heritage

Review A Review on Historical Earth Pigments Used in India’s Wall Paintings

Anjali Sharma 1 and Manager Rajdeo Singh 2,*

1 Department of Conservation, National Museum Institute, Janpath, New Delhi 110011, India; [email protected] 2 National Research Laboratory for the Conservation of Cultural Property, Aliganj, Lucknow 226024, India * Correspondence: [email protected]

Abstract: Iron-containing earth minerals of various hues were the earliest pigments of the prehistoric artists who dwelled in caves. Being a prominent part of human expression through art, nature- derived pigments have been used in continuum through ages until now. Studies reveal that the primitive artist stored or used his pigments as color cakes made out of skin or reeds. Although records to help understand the technical details of Indian painting in the early periodare scanty, there is a certain amount of material from which some idea may be gained regarding the methods used by the artists to obtain their results. Considering Indian wall paintings, the most widely used earth pigments include red, yellow, and green ochres, making it fairly easy for the modern era scientific conservators and researchers to study them. The present knowledge on material sources given in the literature is limited and deficient as of now, hence the present work attempts to elucidate the range of earth pigments encountered in Indian wall paintings and the scientific studies and characterization by analytical techniques that form the knowledge background on the topic. Studies



 leadingto well-founded knowledge on pigments can contribute towards the safeguarding of Indian cultural heritage as well as spread awareness among conservators, restorers, and scholars. Citation: Sharma, A.; Singh, M.R. A Review on Historical Earth Pigments Keywords: red ochre; green earth; black earth; yellow ochre; pigments; wall painting Used in India’s Wall Paintings. Heritage 2021, 4, 1970–1994. https:// doi.org/10.3390/heritage4030112 1. Introduction Academic Editors: Diego Tamburini and Francesco Paolo Romano Since time immemorial, wall paintings have been done in almost all countries. Paint- ings of all kinds, encompassing all types of wall paintings as well, are a valuable part of Received: 17 June 2021 many countries’ cultural heritage. In prehistoric paintings, the artistic style was primitive, Accepted: 23 August 2021 and the techniques were also very basic, with the paint being applied directly onto the Published: 26 August 2021 rock surface. As a result of this, the pigments seep through the pores and coarse surface of rocks. Later, more complex designs and figures were painted on walls, which were often Publisher’s Note: MDPI stays neutral prepared with several layers of plaster [1]. with regard to jurisdictional claims in The uses and evidence of earth pigments in the India begin with the hematite and published maps and institutional affil- quartz crystals found in the Acheulian deposits of the Lower Paleolithic period. One such iations. hematite specimen was discovered in the exposed floor of Hunsgi (Karnataka), locality V, and has a worn facet with characteristic striation patterns, indicating that it was used as a crayon to color or mark a rock surface [2]. Because this material does not occur in its natural state in the area surrounding the site, the site excavators believed that these Copyright: © 2021 by the authors. little hematite nodules were brought-in from afar. Paddaya goes on to say that these Licensee MDPI, Basel, Switzerland. red ochre nodules were probably also utilized for body ornamentation and other similar This article is an open access article purposes [3]. Six other tiny quartz crystals were discovered from the base of the lower distributed under the terms and Paleolithic deposit at Singi Talav (Rajasthan), which was interesting evidence. They were conditions of the Creative Commons virtually fully unchanged and measured 7–25 mm in length, making them too small to Attribution (CC BY) license (https:// have been employed as tools. They had been purposefully transported to the site, as had creativecommons.org/licenses/by/ the Hunsgi hematite nodules, and were collected for their visual attributes [4]. Although 4.0/).

Heritage 2021, 4, 1970–1994. https://doi.org/10.3390/heritage4030112 https://www.mdpi.com/journal/heritage Heritage2021, 4 FOR PEER REVIEW 2

Heritage 2021, 4 1971

collected for their visual attributes [4]. Although these are only inferences, it is impossible to theserule out are the only possibility inferences, of ita functioning is impossible reality to rule involving out the possibilityan aesthetic of sense a functioning among our reality fore- involvingfathers. an aesthetic sense among our forefathers. AccordingAccording toto Wakankar,Wakankar, some some of of the the earliest earliest depictions depictions in in Mesolithic Mesolithic rockrock paintings paintings paintedpainted inin greengreen colorcolor couldcould bebe thosethose belongingbelonging toto thethe upperupper PaleolithicPaleolithic eraera ofof IndianIndian antiquity.antiquity. The The discovery discovery of of green green earth earth (what (what he he refers refers toas to terra as terra verte) verte) in upper in upper Paleolithic Paleo- depositslithic deposits in one in of one the excavatedof the excavated rock shelters rock shelters (III A-28) (III atA-28) Bhimbetka at Bhimbetka [5] could [5]could be the be basis the forbasis this for hypothesis. this hypothesis. The chronological The chronological position inposition time of in the time green of paintings, the green however, paintings, is ahowever, point of contention.is a point of Greencontention. pigments Green were pigments discovered were first,discovered followed first, by followed red paintings, by red accordingpaintings, toaccording some scholars to some [6]. Wakankarscholars [6]. also Wakankar discovered also yellow discovered ochre, manganese, yellow ochre, and terramanganese, verte in and Bhimbetka’s terra verte shelter in Bhimbetka’s III A-28 in shel 1975,ter where III A-28 these in 1975, pigments where were these observed pigments to bewere smeared observed on multiple to be smeared areas in on the multiple shelter IIIareas F-23 in [ 2the,7,8 shelter]. These III early F-23 paintings [2,7,8]. These represent early thepaintings beginning represent of known the beginning or surviving of known rock art or in surviving India because rock art of thein India quality because of pigment of the applicationsquality of pigment in the form applications of fine and in controlled the formlines. of fine According and controlled to Mishra, lines. for theAccording paintings to atMishra, Bhimbetka, for the apart paintings from being at Bhimbetka,apart executed in red orfrom white, being bluish-green executed andin red yellowish or white, colors blu- hadish-green also been andused yellowish on occasions. colors had Since also they been were used only on preserved occasions. in Since fragments they were and were only foundpreserved at the in bottom fragments of the and paint were layer; found green at the painted bottom layers of the tend paint to belayer; the oldest.green painted Many shadeslayers tend of red to werebe the visible, oldest. rangingMany shades from of scarlet red were to pale visible, red toranging dark chocolate.from scarlet Natural to pale mineralsred to dark were chocolate. used to makeNatural these minerals pigments were [2 used,9] to make these pigments [2,9] TheThe largestlargest concentrationconcentration ofof prehistoricprehistoric sitessites andand rockrock paintingspaintings areare foundfound inin CentralCentral India’sIndia’s sandstonesandstone regions,regions, whichwhich spanspan threethree distinctdistinct mountainmountain systems:systems: thethe VindhyachalVindhyachal andand SatpuraSatpura inin MadhyaMadhya Pradesh,Pradesh, Chhattisgarh,Chhattisgarh, andand aa portionportion ofof UttarUttar PradeshPradesh andand thethe AravalliAravalli in Rajasthan. In In all all more more than than a thou a thousandsand rock-shelters rock-shelters with with paintings paintings have have been beenexplored explored and studied and studied by archeologists. by archeologists. It is interesting It is interesting to note that to prehistoric note that paintings prehistoric in paintingsIndia were in first India noticed were first12 years noticed earlier 12 years than earlierthe famous than discovery the famous of discovery the cave paintings of the cave of paintingsAltamira of(Spain). Altamira This (Spain). was done This by was Archib doneald by Carllyle, Archibald a superintendent Carllyle, a superintendent of the Archaeo- of thelogical Archaeological Survey of India Survey (ASI) of Indiain 1867, (ASI) in inthe 1867, Mirzapur in the area Mirzapur of the areathen of United the then Provinces. United Provinces.Like Marcelino Like de Marcelino Santuola, de through Santuola, discovery through of discovery Altamira ofin Altamira1879, Carllyle in 1879, was Carllyle the first wasscholar the to first attribute scholar these to attribute paintings these to the paintings Stone-Age to period. the Stone-Age Some of period.the prominent Some sites of the in prominentIndia with sitesshelters in Indiacontaining with sheltersprehistoric containing paintings prehistoric are Panchmari paintings in the are Mahadeo Panchmari Hillsin of theMadhya Mahadeo Pradesh, Hills Adamgarph, of Madhya Pradesh, Raisen, Mirzapur Adamgarph,, etc. Raisen, Mirzapur Mirzapur, has evidence etc. Mirzapur dating from has evidencethe Lower dating Palaeolithic from the to Lowerthe Mesolithic Palaeolithic period tos, the and Mesolithic was a major periods, center and of wasrock apainted major centershelters of in rock Uttar painted Pradesh shelters [2,10–13]. in Uttar Figure Pradesh 1 shows [2 a,10 list–13 of]. most Figure famous1 shows wall a painting list of most sites famousin India. wall painting sites in India.

