurities (like quartz, calcium carbonates, museum, since they are too large and bulky to be brought etc.), showing different colours from brown to red through into the field (Vandenabeele and Donais 2016). Vis–NIR yellows and violets, depending on the specific nature of Fe hyperspectral imaging technology, a novel method in the oxides/hydroxides present (Siddal 2018) (Fig.  5). Thus, field of rock art studies so far, has been employed for the ochres comprise a wide range of raw materials from geo- first time in the analyses of rock art materials and pigments logical formations bearing iron oxides/hydroxides including from the Palaeolithic Cave of El Castillo (Puente Viesgo, shales, mudstones, siltstones, earthy sandstones and other Cantabria, Spain) (Bayarri et al. 2019). This technique is types of ferruginous deposits (e.g. ferricrete and limonite a powerful 2D spectroscopic diagnostic technology for the ores). Their specific red or yellow hues, and their consequent non-invasive analyses of polychromatic surfaces of artworks definition as red/yellow ochres, are due to the presence of highly employed in the study of easel paintings (Cucci et al. haematite (α-Fe O ) and goethite (α-FeOOH), respectively, 2 3 2016). This imaging method provides a non-invasive way as main chromophores among the other ochres’ constitutive to identify colour materials and maps them on the surface, components. Ochres belong to the wider group of earth pig- representing a promising research tool also to study, preserve ments, defined as natural deposits rich in clay minerals, iron and manage this valuable cultural heritage. oxides, manganese oxides and other minerals that produce a coloured fine powder with high tinting strength (Eastaugh et  al. 2008). As a pictorial pigment, thanks to its natural The palette of prehistoric artists abundance and chemical stability, haematite-based materials have been widely used in art from Pleistocene times—with Despite different chronological periods, artistic traditions, world-renowned sites like the western European Palaeolithic cultures and geographic locations, inorganic pigments from sites of Lascaux (Dordogne, France) or Altamira (Spain)— mineral origins usually characterize the palette of prehistoric to the present by all cultures of the world (Eastaugh et al. 1 3 196 Page 8 of 20 Archaeol Anthropol Sci (2021) 13:196 Fig. 3 Colours used in Spanish Levantine rock art. A Red. B Black. C Red infill and white outline. D White 2008). Focusing on Western and Mediterranean European the dehydration of goethite can synthesize it (Cornell and studies, haematite and red ochres have been the main com- Schwertmann, 2003; González et al. 2000). Specifically to ponents of all prehistoric red pictograms, from Palaeolithic the heating procedures, yellow goethite, or high goethite con- rock art, known for the richness of pictorial recipes (Clottes tent materials like yellow ochre, turns its yellowish colour to et  al. 1990; Chalmin et al. 2003, 2004a; de Balbín Behr- red shades upon heating at temperatures above 250–300 °C, mann and Alcolea González 2009; Iriarte et al. 2009; Menu forming disordered haematite whose complete crystallization 2009; Hernanz et. al 2011; Jezequiel et al. 2011; Olivares happens at higher temperatures (> 850 °C), due to a topo- et al. 2013) to the subsequent post-Palaeolithic traditions tactic transformation that involves the loss of water by the such as Levantine rock art (specific to Mediterranean Spain) and the more recent Schematic rock art (Rosina et al. 2018; Domingo et al. 2021). Although haematite and haematite-rich earths occur naturally, heat treatment or mechanical processes inducing Fig. 5 Optical microscope image of an ochre powder sampled from the soil of Coves Llongues site (Castellón, Spain). The image shows the heterogeneous composition and texture of the powder character- ized by crystals of different colours and sizes. From micro-Raman analyses (data not shown), this ochre is mainly composed of calcite, Fig. 4 Fragment of red pigment (haematite and calcite) gypsum, haematite and magnetite 1 3 Archaeol Anthropol Sci (2021) 13:196 Page 9 of 20 196 iron (III) hydroxide. For archaeologists, understanding the (Salomon et al. 2012), at Solutrean levels at Les Maîtreaux pigment production methods is an indirect way to assess the (Bossay-sur-Claise, Indre-et-Loire, France) and the Mid- level of technological and cognitive development of prehis- dle Magdalenian levels of Blanchard cave (Saint-Marcel, toric communities. In this sense, and in the field of archaeol- Indre, France) (Salomon et al. 2015), at Troubat (French ogy, several research efforts initiated by Marie Pierre Pomies Pyrenees), dated to 10 ky BP (Pomiès et al. 1999), at the and coworkers have been successfully performed over the Italians Late Epigravettian site of Riparo Dalmeri (Trento, years to analytically distinguish haematite synthesized by Italy) (Gialanella et al. 2011) and the (Proto) Aurignacian heating from natural haematite (Pomiès et al. 1998 and 1999; levels of Fumane Cave (Verona, Italy) and in the Late Epi- Gialannella