FigureFigure 1.1. LocationLocation ofof mostmost famousfamous muralmural paintingspaintings inin India.India.

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Wall paintings are exposed to a wide range of climatic conditions due to their location in many large and small geographical regions throughout the country [1]. They were executed on the rock surface, making use of the natural porosity of the rock exterior to secure the colors. The pigment was most likely powdered using a mortar and pestle or within natural depressions of rocks, combined with water, and applied with twig brushes. To remove the pulp and reveal the fibers, one end of the twig is pounded. It has been believed that palmetto twigs were most likely chosen since they are known to be the best among other materials. Considering sandstone shelters, when painting them, the pigment seeps into the porous rock surface and becomes permanently embedded in it, making it impossible to remove, even when washed. Only natural weathering of the granite surface can cause the paintings to deteriorate. It is believed that transparent and opaque color techniques were widely used to rock surfaces. It is a more relied upon technique than the stencil technique, which is traditionally used to make negative handprints. In the transparent color technique, the colors used were heavily diluted in water, except for the emerald green and white colors. For the first time, man-made mud brick structureswere observed during the Neolithic period around 6000 B.C.E where the structures were made by laying a smooth layer of fine mud plaster over a brick wall. Simultaneously, the need for a binding material, such as glue or gum, to set the color onto the smooth mud base became a necessity. As painting techniques developed, first of all a plaster layer was applied on the wall which was later painted upon [14,15]. Tempera has been the mainstay of Indian wall painting for centuries. The basic feature of this technique is the use of a binding medium for emulsifying the pigment in gum Arabic, animal glue, egg yolk, etc., which achieve the adhesion between the pigments and the dry background [14]. The paintings in southern India were mostly executed according to the tempera technique where walls were prepared with mud plaster or rock cuts as late as 6–7th C.E. century, such as Ajanta, cave no. 10. The Buddhist paintings in Bagh (Madhya Pradesh) executed in a similar technique immediately follow the Ajanta period. Some wall paintings in monuments and temples in South India were regarded be executed in lime medium (secco) by Paramasivan. The secco technique is done on dry lime plaster. The pigments are mixed with lime water, sometimes with the addition of a little skimmed milk. Some examples of secco paintings are Sitannavasal, Pallava paintings in Kaliasanatha temple, Kanchipuram, and Lepaskhi [1]. The art of wall painting in Rajasthan evolved into what is known as Rajasthani style after the 17th century C.E. The Indian painters elaborately prepared lime plaster which was laid on walls in several thin layers, each well compacted to a total thickness of a quarter to a half inch to cover crevices and joints. This was overlaid with thin lime plaster and again a specially prepared milk of lime of was applied to the wet wall. Several coats were applied, followed by rubbing with a stone each time. The final application was done with the milk of lime followed by polishing the surface with an agate stone to produce a smooth glaze that later received the pigments prepared in water with a gum medium and occasionally glue in the case of certain pigments, especially black. There are several notable paintings which were executed using the Rajasthani style such as Badal Mahal (Nagaur Fort), Lal Baba Temple (Jodhpur), and Amer Palace (Jaipur) [1,16]. The uses of earth pigments in India’s painted works has continued since prehistoric times. Because of their high coloring potential and stability under a variety of environmen- tal conditions, light, oxidation, and corrosion, these painting materials have been widely used [17]. Earth pigments can be used in almost any architectural background for the execution of wall paintings. Iron-rich ochres, green earth, wads (manganese-rich ochres), white earth (calcite, kaolinite, and gypsum), umbers, and vivianite-rich blue earth are the broad categories which are combinations of several chromophore minerals as well as accessory phases such as carbonates, clays, and quartz, rather than pure, single mineral colors. As deposits on the Earth’s surface, they would have been both evident and desired sources of pigment, and it is this category of pigments that is most essential in the evolution of prehistoric art [18]. Table1 listed earth pigments used in India’s wall paintings. A detailed explanation of earth pigments will be provided further as a separate section below. Heritage 2021, 4 1973

Table 1. Chronological development of pigment used in Indian mural painting with techniques.

Earth Pigment Color Name of Pigment Chemical Formula Red Red Ochre α-Fe O Ochre 2 3 Purplish red Indian Red Fe2O3

Yellow Yellow ochre Fe2O3·H2O or α-FeO(OH)

Brown or Reddish brown Umber Fe2O3·(H2O)+MnO2·(nH2O)+Al2O3

Yellow-brown Sienna Fe2O3+MnO2 3+ 2+ Celadonite K[(Al,Fe ),(Fe ,Mg)](AlSi3,Si4)O10(OH)2 Green earth Green 3+ Glauconite (K,Na)(Fe ,Al,Mg)2(Si,Al)4O10(OH)2

Calcite CaCO3 White earth White Gypsum CaSO4·2H2O Kaolinite Al2[Si2O5][OH]

Wade Black Manganese ochre (Pyrolusite) MnO2 2+ Blue Earths Blue Vivianite Fe3 [PO4]2·8H2O

The objectives of this paper include an overview on the uses of earth pigments in Indian wall paintings and their analysis and information. As human imagination has no limit when considering materiality and invention, the task at hand become arduous. The paper will also focus on wall paintings technique, scientific examination of pigments and will individually elucidate on earth pigments.

2. Earth Pigments The term “earth pigments” refers to inorganic, naturally occurring mineral pigments that are employed as colorants. Earth pigments can be separated into non-clay pigments and pigments with the chromophore element contained in the clay’s crystal structure based on its coloring agent. The color is determined by the presence of non-clay pigments, such as those found in ochres, or by the presence of any chromogenic ingredient in the crystal structure. The natural color hue can be influenced by drying intensity and even more so by persistent high-temperature heating [19].

2.1. Ochres According to geology, ochres are oxides or oxide hydroxides of metal which form in a near surface setting. Iron-rich ochres are the most common ones, although copper and cobalt ochres have also been used as pigments [20]. Ochres are a form of inorganic pigment that comes from natural minerals. The word “ochre” is a common term that refers to substances that range in color from yellow to deep purple and have an iron oxide chromophore [21]. Types of ochres include red ochre, yellow ochre, purple ochre, brown ochre, sienna, umber, and a variety of other names depending on their hue. Natural iron oxide pigments, unlike manufactured pigments, vary in color depending on the composition of the region of the earth from which they are mined. The color tends to be influenced by three primary factors where the existence of the iron oxide chromophore is the first consideration (principal coloring ingredient). The darker red ochres are more likely to contain hematite (Fe2O3), whereas the paler yellow ochres are more likely to contain goethite (FeOOH or Fe2O3·H2O, hydrated iron oxide). The existence of other metal oxides or clay minerals (secondary coloring ingredients) is the second factor to consider while the particle size distribution within the material is the third factor to consider. This last element is thought to be responsible for the color spectrum of brick red to violet found in the pigment known as caput mortuum, where Fe2O3 is the chromophore [22]. The earth’s color is determined by a combination of these variables. The wide variety of potential yellow, red, and brown is due to the numerous ways and combinations in which these ingredients can mix [23]. Heritage 2021, 4 1974

When the colors are different, distinguishing between pigments is easy. When color tones are identical, however, the distinction becomes more complicated, and classification may be incorrect. This is one of the most serious issues with red ochres such as hematite, caput mortuum, red or warm ochres, umbers, and raw or burnt sienna which come in a range of red color tones. Aluminosillicates or lower amounts of other oxides may occur with natural mixtures which causes a minor difference in color tones. Their recognition becomes more difficult since they were almost always mixed with other pigments rather than used in their pure form [24]. According to Bednarik [25], the states of hydration, reduction, hydrolysis, oxidation, adsorption, grain form, and size distribution of the several components within the pigments are all factors that influence the final tone of the pigment in question. The degree of hydration of the pigment which is equivalent to the amounts of the two main ochre-coloring minerals present (hematite to goethite ratio) is widely recognized as the most important factor that affects color [22]. As a result, anhydrous oxides (hematite) are more prevalent in purple and red shades of pigment. The lighter tones suggest hydration with goethite serving as the primary ferrous colourant whereas darker ochres contain several phases of iron hydroxides/oxides and manganese oxides. Brown earth and umbers, which are sometimes represented as ochre variants [26], are pigments in which the manganese oxide content exceeds 5% of the total colorant matter within the pigment. However, their overall features and structure indicate otherwise. The umbers, in particular, contain between 5–20% manganese oxides which have a substantial impact on the pigment’s physical properties. Besides color, accessory minerals may have affected a negative impact on ochre properties. Calcite, feldspars, quartz, dolomite, and other carbonate minerals, as well as clay minerals and probably gypsum, are examples of accessory minerals found in ochres [27]. Ochres also have excellent pigment properties, such as non-toxicity, excellent hiding ability, and tinting strength [28]. The continued and broad use of ochres can be attributed to a number of factors, including their abundance in Nature, suitable optical and handling characteristics, and relatively simple methods of preparation. These pigments are also among the most long-lasting pigments in the industry today, with exceptional resistance to water, light, and changing environmental conditions and, dilute acid and alkali attack [29]. Since ochres absorb ultraviolet light, they appear to shield their binding medium from degradation, in addition to extending the paint’s overall permanence [28]. Manufacturers denote synthetic iron oxide pigments with names commonly reserved for earth pigments, such as yellow ochre for an artificial yellow iron oxide, which complicates the issue. The term “iron oxide pigment” is commonly used to describe both natural and man- made materials that contain mixes of iron oxides and iron oxide hydroxides while the nomenclature earth and ochre are acceptable when it is evident that the colour comes from a natural source [15,30]. The use of heat to manipulate color dates back to 298,000 B.C.E., demonstrating the scientific temper of the prehistoric people for artistic purposes. Synthetic ochre was prepared by the irreversible process of calcining or boiling raw yellow soil to produce a variety of hues such as red, orange, brown, and mid tones of these colors. The dehydroxylation of hydrated iron oxides to oxides is involved in this procedure, with the final colour variation based on the initial material, temperatures, and heat treatment duration [31]. Solid-state transformation by heating iron ores or iron salts such as iron sulfates (FeSO4), iron chlorides (FeCl2/FeCl3), iron hydroxides (FeOOH), iron carbonate (Fe2CO3), and magnetite (Fe3O4) in an oxidizing atmosphere is one of the most extensively used ways of synthetic ochre processing. Methods for making synthetic therapeutic iron oxides by burning iron filings with various salts have been documented in India since the Ayurvedic period (600 B.C.E. to 800 C.E.) [32].