et al. 2011; Salomon et al. 2012, 2015; Cavallo gravettian sequence at Tagliente rock shelter (Verona, Italy) et al. 2018). In particular, thanks to the complementary use (Cavallo et al. 2018). So, while the technologies to obtain red of X-ray dir ff action (XRD) and transmission electron micros - pigments from yellow raw materials were already known in copy (TEM) microanalyses, integrated with other comple- the Palaeolithic, it seems prehistoric artists did not resort to mentary analytical methods, and the study of non/archaeo- this technique to produce their art, neither in the Palaeolithic logical samples, nonuniform broadening of diffraction peaks nor in later periods. Or at least, it has not yet been proven. and residual dehydration pores of single crystals can be con- Cinnabar (HgS), the bright red form of mercury (II) sidered as main indicators of previous heating. Moreover, sulphide that represents the most common ore of oxidized when the archaeological and geological contexts are well mercury found in nature, is another mineral with colour- known, this research protocol can also distinguish between ing properties sourced since more recent prehistoric times a deliberate, and perhaps perfectly mastered, heating and an (Fig. 6). While it has been identified as early as in the Pre- accidental one (Salomon et al. 2012, 2015). This knowledge Pottery Neolithic and the early Neolithic funerary and occu- is extremely important for the study and understanding of pation deposits from the Middle East and Spain (Mellaart prehistoric pigments, including those used to create rock art. 1967; Molleson et al. 1992; Martín-Gil et al. 1995; Martínez In fact, for many years, heating has been assumed the motive et al. 1999; Goren et al. 2001; García-Borja 2004; Hunt et al. for the high frequencies of red rocks used in archaeological 2011; Domingo et al. 2012), examples of cinnabar use in campsites and the red pigments in rock art paintings from prehistoric rock art are unknown. However, at the famous Western Europe (Salomon et al. 2015). Thus, this research Neolithic site of Çatalhöyük (Turkey), this particular pig- protocol has been effectively adopted to examine prehistoric ment was used both alone or mixed with red ochre to pro- pigments from different sites, contexts and archaeological duce wall paintings. The mixed use of this mineral has been levels. As an example, and contrary to what it was previously interpreted as intentional, to achieve a brighter red colour thought, several studies showed that no heat treatment had and/or related to the potential symbolic meaning of this been applied to the red pigments sampled from wall figures more rare and harder to source raw material (Çamurcuoğlu and cave deposits at Lascaux (Dordogne, France) cave, iden- 2015). tifying four different types of natural haematite (hexagonal lamellar, trapezoidal lamellar, fibrous and almost amorphous Black pigments haematite). This implies that the large variety of red hues used during the Solutrean and Magdalenian periods char- Black prehistoric paintings have been produced with two acterizing the majestic paintings from Lascaux were natural different classes of natural pigments. Organic blacks, char - and the Palaeolithic artists knew where to find them (Chalmin acterized by carbon-based pigments, mainly in the form of et al. 2004a; Vignaud et al. 2006; de Balbín Behrmann and charcoal or soot, and mineral blacks, based on manganese Alcolea González 2009; Menu 2009). Similarly, in Arcy-sur- oxides/hydroxides, are the principal components identified Cure (Yonne, France), where the prehistoric living area also has rock art and where the red pigment found on the ground Fig. 6 Red powder (cinnabar has been interpreted as a workshop to prepare the paints, the and quartz) preserved inside experimental protocol showed that such haematite was not a shell at the Neolithic site of the result of dehydration of goethite present in the neighbour- Cova de l’Or (Beniarrès, Ala- ing cave of Saint Moré (Chalmin et al. 2003; Salomon 2008). cant, Spain) Overall, no direct cases of heating have been documented in pigments used to produce rock paintings during the European Palaeolithic period so far (Menu 2009; Salomon 2008; Salo- mon et al. 2015). If we move beyond the art and focus on pig- ments identified in archaeological deposits, the use of heated yellow ochre pigments has been reported at Mousterian lev- els of Es-Skhul (Mount Carmel, Israel) dated to 100 ky BP 1 3 196 Page 10 of 20 Archaeol Anthropol Sci (2021) 13:196 in black pictographs worldwide (Chalmin et al. 2003; Vig- Behrmann and Alcolea González 2009). In Gargas (Hautes- naud et al. 2006; Salomon et al. 2008; de Balbín Behrmann Pyrénées, France), famous for preserving more than 250 and Alcolea González 2009; Menu 2009; Chalmin and Hunt- “negative hands” (or hand stencils) painted in red and black ley 2017; Stuart and Thomas 2017; Gallinaro and Zerboni and only one in white, several black negative hands were 2021; Domingo et  al. 2021; Sepúlveda 2021). In nature, made with charcoal (“Hand Sanctuary”), and the others with carbonaceous matter can be found as geological deposits of manganese oxides (“Entrance Gallery”), in which manganite graphite, coal, etc., but disordered and heterogeneous amor- in association with other Mn-based oxides like pirolusite and phous carbonaceous matters like charcoal or soot can be criptomelano has been identified (Chalmin et al. 2006). made by firing organic substances including wood or bone If we move to post-Palaeolithic art, and more specifically (Coccato et  al. 2015). Manganese oxides/hydroxides are to Spanish Levantine rock art, amorphous carbon from veg- naturally occurring minerals present in soil and sediments. etal origin occurred more frequently than manganese-based They are frequently found as coatings on rocks and nodules. pigments (Fig. 7) (Domingo et al. 2021). While the num- According to the chemical composition, valence states of ber of sites with black pigments analyzed is still low, this the manganese metal (II, III, IV or mixed) and crystalline preliminary finding could suggest a better access to vegetal structure, more than 20 different mineralogical varieties can organic matters to be charred and employed as pictorial be distinguished among them. They can be divided into two material, than to manganese sources (Domingo et al. 2021). main families based on the presence or absence of additional Something similar happens with black pigments in Latin foreign cation (Chalmin et al. 2008). Manganite MnOOH, America where charcoal has been detected randomly in all pyrolusite MnO , bixbyite Mn O , hausmannite Mn O and, prehistoric cultures (Sepúlveda 2021). This does not mean 2 2 3 3 4 on the other hand, romanechite Ba Mn O ‧xH O, hollandite that the prehistoric Levantine painters were not ingenious in 2 5 10 2 BaMn O ‧xH O represent some of the most recurring min- finding their raw materials. For example, at the Los Chapar - 8 16 2 erals taking part of such two categories, respectively. They ros site (Albalate del Arzobispo, Spain), pigment analysis can be found in a large variety of natural settings, also in the revealed the use of manganese oxides/hydroxides, whose mixture, and in the form of wads, a general term to describe precise mineral nature was not exactly characterized due to dark brown to black coloured earth pigments and materi- the low crystallinity of the analyzed compounds, as black als in which manganese oxide/hydroxide are contained ca. pigment. Similarities between the analyses of the Levantine 50% (Siddal 2018). In Western European Palaeolithic rock pigment and a dendrite mineralization located close to the art, the use of both types of black pigments is equable in rock art site suggest local procurement strategies (Pitarch both French and Spanish sites. In fact, there is no system- et al. 2014). atic prevalence of the use of the organic black with respect Driven by the same motivations that led archaeologists to the inorganic one, even the former was used mainly for and scientists to deeply study the goethite-haematite thermal drawing outlines. In some sites, both are present (Menu and transformation system, also manganese oxides/hydroxides Walter 1992; Chalmin et al. 2003, 2006; Vignaud et al. 2006; have been highly examined under heat treatment to compre- Menu 2009; de Balbín Behrmann and Alcolea González hend their transformation mechanisms and to gain insights 2009; Gay et al. 2020). For instance, in Ekain Cave (Basque into black pigment processing technologies during the Pal- Country, Spain), dating to the Magdalenian culture, black is aeolithic. In fact, some analytical studies and archaeological the dominant colour and charcoal is the primary black pig- findings suggested to archaeologists a possible use of heated ment used to create the famous horses (Chalmin et al. 2003). black pigments by prehistoric artists (Smith et  al. 1999; Only two uncommon figures, one horse and two bears, have Guineau et al. 2001; Chalmin et al. 2008). Thus, despite the been painted with manganese oxide. This uncommon use, absence of any colour change in the black pigments, it was compared to the other paintings, suggested to archaeologists supposed that the calcination could potentially induce modi- that this pigment was precious or symbolic. On the contrary, fications of the microstructural features, such as dehydra- in Lascaux (Dordogne, France), only manganese black pig- tion, a loss in the cohesion of the matter, facilitating grind- ments with different mineral nature have been identified in ing (Guineau et al. 2001; Chalmin et al. 2008). To verify the black figures. Their mineral composition is similar to that these assumptions, Emily Chalmin and coworkers studied of several black crayons found next to the cave walls (Chal- the thermal transformation of manganese oxides/hydroxides min et al. 2003, 2004a, b). Similarly, in the Great Ceiling at systems both in artificial and several archaeological sam- Rouffignac Cave (Dordogne, France), at least three different ples. They found an analytical protocol to follow in order to types of barium-bearing manganese oxides (that could be recognize the