2.1.1. Red Ochre The name is attributed to the reddish color from the mineral hematite, which is occasionally found as fossilsized ores, secular iron ores and micaceous iron ores. The Heritage 2021, 4 1975

name hematite, derived from the Greek word “haima” meaning blood, aptly describes its usual red hue. Hematite is typically formed as a result of the oxidation of biotite (K(Mg,Fe)3AlSi3O10 (F,OH)2),magnetite (Fe3O4), (FeTiO3), goethite (α-FeOOH),and il- menite (FeTiO3)[28]. The latter case tends to be diagenetic, with increasing temperature and burial depth favoring the transformation [33]. The transformation of geological ochres to ochre pigments is simple and requires a chain of operations that includes removing larger impurities (such as organic contaminants and plant roots), grinding, sieving, and levigation before intermixing withaa medium to make paint. Hematite grain size influences color as well, with a general shift from red to purple beds as the crystal size increases [28]. Goethite is also one of the most common iron-bearing minerals in red beds, and is more common in younger deposits with a distinct yellow-brown appearance [34]. One of the biggest issues with red ochres is in that tracing them back to their source which is extremely difficult, particularly after they’ve been heavily processed. The presence of carbonate or quartz along with the crystalline nature, color, and particle size, can help distinguish broad sedimentary environments. The character and mineralogy of surviving ochre deposits in the area of an archaeological site can be used to determine the possible provenance of local use. Red ochres are a universal pigment that can be employed in works of art from many periods and cultures. From the Pleistocene period to the present day, it has been used as a pigment [35]. Ajanta, Ellora, Badami, Bagh, and other sites have Buddhist paintings rendered with red and yellow ochre pigments [36]. Red ochres are non-toxic and are used in the production of paints that not only dry easily but also completely cover surfaces. Ochre sightings have been recorded in many regions throughout the world. In India, red ochre deposits can be found primarily in Bharatpur, Bhilwara, Bikaner, Chittorgarh and Udaipur districts in Rajasthan; Gwalior, Katni and Rewa districts in Madhya Pradesh; Anantapur, Kadapa, Visakhapatnam districts in Andhra Pradesh; Bhavnagar, and Kachchh and Patan districts in Gujarat; Ballari and Bidar districts in Karnataka, and Chandrapur district in Maharashtra [37]. Indian red (hirmize) is also a natural iron ore or hematite with a rich purplish-red color and a ferric oxide content of over 90%. Some of the reds exported from India come from roasting lighter-colored ores, but the majority of the specimens are genuine natural ores. It was assumed that the some of the hematite was imported from the Forest of Dean and some from Ormuz in the Persian Gulf. The faint purplish tint of this pigment is its most distinguishing characteristic in terms of color. Indian red is sometimes marketed as an admixture of iron oxide with other materials, most likely the result of judicious mixing of purple-brown, red ochre, or “light red” and cheap white substances [38].

2.1.2. Yellow Ochre Natural yellow ochre (yellow earth) also known as limonite (hydrated iron hydroxide, FeO(OH)·nH2O which consists of a mixture of several iron-containing minerals includ- ing goethite (iron oxyhydroxide, FeO[OH]), akageneite, lepidocrocite, and jarosite, with goethite being the main component. Goethite is a type of pedogenic crystalline iron oxide hydroxides that can be found in rocks, soils, and ochre deposits [28]. Because of this, goethite-based earths are the most widely used yellow pigments in antiquity. However, yellow ochre became a regular artists’ material as the palette grew beyond red and black, and the usage of goethite-rich yellow ochres, in particular, became temporally and globally widespread [34]. The second main pigment is potassium jarosite. The finding of jarosite in Mars meteorites has spurred renewed interest in these minerals and their petrogenes is occurs in supergene settings, as well as their relationship with mine waste [39–42]. Yellow ochre is prepared by washing the natural mineral to remove sand and other impurities, then drying, grinding, and sieving it [43]. Some pigments can be safely com- bined with yellow ochre. Yellow ochre is non-toxic and stable, with excellent hiding ability and permanence in all media. Yellow earth is converted to burnt yellow earth by heating below 800 ◦C for several hours, where its constituent goethite is thermally converted to red iron oxide having hematite crystal structure. It has been known that heating yellow earth Heritage 2021, 4 1976

produces a red pigment. This technology seems to have been used in the Paleolithic era, and it is observed that the method had entered written history by the time of the Assyrian cuneiform tablets [44]. The transition from goethite to hematite when burnt can be easily identified using X-ray diffraction [44–47]. Depending on the temperature at which the goethite is heated, the product hematite is formed. Using X-ray diffraction, it is possible to separate burnt yellow earth pigments from the natural red earth [48]. In early 20th C.E. India, yellow ochre deposits were found near Katni, and several cen- tral Indian states such as Sohawal (Uttar Pradesh), Gwalior and Panna (Madhya Pradesh), and Baraunda (Haryana). Yellow ochre was also found as inclusion within laterite soil of various localities such as Cretaceous rocks (Trichinopoly, Tamil Nadu) and Tertiary beds (Myingyan district, Burma) [38]. Today’s, yellow ochre deposits can be found in Andhra Pradesh’s Guntur and Kurnool districts, Madhya Pradesh’s Jabalpur, Mandla, Satna, and Shahdol districts, and Maha- rashtra’s Nagpur district. According to Indian Minerals Yearbook (2015) data based on the United Nations Framework Classification for Resources (UNFC) scheme, the total reserves/resources of ochre as of 1.4.2015 are estimated to be 167.79 million tones. Around 36.93 million tons of these resources fall into the ‘Reserves’ category, while 130.86 million tons fall into the ‘Remaining Resources’ category. Around 87% of the total resources are red ochre, 11 percent are yellow ochre, and the remaining 2% are grade “Unknown.” Rajasthan has about 78% of the resources, followed by Madhya Pradesh with 11%, Andhra Pradesh with 7%, and Gujarat with 2%. Karnataka, Maharashtra, Jharkhand, and Uttar Pradesh have the remaining 2% of the total [37].

2.1.3. Umber Umber is a naturally occurring iron oxide and manganese oxide-containing ore which is used as brown and reddish-brown earth pigment [21]. It has been used for thousands of years and has earth tones ranging from cream to brown, depending on the amount of iron and manganese compounds present. It is also completely stable and darker than ochre and sienna, which are similar earth pigments and can be, safely mixed with other pigments. The best variety comes from Cyprus which is distinguished by the presence of manganese dioxide [48,49]. Umber is made by mining the ore followed by grinding and washing it which leaves a mixture of rust-stained clay. In its natural state, it is known as raw umber. The brown red color of umber intensifies when calcined and is known as burnt umber due to the loss of water (dehydration). Raw earth umber (raw sienna earth) consisting of iron oxide, aluminum oxide, and manganese oxide while burnt umber (burnt sienna earth) consisting of iron oxide, clay, and manganese oxide [21]. Being a mineral pigment with yellowish-brown to greenish brown color, derived from natural earth colored iron and manganese oxides, umber is normally used in tempera, paint and water color paintings. Because of their high oil adsorption, umbers need about 18% oil to coalesce with oil paints. As a result, the later oil films darken over time. Umber’s chemical composition is closely linked to its iron oxide content, much like sienna’s. The increased manganese content distinguishes umber from other colors. Clay, talc, and calcium carbonate are other naturally occurring substances in umber that do not effect its color. The particles of umbers are heterogeneous and rounded in appearance. Burnt umber particles are almost similar to raw umber particles. Umbers with high tinting strength are the ones which have high content of iron and manganese within them. Alkalis and dilute acids have no effect on umbers [21].