application of heat treatment to this kind of assimilated to different black raw colouring materials) were black pigments using scanning electron microscopy com- used. Meanwhile, only charcoal has been detected in the bined with energy-dispersive X-ray analysis (SEM–EDX), black samples belonging to Grande Grotte of Arcy-sur-Cure X-ray diffraction (XRD), transmission electron microscopy (Yonne, France) or Altamira (Cantabria, Pain) (de Balbín (TEM) and X-ray absorption near edge structure (XANES) 1 3 Archaeol Anthropol Sci (2021) 13:196 Page 11 of 20 196 to minimize damaging the paintings, in Western European Palaeolithic caves, both French and Spanish researchers have focused on determining the age of spectacular rock paintings by dating charcoal pigments, obtaining more than a hundred dates so far (Steelman and Rowe 2012; Ochoa et al. 2021). Standard procedures have been adopted for dating archaeo- logical charcoal, using acid to remove carbonates and com- bustion to collect carbon for AMS C dating. Most dates obtained on pictographs worldwide have been on charcoal pigmented paintings. There are about 150 publications on dating charcoal pigment in rock art that involve at least six laboratories (Rowe 2012), providing variable and sometimes contested results (Ochoa et al. 2021). A balance between the need to date the art and the impact of such actions should be found since while sampling large paintings like the ones found in Palaeolithic art may cause only small scars to the charcoal drawings, dating much smaller Levantine paintings may result in the destruction of a large part of the motifs to obtain enough matter for dating. Fig. 7 Black Levantine deer from coves de la Saltadora IX (Cas- tellón, Spain) painted with manganese-based pigment Yellow pigments (Chalmin et al. 2003, 2004a, b, 2006, 2008). In particular, The prehistoric yellow pigments are usually characterized manganese oxides/hydroxides can undergo a series of suc- by yellow ochres (see Red pigments for the definition of cessive phase transformations involving oxidation/dehydra- ochres and earth pigments) whose brownish-yellow typi- tion/reduction reactions depending on the heating tempera- cal colour is due to the presence of goethite (α-FeOOH), ture and on the specific nature of the original mineral. As an iron (III) oxide-hydroxide natural occurring mineral, an example, at 360 °C, the monoclinic manganite (MnOOH) as the main chromophore. Similar to what happens for the phase is transformed into tetragonal pyrolusite (MnO ) by use of haematite and red ochres, the use of goethite and oxidation and dehydration. At 560  °C, this pyrolusite is goethite-rich materials is common to all prehistoric tradi- reduced as well into cubic bixbyite (Mn O ); at the end, tions worldwide to create yellow paintings. However, they 2 3 bixbyite is transformed into tetragonal hausmannite (Mn O ) are uncommon in works of art prior to the Late Neolithic 3 4 at 950 °C and so on (Chalmin et al. 2004a, b, 2008). Two (Siddal 2018). Regarding Western European Palaeolithic different protocols have been defined depending on the rock art, according to Menu (2009), about 1% of the paint- presence or not of foreign cations in the manganese-based ings were completed with yellow or brown colour, some of mineral, based on the evaluation of specific morphological, which are displayed on the Lascaux site. In this case, they chemical and structural criteria to be followed during the are based on yellow ochre (Chalmin et al. 2006; Vignaud changes induced by heating. The complete description of et al. 2006; Menu 2009; de Balbín Behrmann and Alcolea all heating patterns that could occur to manganese oxides/ González 2009). Moreover, in some works from the end hydroxides when calcined is well summarized in Chalmin of the Magdalenian, jarosite, a basic hydrous sulphate of et al. (2008). From their results, they concluded that not potassium and iron KFe (SO ) (OH) , has been also found 3 4 2 6 heating treatment had been applied to any of the various sporadically. Jarosite is a beautiful yellow mineral, quite black Mn-based pigments they studied from the paintings rare, available in Ariège near caves (Menu 2009). Jarosite of various prehistoric sites such as Lascaux, Ekain, Gargas, has been also detected in several prehistoric yellow figures Labastide, Combe Sauniere and Roucador (Chalmin et al. from Latin America (Sepúlveda 2021). Furthermore, while 2003, 2004a,b, 2006, 2008). it is not specifically rock art, it is important to mention the Finally, to rock art research, the identification of carbon- unique collection of Palaeolithic painted portable art coming based organic pigments is of special interest since it opens from Parpalló Cave, (Gandía, Spain), one of the most impor- the way for radiocarbon dating. Dating rock art is one of the tant Palaeolithic sites in the Spanish Mediterranean region. major challenges faced by archaeologists, and it is absolutely With over 5600 decorated plaquettes, this unique site has necessary to place the art in the cultural context (Steelman provided a reference collection for the study of the Palaeo- and Rowe 2012; Ochoa et al. 2021). Not without techni- lithic art in Europe since it covers the entire archaeological cal difficulties and strict protocols to be followed in order sequence from the Gravettian to the Magdalenian periods 1 3 196 Page 12 of 20 Archaeol Anthropol Sci (2021) 13:196 (32–14,000 cal. BP). The plaquettes are characterized by compounds used for the creation of white paintings (Stuart zoomorphic and sign depictions and, in addition to the pre- and Thomas 2017; Chalmin and Huntley 2017; Gallinaro and dictable use of red and black pigments, a large amount of Zerboni 2021; Sepúlveda 2021). Interesting is also the use of those are painted with yellow materials, identified as yellow calcined bones in Argentina (Wainaright et al. 2002). ochres (Roldan et al. 2016). White pigments Prehistoric paints (binders, recipes and application techniques) The occurring of white colour in Western and Mediterra- nean European prehistoric rock art is not frequent. Prehis- In prehistoric times, the production of the artworks required toric European artists did not commonly employ white pig- significant advanced planning to collect the raw materials ments or at least they have not been as well preserved as used to prepare the sourcing, processing and application red and black paintings. Both ethnography and archaeology tools, the crayons and the paints necessary to create paint- have emphasized the problematic conservation of white pig- ings. The complexities of this process and the amount of ments, which may be providing a wrong picture of the col- time invested by prehistoric artists demonstrate that they our preferences of prehistoric artists (e.g. Chaloupka 1993; were not based on improvisation (Fiore 2007). The range of Chippindale and Taçon 1998; Domingo 2005; Domingo et al. mineral and organic pigments described above were used in 2018). During the Palaeolithic, white paintings have been prehistoric times either for dry use (as crayons) to produce only found once on a negative hand in the Gargas Cave, in drawings (with astonishing examples in places like the sites the Pyrenees, consisting of talc (Mg Si O (OH) ) and clay of Chauvet or Ekain, to name a few) or as the bases to pro- 3 4 10 2 (Menu 2009). Later on, during the post-Palaeolithic, and duce paint for their monochromatic and polychromatic crea- more specifically within the Levantine rock art context, a few tions (like the famous polychrome bisons of Altamira Cave). examples demonstrate a minor use of white pigment to pro- In this case, the raw pigments were finely ground, sometimes duce both monochrome and bichrome paintings (Domingo even sieved and finally mixed with a liquid medium (vehicle) et al. 2021). Hernanz et al. (2008) analyzed a bicolour bull and other additives and natural binding substances (animal composed of red and white brushstrokes in the Marmalo IV fat or plant extracts) to facilitate adherence. Different granu- shelter of Sierra de las Cuerdas (Cuenca). Compounds like lometries reflect the quality of the grinding and/or sieving α-quartz (α-SiO ), anatase (T iO ), apatite (Ca (PO ) ), mus- process and the skills of the artists (Hernanz et al. 2008). 2 2 5 4 3 covite (KAl (Si Al)O (OH,F) ), gypsum (CaSO ·2H O) While little archaeological information on binders is 2 3 10 2 4 2 and illite ((K,H O)(Al,Mg,Fe) (Si,Al) O [(OH) ,(H O) available, ethnoarchaeology demonstrates that the use of 3 2 4 10 2 2 ]) were detected in the white lines of the painted figure. In binding agents such as honey, plant resin, natural wax, ani- particular, the white traces in the composition of the painted mal fat, blood and others (Ravenscroft 1985) is necessary animal seem to enhance the perception of the muscles of the for the art to survive, especially in the open air, since paint- red bull. Microstratigraphic studies revealed that the white ings produced without binders disappear in a few years or layer was superimposed to the red one. A similar use of the decades depending on their exposure (Domingo et al. 2018). white pigment for highlighting and emphasizing details of Today, the problematic identification of these substances painted figures had been found in other rock art sites of the is most likely related to the low residual amount of their Valltorta-Gasulla complex (Civil and Centelles sites), again constituent organic macromolecules (carbohydrates, lipids, employed to underline details and adornments in human fig- proteins as main classes and their residuals) in the pictorial ures (Domingo 2005; Domingo et al. 2021). Furthermore, paints due to their chemical transformations caused by their another example of white painting found in the Iberia pen- aging and degradation as well as to the intrinsic limits and insula is located at the rock-art shelter Abrigo del Águila technical constrains of the experimental techniques used (Badajoz), belonging to Iberian Schematic rock art tradition so far for identification purposes (Domingo et al. 2021 ). (Rosina et al. 2018). The micro-Raman analyses pointed out Moreover, the potential carbohydrates, lipids and