2.1.4. Sienna Sienna is an iron oxide and manganese oxide-based earth pigment while raw sienna is a yellow-brown pigment which occurs only in its natural state. Raw sienna’s chemical breakdown is roughly 90% iron oxide (yellow) with minor amounts of manganese oxide, which distinguishes it from pure yellow ochre. Burnt sienna is produced by heating raw sienna to 537–1093 ◦C before the iron oxide is mainly converted to hematite. Sienna was one Heritage 2021, 4 1977

of the first pigments used for painting and can be found in prehistoric cave art. However, it was not until the 14th century C.E., at the dawn of the Renaissance period, that the pigment was further refined for artistic use. It gets its name from the Italian city-state of Siena, where it was created. During this time, the Italians improved the pigment’s variety of colors by roasting sienna, resulting in raw sienna and burnt sienna pigments. Earth colors were used extensively in Renaissance painting techniques. It is stable at high temperatures but not acid resistant, and is compatible with all other pigments; so it is often mixed with a variety of others [18,50].

2.2. Wads: Manganese Ochres Soot is the natural choice of black pigment for any society since it is widely available and is a high purity carbon-based black pigment. Alternatively, woody plant material (as well as bones and ivory) can be quickly burned to create high-quality black pigments. Mineral blacks, such as manganese ochre or wad, are among the first examples of black pigment for artistic applications. Wad is an old English term for black soil used by miners which refers to manganese- rich earths, as well as graphite deposits. Manganese (Mn) is one of nature’s most abundant elements, accounting for one-tenth of all elements found in the Earth’s crust. According to geochemistry, Mn is found in minerals formed during the early stages of magmatic crystallization. Mn is easily oxidized near the Earth’s surface, forming several oxide- hydroxide minerals; however, it melts and can be abundant in late-stage deposits such as pegmatites; Mn is easily oxidized near the Earth’s surface, forming several oxide-hydroxide minerals; however, it melts and can be abundant in late-stage deposits such as pegmatites. Manganese ochres are made up of a complex mix of manganese oxide and hydroxide minerals, as well as iron oxides [51]. Simple oxides like MnxOy or mixed oxides like AxMnyOz, where A is K or Ba, reveal their sedimentary origin. The black mineral pyro- lusite (MnO2) is the most prevalent one, while other minerals that contain manganese include rhodonite(MnSiO3), rhodochrosite (MnCO3), manganite (MnO(OH), cryptomelane 4+ 3+ 4+ 3+ (Kx(Mn ,Mn )8O16), alabandite (MnS), and hollandite (Ba(Mn 6,Mn 2)O16)[52]. Iden- tification of the provenance of wads has proven to be extremely difficult due to their lack of documentation in geological literature. This material also has properties that make it useful for lighting fire, but it wasn’t always used as a pigment in this sense.

2.3. Green Earths (Terreverte) Green earth, a siliceous mineral with a dull grayish-green hue, is found all over the world and has long piqued artists’ interest [53]. Green earth has been discovered in some early Bhimbetka rock paintings, but there appears to be a general lack of black, such as carbon black or soot, in the primitive Indian paintings. The pigment was used by American Indians as well as artists from Pompeii and Ajanta caves in India. Perhaps the most well- known use of the pigment for the green under painting and shadows in medieval era was for painting’s flesh colors. Green earth was perfect for the artist because it was lightfast and easy to prepare by crushing and grinding, even though the hue was not as strong in chroma as malachite and azurite. The pigment is still sold in modern times from high-quality deposits found on Cyprus [54]. Green earths, also known as terreverte, are grey to blue green pigments made mainly 2+ 3+ from two closely related clay minerals, celadonite (K[Mg,Fe ]Fe [Si4O10][OH]2) and 2+ 3+ 3+ glauconite ([K,Na][Mg,Fe ,Fe ][Fe ,Al][Si,Al]4 O10[OH]2). Despite their chemical simi- larities, glauconite and celadonite are distinguished by a significantly higher number of trivalent ions in the octahedrally coordinated layer and a partial substitution of Al3+ for Si4+ in the tetrahedrally coordinated layer [55,56]. Celadonite is a relatively pure mineral that can be present in small amounts in vesicular cavities (amygdules) or volcanic rock fractures. Glauconite, a less pure but more commonly dispersed mineral, is often present in the form of small greenish pellets (green sand). Other greenish clay minerals may have been mixed into green earth pigments occasionally. One explanation for this is the morphological rather Heritage 2021, 4 1978

than the chemical characterization of the green pigment, and they may contain other clay minerals such as montmorillonite, chlorite, and kaolinite [56]. Although the chemical compositions of the two main source minerals, glauconite and, celadonite, are identical, traditionally the minerals were considered apart disparately, with glauconite attributedto a sedimentary origin and celadonite derived from altered basaltic rocks. Only recently has research allowed for an unmistakable distinction between the two minerals based on fractional differences in ionic substitution. Unfortunately, the name glauconite is used to characterize both a specific micaceous mineral and a specific morphological type (green sand). This arose from a long-standing inability to properly identify the components of glauconite pellets. Grissom [54] examined the terminology of green earth pigments, their materials, and their appearance in works of art. Green earth exhibits slight light scattering ability in oil due to its low refractive index of about 1.62 [56], where the resulting paint is relatively translucent. Apart from this the tinting ability and hiding power of the pigment are both poor. When the pigment is glazed over white or used in conventional water-dispersed mediums like glue or egg tempera, which usually produce films with high pigment volume concentration, the highest saturation (chroma) is achieved. Green earth is partly soluble in acids and alkalis, making it easy to obtain enough ferrous and ferric ions for micro- chemical testing. Burnt green earth is formed when the pigment becomes brownish when heated. Key elements of celadonite and glauconite (iron, silicon, aluminium, magnesium), as well as small amounts of potassium-replacement ions (calcium, manganese and sodium) along with trace amounts of titanium were identified in dozens of samples of green earth examined in India. The elements that were not present were beryllium, boron, arsenic, bismuth, cadmium, mercury, cobalt, nickel, molybdenum, tin, strontium, vanadium, zinc, and zirconium [57,58]. Green earths were and continue to be the most widely available pure green pigments, and as a result, they are well-known in the art world. Green earth is commonly used in Indian wall paintings and has been discovered in large quantities. The color green is prevalent in the Buddhist frescoes painted on lime and mud plasters in the caves of Ajanta, Maharashtra, India, from the 2nd Century B.C.E. to the 6th Century C.E. [59], and M. Singh and Arbad [36] identified the green pigment as celadonite which was derived from altered basalt.

2.4. White Earths Kaolinite, calcium carbonate and gypsum were used as white pigments since pre- historic times. M. Singh reported the kaoline, and calcium carbonate were used as white pigments, and often also with gypsum in Ajanta’s wall paintings [60].

2.4.1. Calcite and Gypsum

In all cultures around the world, calcium carbonate (CaCO3) and calcium sulfate {gypsum (CaSO4 2H2O), anhydrite (CaSO4), and other hydration states of calcium sulfate} were invariably used for backgrounds and white pigments. They can be referred as simply as white or calcium-based white [20]. Calcium carbonate in different forms has played a significant role in art since ancient times. Calcite is the most common natural source of calcium carbonate. It is mostly found in sedimentary rocks like limestone and chalk, but it’s also found in metamorphic rocks (marble) and igneous rocks in rare cases. Calcite and its dimorph form aragonite are the principal components of some mollusk shells, but aragonite (the less stable type) is more likely to be found in living or fossilized lower organisms, which is converted to calcite with climate changes, especially when heated [54]. Since pure calcium carbonate is white, it has a wide range of applications in the arts and industries, both in powdered and large forms. Some modern paints also use powdered whites as the primary pigment white, as well as bulking agents and extenders for white hiding and colored paints. Calcium carbonate pigments such as chalk, calcite, precipitated chalk, shell white, lime white, and coral have all been employed in the history of painting Heritage 2021, 4 1979

materials. Aragonite and vaterite are two less common polymorphic forms while calcite is frequently found as single large transparent crystals. The varieties range from coarse granular to impalpable. Both of these types of calcite can be found in paintings, both in the support structures and pictorial layers, along with several quantities of common impurities like dolomite, quartz, magnesite, clays, and coloring agents like carbon and hematite. In fresco painting, marble dust or ground marble was used [61]. Powdered forms of all kinds of calcium carbonate are white if relatively pure, but they lack the strong scattering and hiding power of heavy-metal whites when used in drying oil-based paints. Depending on the amount of impurities present, particularly iron oxide, natural chalk is typically a yellowish-white rock or grayish white. When exposed to light, all types of calcium carbonate become permanent. Hydrogen sulfide gas or contact with sulfide pigments does not darken them. Except for alkali-sensitive colors like Prussian blue, which may be discolored by lime white, which can maintain its alkalinity for a long time, they are compatible with most other pigments. However, acids found in modern industrial and urban environments are harmful to calcite (particularly the finely crystalline and porous varieties). Since calcium sulfate has a larger volume than carbonate when produced in the presence of sulfuric acid, it causes spalling and flaking of lime surfaces [62]. The mineral gypsum is made up of hydrated calcium sulfate (CaSO4 2H2O). Selenite is the name given to the mineral when in well-developed crystals. Satin spar is a fibrous vast variety with a silky lustre that is transparent and opalescent. Gypsum comes in a variety of types and is extremely economically valuable. It is colorless or white, but due to the presence of impurities, it may be tinted light brown, grey, yellow, green, or orange. Anhydrite (CaSO4) is a natural mineral that contains calcium sulfate but is devoid of all water of crystallization. This can be observed as large opaque white mineral underlying gypsum in several locations. The two layers are undergo net-mixing in an intermediate region, so it’s not unusual to find gypsum samples containing anhydrite, and vice versa. In terms of crystal habit and other physical properties, gypsum differs from anhydrite due to the two molecules of water used in crystallization. The former can be used in a variety of ways [63]. Paramasivan reported that the calcium carbonate (lime plaster) levels found during analysis were also quite low and present in the form of impurities only. He chemically examined the fine plaster layers of several Indian wall paintings after separating the paint film from rough plasters. He treated rough plasters with dilute hydrochloric acid, which dissolved the fine plaster giving efflorescence with emission of carbon dioxide. The presence of calcium and traces of sulfate in the solution indicated that a lime-calcium sulfate mixture was used as lime plaster over the rough plaster. Calcium sulfate is an impurity in the lime, according to him. Calcite and gypsum both were used either as white pigments or ground in many rock and cave paintings of India [64–69]. Through his researchSingh has identified calcite as the white pigment used at the Ajanta and Ellora paintings [70,71].

2.4.2. Kaolinite Kaolin is a type of natural clay rock that is mostly composed of the clay mineral kaolinite, which has the chemical composition (Al2[Si2O5][OH]4). The structural layer of 4− kaolinite is made up of two sheets, one of which is made up of tetrahedra of [SiO4] (“T”) 6− and the other of which is made up of octahedra of [AlO3(OH)3] (“O”), with a T/O ratio of 1:1 and the net charge of a layer iszero [72]. The lack of or random displacement of two-sheet layers along the b axis indicate whether the kaolinite structure is well or poorly organized [73]. With a soft consistency and earthy texture, kaoline is abundant locally in combination with hydrothermally altered granites and volcanic clastic rocks, and it can be broken easily and molded or formed, particularly when wet. In spite of this, it is yet to be widely recognized as a pigment in its own right. While kaolin is a dull and uninteresting mineral in and of itself, it does occasionally form interesting pseudomorphs, especially after feldspars. The word kaolin refers to both a group of closely related clay mineral and a particular member of that group. Many Heritage 2021, 4 1980

commercial kaolinite mines exist, where this mineral is extracted in large quantities for various industrial applications [74]. Works bySingh have evinced the use of kaolin for executing floral designs in Ajanta. The Ajanta caves belong to the 2nd B.C.E. and painting work was ere executed from the 4th C.E. Singh has suggested that kaolin was used in combination with different pigments such as red and yellow ochres as well to change the tone and hue of the paintings [75].

2.5. Blue Earths 2+ The mineral vivianite (Fe3 [PO4]2·8H2O) refers to the blue earth, an iron phosphate hydrate that forms naturally in peat bogs and is also known as “blue ochre” [19]. It can also be found in organic-rich habitats, such as the insides of fossilized mollusk shells, and also is found in traces quantity within bones, rotting wood, and other organic matter. In combination with hematite, siderite, or anapaite, vivianite is formed as radiating clusters of acicular (needle-like), prismatic, or fibrous bluish-green crystals. Vivianite is a dark blue or green mineral that is normally stable, but it can be colorless when first exposed. This color transformation is unique to vivianite, which is found in peat bogs [76]. Since vivianite has a low tinting intensity, it is rarely reliably opaque unless applied in thick or multiple coats, allowing the substrate to show through. Vivianite is not as reflective as other pigments when visually recognizing it. Unlike “brighter” ultramarine blue and darker, more concentrated Prussian blue, vivianite absorbs light rather than reflecting it, even though a lipid binder is used [77]. Vivianite is seldom found in archaeological contexts in the ancient world, but fur- ther identifications of this peculiar pigment may be produced soon. Vivianite has been discovered in several easel paintings from the historical period and it has been found in medieval art in France. However, vivianite as a blue pigment could not be detected in Indian painting, but its existence cannot be denied since the absence of a discussion of these minerals in the literature is simply an absence of analysis rather than proof of a mineral’s non-existence or rarity in a specific place.