proteins the presence of anatase and the authors assumed that the that could have been used as binders in prehistoric times white figures could have been made using minerals from the are also some of the nutrients used by microorganism (like illite-kaolinite group. Moving from European borders, white fungi, bacteria, lichens and so on) for growth and they could pigments are most frequently found in prehistoric rock art be fixed as calcium oxalates at the end of the feeding actions coming from other parts of the world, like in Australian, Afri- (Rampazzi 2019; Domingo et al. 2021). Thus, should any can and American rock art creations. In particular, kaolinite residual amounts be left, the detection would be challenging (Al Si O (OH) ), huntite (CaMg (CO ) ), quartz (α-SiO ), (Spades and Russ 2005). 2 2 5 4 3 3 4 2 gypsum (CaSO ·2H O), calcite (CaC O ), and calcium The use of lipid binders was detected at various Palaeo- 4 2 3 oxalates (CaC O ·(H O) ) are some of the most detected lithic sites, such as Fontanet, Enlène and Les Trois Frères, 2 2 2 x 1 3 Archaeol Anthropol Sci (2021) 13:196 Page 13 of 20 196 (Pepe et al. 1991). At some sites of different chronologies, the dangers of making direct assumptions such as this since the these organic binders were interpreted as consistent with ani- use of milk as a binder has been also detected among hunter- mal fats, including for example the Palaeolithic sites of Tito gatherer communities living in South Africa 49,000 years ago Bustillo (Navarro and Gómez 2003), some Levantine paintings (Vila et 2015). Moreover, as the authors of la Saltadora study of la Saltadora site (Roldan et al. 2018) or the more recent art say (Roldán et al. 2018), there is still no direct evidence that of the dolmen of Dombate, where the use of milk fat and but- the detected casein is not a ubiquitous contemporary contami- ter was suggested (Bello and Carrera 1997). Further examples nant since it has been identified both in un/pigmented areas so have been also reported in other regions around the world (e.g. more scientific efforts have to be spent to resolve this question. Boschín et al. 2002; Prinsloo et al. 2008; Moya et al. 2016; Among other uses, milk and casein have been also documented Brook et al. 2018). Nevertheless, attention should be paid in cultural heritage studies as a fixative or stabilizing agent to whether organic molecules identified today are really of in different kinds of more recent painted and stone artworks prehistoric origin. For example, fatty acids, among the main (Chamberly et al. 2009; Snethlage and Sterflinger 2011). constituent of lipids, have been identified equally both in the The use of blood as an agent has not been detected in any paint and in natural rock coating, composed mainly by calcium European site, and it is rare in other regions, with only a few oxalate and to a lesser extent by gypsum and clays, in micro- references from Australian (Loy et al. 1990) and African samples from the Lower Pecos Region of southwestern Texas sites (Lewis-Williams 1994: 281; Williamson 2000). Fibres (Spades and Russ, 2005). The authors attributed such con- and plant extracts have been also suggested as potential tents to microbial activity on the rock surfaces due to lichens, binders in Australia (Watchman and Cole 1993) and South bacteria and others that naturally live on the rock surface and America (Boschín et al. 2002). they indicated that fats or oils were either not used to prepare Other inorganic additives intentionally added to pre- the paints or that if such binders were used, they had already historic paintings include clays (e.g. Baffier et  al. 1999; degraded when analyzed by gas chromatography–mass spec- Hernanz et  al. 2008; Hamenau et  al. 1995); quartz (like trometry (GC–MS). Thus, the presence of this kind of accre- in Lascaux, Clottes 1997); quartz and amber in Altamira tions commonly correlated to the paints and often fossilized on (Groenen, 2000); K-feldspar at La Vache, Salón Noir de them could create misleading interpretations when investigat- Niaux and de Fontane (Clottes, 1997); quartz and K-feldspar ing organic molecules. Not only patinas, but also the analyses in Arenaza (Garate et al. 2004); talc in some Schematic art of raw ochres collected close to several rock art sites in Aus- sites (Hameau et al. 2001) and mixed with biotite in Niaux tralia showed a high amount of organic matter in the pigments (Clottes, 1997), burned bones in Western European Palaeo- themselves, such as lichens and bacteria (Ridges et al. 2000). lithic (de Balbín Behrmann and Alcolea González 2009), Thus, the identification of biological molecules such as lipids Levantine (Hernanz et  al. 2008) and Schematic art (e.g. and proteins, on the rock art pictographs, has to be carefully Hameau et al. 2001). This variety of additives, often used considered since they could also belong to the microorganisms to obtain different colour hues or textures, has been used to living on rock surfaces, coatings and pigments, like lichens talk about the preparation of different paint recipes in Pal- (García et al. 