3. Materials and Methods (Scientific Examination of Pigments) Since the purpose of this paper was to analyze earth pigments used in Indian wall paintings, it was important to determine the techniques that were suitable for characteriza- tion, as will be mentioned below, and in Table2. There are several instrumentation techniques for characterizing earth pigments which have been practiced and described in literature. The characterization is done through direct and oblique lights which help in providing visual information and condition of pigment layer. The surface characterization study can be done by preparing the cross-section of pigment sample which is prepared by embedding the pigment fragment in the epoxy resin, then polishing, and mounting on glass slides. The cross-section of the pigment sample can be seen in reflected light at different magnifications which enables to provide information on the order of pigment layers, thickness of layer, texture and color of those layers, and pigment particle size. Optical microscopy (OM), UV fluorescence, scanning electron microscopes (SEM), atomic force microscopy (AFM), and other imaging techniques can be used to examine cross-section samples. Cross-sections also provide a safe platform for conducting micro-chemical tests away from the actual painting or surface. The examination of a sample in cross-section is the initial stage in determining what a sample is made up of and developing a testing regimen [78]. X-ray based techniques including X-ray fluorescence spectroscopy (XRF), X-ray diffrac- tion (XRD), laser-induced breakdown spectroscopy (LIBS), and X-ray photoelectron spec- troscopy (XPS) and energy dispersion X-ray (EDX) are the commonly used as a preliminary investigation techniques either used solely or employed with other analytical and physic- ochemical approaches to provide a comprehensive understanding of all the components present, determination of material’s crystallography, detection of a wide range of major, Heritage 2021, 4 1981

minor and trace elements, determination of the valence and electronic levels of specific elements, and determination of elementary information in various pigments respectively. FTIR and Raman spectroscopy both use the interaction of infrared rays (IR) with materials to gather knowledge about organic and inorganic molecular bonds. Both these techniques are useful methods in characterizing molecular chemistry of materials [79]. FTIR is very valuable technique for identifying organic binding medium in the pigment sample whereas Raman is frequently utilized for the investigation of organic and inorganic pigments. FTIR can identify complex anions in inorganic compounds (such as sulphates, carbonates, and silicates), but it cannot distinguish simple anions (such as oxides and sulfides). FTIR is generally preferred for differentiating earth ochres because it provides much information about the clay proportion inside the ochre than Raman methods [17,80,81].

Table 2. Applications of each technique for characterizing pigment used in wall paintings.

S.No. Analytical Technique Instrument Used Applications Morphology characterization including phase Optical Microscopy information, grain size and presence of defects. Imaging technique Surface characterization and cross-section 1. SEM analysis. AFM Evaluation of surface properties. XRF Major and trace elemental analysis. XRD Identification of crystalline phases. Characterization of surface contamination or XPS corrosion products. 2. X-Ray Technique NAA Elemental characterization. LIBS Elemental and cross-section analysis. Distinguish between lattice structures and Mossbauer spectroscopy geometries of coordination particularly for iron-containing pigments. Identification of organic and inorganic Raman 3. Molecular Methods pigment. FTIR Identification of organic functional groups. Identification of material’s chemical, structure TG and textural nature. 4. Thermal gravimetric analysis Providing data on structure decomposition, DTA phase transformations, crystallization, sublimation, etc. 5. Ion beam analysis technique PIXE Identification of elements at trace level. Identification and quantification of unknown GC-MS/Py-GC-MS organic compounds at molecular level. 6. Mass-spectroscopy based technique ICP-MS Analysis of traces of inorganic elements.

Thermal gravimetric analysis consists of three methods which are thermogravimetry (TG), differential thermal analysis (DTA), and differential scanning calorimetry (DSC). TA method is used for analyzing the association between the physicochemical and thermody- namic parameters with temperature fluctuations. TG measures variations in the weight of materials caused by temperature variations (weight loss curve), which are intimately related to their chemical, structural, and textural properties. DTA measures the temperature difference between the material under study and an inert reference material during heating under identical conditions. As a result, the DTA curve provides information on all of the transformations that occur during heating, such as sublimation, crystallization, phase transformation, structural disintegration, and so on. DSC is a thermo-analytical technique Heritage 2021, 4 1982

for measuring the energy difference between a target sample and a reference material as temperature changes. DSC which quite corresponds to DTA is used to characterize a wide range of characteristic properties of samples [72,82,83]. Apart from identification of pigments, mass-spectroscopy based techniques, e.g gas chromatography-mass spectrometry (GC-MS)] are currently recognized as the best ap- proach for distinguishing organic components in micro-samples of painting layers such as proteins, waxes, terpenic resins, polysaccharide gums and drying oils. The approach provides basic information of organic compounds which evaluates the best circumstances for long-term conservation and to planning restoration [78].

4. Discussion on Earth Pigments Used in India’s Wall Paintings Table3 lists the chronological development of pigment used in Indian wall painting, their techniques, analytical instruments used in identification and locations. The Bhimbetka site is the most widely studied and investigated of the many prehistoric sites identified in India. The artwork is done on calcareous sandstone, which is produced from argillaceous parent rock. M. Singh examined the pigments in Bhimbetka were calcite, gypsum, hematite, whewellite, and goethite using portable Raman and EDX analysis [84]. The wall paintings at the Buddhist temples of Jogimara date to the 2nd century B.C.E. and were executed as a secco onto the wall that had been roughly levelled and covered with a thin clay render. A rough plaster of ferruginous earth admixed with clay and reinforced with vegetable fiber and paddy husk was first laid on the rock surface at Ajanta (2nd century B.C.E. to 6th century C.E.). Over this, a fine thin clay plaster was applied. The pigments used were red ochre, yellow ochre, lime and gypsum, terreverte, lapis lazuli, and carbon (Figure2). The painting was executed as tempera using animal glue as the binding medium. From the 7th century C.E. onwards, substantial use of lime as a significant ground was observed, with the most notable example being the south India Pallava paintings at the Kailashnatha Temple, Kancheepuram, painting of the early Pandian period at Sittannavasal (9th century C.E.), Chola paintings at Tanajavur, (11th century C.E.) and later paintings of the Vijayanayar, Nayaka, and Mahratta period (6–18th century C.E.) [9,85–87]. A majority of the paintings in India were created on lime plaster or mud plaster ground, with animal glue or another gelatin-based binding medium. In addition to prehistoric earth colors, painters began to use minerals such as lead white, orpiment, realgar, cinnabar, litharge, malachite, and verdigris, as well as dyes such as dragon’s blood, madder, and indigo. Lapis lazuli, lead, Indian yellow, tin yellow and azurite, and other pigments were introduced later. Synthetic pigments such as cadmium and chrome yellows, synthetic ultramarine, Prussian blue, Scheele’s green, cobalt blue, and others are, without a doubt, relatively new [11,87]. According to Subbaraman, the selection of pigments used in Indian mural painting is somewhat restricted and thus has remained consistent over a wide geographic area for nearly 2000 years [15]. From prehistoric to Mughal times, the pigments used in India have remained nearly similar without much difference [70]. Parmasivan did pioneering work on Indian mural paintings in the 1930s by researching the paintings of Ajanta, Sittanavasal, Thanjavur (Figure3), and Lepakshi, among others, to identify the painting’s methods and materials. He identified the white pigments in Vijayalaya Cholisvaram, Tamil Nadu to be from lime, black from wood charcoal, yellow from yellow ochre, red from red ochre, green from green ochre, and bluish-greenfrom a mixture of terreverte and ultramarine [64]. Similarly, pigments such as yellow ochre, red ochre, carbon, lime, terreverte were also found at Badami in Karnataka and Kanchi Kailasanathar temple in Chennai [65,66]. Identified pigments in Bagh cave were red ochre, yellow ochre, lapis lazuli, terreverte, carbon, and lime [60]. Parmasivan also found grounds to believe that they were probably in the true fresco technique but was unable to firmly establish this. He examined the 10 pigment samples of Chola paintings using X-ray diffraction which helped to identify that in all the cases, the d lines of the actual compounds constituting the pigments strongly interfered, making the identification of the pigments almost impossible. This seemed to indicate that carbonization had taken place Heritage 2021, 4 1983