2001), bacteria (Roldan et al. 2018), fungi and aeolithic times (Menu and Walter, 1996; Baffier et al. 1999; algae. Thus, they cannot be immediately attributed to origi- Hameau et al. 2001; Chalmin et al. 2003; Garate et al. 2004, nal binders used to produce prehistoric paint (Hernanz 2015). among others), reflecting elaborated technologies and dif- This issue has to be also taken into account when considering ferent cultural choices in paint preparation. The degree of radiocarbon dating rock painting samples (Bednarik 2002) paint homogeneity of the rock art panels or sites may pro- since organic matter from the natural occurring environment vide information for discussing the completion times of the is undistinguishable from that coming from organic materials artworks. For instance, Garate et al. (2004) deduce that the used as part of the prehistoric paints or binders. Another exam- paintings of Arenaza result from a single intervention based ple regarding proteinaceous binders is found at la Saltadora site on the consistency of the paints used, while Groenen (2000) in Spain, where the presence of casein peptides of animal ori- suggests that the production of the hand stencils from Gargas gin has been identified on both pigmented and non-pigmented stretched over a period of time considering the variety of areas by proteomic approaches, as described by Roldán et al. recipes detected. (2018). The presence of casein in Levantine pigments suggests Once the pictorial mixture was ready and depending on the authors the use of milk as binding media. If finally proven, the period and region, the paint was applied using a variety these results would be highly interesting from the archaeologi- of techniques. For example, European Palaeolithic artists cal point of view, and more specifically for the chrono-cultural used different types of brushes and pads, hands and fingers debates surrounding the authorship of Levantine paintings, and the blow painting techniques (i.e. blowing the paint since the use of milk could be interpreted as a conr fi mation directly from the mouth or through hollow tubes), while that it was created by farming communities and not by the last Levantine artists only used a variety of brushes, as deduced hunter-gatherers. Nonetheless, another recent finding warns of from the fine strokes characteristic of this tradition (Menu 1 3 196 Page 14 of 20 Archaeol Anthropol Sci (2021) 13:196 2009; D’Errico et al. 2016). The nature of the brushes is of production seems to be strongly influenced by cultural unknown, though, since they are not preserved in the archae- decisions and choices, traditions and probably even beliefs. ological record (Domingo 2020). Physico-chemical analyses have also potential as a tool to identify whether pigment remains located on the walls of caves and rock shelters are natural formations or inten- Conclusions tionally produced by humans, and also as an authentication tool to confirm whether any new finds are truly prehistoric The systematic application of scientific analyses from differ - (Garate et al. 2004), even though subject to certain limits ent disciplines (physics, chemistry, mineralogy, petrography, (García et al. 2001). geology and biology) to the study of prehistoric pigments Furthermore, physico-chemical approaches are also and paints have improved the way prehistoric art and colours important to advance knowledge on pigment conservation, are analyzed and understood today, allowing the discovery of interest to understand how the art has survived, predict the of multiple uses of different raw materials with colouring long-term behaviour of pigments and bedrocks and identify properties in prehistoric times and expanding the frontiers potential risks. They are also crucial to develop best conser- of archaeological knowledge on one of the most fascinating vation practices and protocols, giving careful consideration legacies of the past: rock art. to the fact that any materials introduced (modern pigments As discussed in this paper, building a systematic knowl- used to tone areas of bedrock loss, materials for consolida- edge about the raw materials and their potential sources, tion and so forth) or removed (crusts) in any conservation the techniques, instruments and processes involved in the interventions could impact archaeological approaches to past production of prehistoric art and exploring their patterns pigments, paints, technologies and practices. of change over space and time are questions of interest to Today the range of portable non-invasive spectroscopic archaeological research to gain information on the palette, techniques available to archaeologists has been a push for the the technologies and the socio-cultural practices of ancient scientific analysis of prehistoric art and pigments, minimizing artists as well as on aspects of social dynamics and produc- impacts on this unique and fragile heritage. They have opened tive processes. Such an approach is showing that while the up new opportunities for direct on-site analysis, enabling the amount of minerals and colours used in prehistoric art is application of new analytical research approaches to the study limited, the patterns of production of different regions or of rock art and providing guidance to avoid or at least mini- periods are different, demonstrating that the exploration of mize the need to resort to sampling and the use of invasive the non-visual aspects of the art offers new avenues to track analytical methods (whether non-destructive or destructive). past social identities (see for example Vergara and Troncoso, While sampling is still necessary, portable non-invasive meth- 2015). As Gosselain (1992) states, the visual aspects of the ods allow us to perform more targeted sampling, which should artefacts (in rock art, variations in form and subject matter) only be performed as a last resort when no other non-invasive can be easily replicated, while non-visual aspects (or those techniques can answer our research questions. This sampling that we will have to explore through archaeometry, such as strategy reduces potential impacts on the art. the nature of the raw materials used and the transformation What is clear from this review is the importance of mul- practices, pigments recipes and so forth) are more difficult titechnical and multistep multidisciplinary approaches in to copy, thus providing more opportunities to explore the studying prehistoric pigments and paints to gain a more more stables aspects of social identities (Domingo and Fiore, comprehensive understanding of the many uses of these 2014). particular archaeological remains and the many aspects of As debated along this paper, and broadly speaking, while past cultures they can shed new light on. We are confident prehistoric humans were constraint by a limited number of that in the next few years, continued technological advances raw materials available in nature (mainly 4 colours—red, in analytical techniques will improve our approaches to rock black, yellow and white—were used all around the globe), art, opening new avenues of research now still unthinkable. analytical approaches are demonstrating certain variability in different steps of paint production (raw materials used, Author contributions Both authors contributed equally to this work. grain sizes, recipes, etc.) and application between different traditions. These variations do not simply result from envi- Funding This research has been supported by several research grants ronmental constraints, such as the availability of certain raw directed by Inés Domingo: HAR2016-80693-P funded by the Spanish materials and no others since the absence of local supplies Ministry of Science, Innovation and Universities and the ERC-CoG LArcHer project, funded by the European Research Council (ERC) was solved through different strategies, such as long-distance under the European Union’s Horizon 2020 research and innovation procurement or the development of exchange networks. Thus, programme (grant agreement No 819404). the variability observed in the different steps of the process 1 3 Archaeol Anthropol Sci (2021) 13:196 Page 15 of 20 196 Data availability Not applicable. Beck L, Genty D, Lahlil S, Lebon M, Tereygeol F, Vignaud C, Reiche I, Lambert E, Valladas H, Kaltnecker E, Plassard F, Menu M, Paillet P (2013) Non-destructive portable analytical techniques Code availability Not applicable. for carbon in situ screening before sampling for dating prehistoric rock paintings. Radiocarbon 55(2–3):436–444 Declaration Beck L, Rousselière H, Castaing J, Duran A, Lebon M, Moignard B, Plassard F (2014) First use of portable system coupling X-ray dif- Competing interests The authors declare no competing interests. fraction and X-ray fluorescence for in-situ analysis of prehistoric rock art. Talanta 129:459–464 Open Access This article is licensed under a Creative Commons Attri- Becker H (2021) Pigment nomenclature in the ancient Near East, bution 4.0 International License, which permits use, sharing, adapta- Greece, and Rome. Archaeol Anthropol Sci. https:// doi. org/ 10. tion, distribution and reproduction in any medium or format, as long 1007/ s12520- 021- 01394-1 as you give appropriate credit to the original author(s) and the source, Bednarik R G (2002) The Dating of Rock Art: a Critique. J Archaeol provide a link to the Creative Commons licence, and indicate if changes Sci 29:1213–1233Bello J Mª, Carrera F (1997) Las pinturas were made. The images or other third party material in this article are del monumento megalítico de Dombate: estilo, técnica y com- included in the article's Creative Commons licence, unless indicated posición. In: Rodríguez A (ed.) O neolítico atlántico e as orixes otherwise in a credit line to the material. If material is not included in do megalitismo: Actas do Coloquio Internacional (Santiago de the article's Creative Commons licence and your intended use is not Compostela, 1–6 de Abril de 1996). 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Journal

Archaeological and Anthropological SciencesSpringer Journals

Published: Nov 1, 2021

Keywords: Prehistoric art; Analytical chemistry; Pigments; Paints; Binders

References