and the pigment particles were surrounded by calcite. It is of interest in this context that there are several old Indian texts from the 9th century C.E. onwards that deal with the tempera painting technique. All of them mention binding media like gums and glues of different types but with no references to the use of lime medium [68]. The study of pigments has piqued the interest of many mural restorers over the last few decades. The pigments used in Ajanta-Ellora have been identified by Lal [88] in 1967 and Bharadwaj in 1983 [89]. Except for black, the colors employed at Ajanta-Ellora were said to be mineral-based except for the lamp black. Ajanta painters used lime and kaolin as clay for white, lapis lazuli for blue, red ochre for red, yellow ochre for yellow, charcoal (lamp black) for black, and gluconate or terra verte for green. All of the pigments were residual products from the alteration of volcanic rock including red, green, white, and yellow. These pigments were easily available locally except for lapis lazuli which appears to have been imported because of its scarcity in the region. According to Lal, there is no indication of the usage of copper compounds such as azurite for blue, and malachite for green in Ajanta caves [21,87]. Terra verte, also known as glauconite, is a green ferrous silicate complex that is formed as a by-product of basalt formation. There existed no evidence regarding the scientific study of pigment samples from Ajanta and Ellora until the recent researches by Singh, which aided in identifying the pigments at Ajanta as yellow ochre, red ochre, green earth, carbon black, lapis lazuli, and kaolin/shell Heritage2021, 4 FOR PEER REVIEW 14 lime [36,70] whereas hematite, cinnabar, green ochre, orpiment, and lime as pigments at Ellora (Figure4)[71].

Figure 2. Painting showingdevoteesat AjantaAjanta (cave no-10), Maharashtra.

A majority of the paintings in India were created on lime plaster or mud plaster ground, with animal glue or another gelatin-based binding medium. In addition to pre- historic earth colors, painters began to use minerals such as lead white, orpiment, realgar, cinnabar, litharge, malachite, and verdigris, as well as dyes such as dragon’s blood, madder, and indigo. Lapis lazuli, lead, Indian yellow, tin yellow and azurite, and other pigments were introduced later. Synthetic pigments such as cadmium and chrome yel- lows, synthetic ultramarine, Prussian blue, Scheele’s green, cobalt blue, and others are, without a doubt, relatively new [11,87]. According to Subbaraman, the selection of pig- ments used in Indian mural painting is somewhat restricted and thus has remained con- sistent over a wide geographic area for nearly 2000 years [15]. From prehistoric to Mughal times, the pigments used in India have remained nearly similar without much difference [70]. Parmasivan did pioneering work on Indian mural paintings in the 1930s by research- ing the paintings of Ajanta, Sittanavasal, Thanjavur (Figure 3), and Lepakshi, among oth- ers, to identify the painting’s methods and materials. He identified the white pigments in Vijayalaya Cholisvaram, Tamil Nadu to be from lime, black from wood charcoal, yellow from yellow ochre, red from red ochre, green from green ochre, and bluish-greenfrom a mixture of terreverte and ultramarine [64]. Similarly, pigments such as yellow ochre, red ochre, carbon, lime, terreverte were also found at Badami in Karnataka and Kanchi Kailasanathar temple in Chennai [65,66]. Identified pigments in Bagh cave were red ochre, yellow ochre, lapis lazuli, terreverte, carbon, and lime [60]. Parmasivan also found grounds to believe that they were probably in the true fresco technique but was unable to firmly establish this. He examined the 10 pigment samples of Chola paintings using X-ray dif- fraction which helped to identify that in all the cases, the d lines of the actual compounds

Heritage2021, 4 FOR PEER REVIEW 15

constituting the pigments strongly interfered, making the identification of the pigments almost impossible. This seemed to indicate that carbonization had taken place and the pigment particles were surrounded by calcite. It is of interest in this context that there are Heritage 2021, 4 several old Indian texts from the 9th century C.E. onwards that deal with the tempera1984 painting technique. All of them mention binding media like gums and glues of different types but with no references to the use of lime medium [68].

Figure 3. WallWall painting painting from from Brihadeeswara Brihadeeswarartemple,rtemple, Thanjavu Thanjavur,r, Tamil Nadu.

TheAditya study Prakash of pigments Kanth identifiedhas piqued the the 16th interest century of many C.E. Orchahamural restorers fort’s (Figure over the5) pig- last fewments decades. as yellow The ochre pigments for yellow, used copper-basedin Ajanta-Ellora pigment have been for green, identified lapis lazuliby Lal for [88] blue, in 1967 and andmixtures Bharadwaj of lead in carbonate, 1983 [89]. calcite, Except and for gypsum black, the for colors white [employed58]. Cinnabar at Ajanta-Ellora and red lead were saidcommonly to be mineral-based associated with except earth for pigments. the lamp These black. pigments Ajanta painters have been used used lime with and redkaolin ochre as clayin 17–18th for white, century lapis C.E. lazuli wall for painting blue, red of oc Chattahre for Chowk, red, yellow Red fort. ochre Sharma for yellow, [57] identified charcoal (lampthe pigments black) for at black, Chatta and Chowk gluconate where or red terra paint verte layers for green. were All attributed of the pigments to the mixture were re- of sidualhematite products (Fe2O3 ),from cinnabar the alteration (HgS), and of cadmiumvolcanic rock sulfide including (CdS). Thered, utilizationgreen, white, of a and mixture yel- low.of mercury, These pigments iron, and were cadmium easily compounds available lo hascally served except as for clear lapis evidence lazuli which to specific appears tones to haveon the been painted imported surfaces. because The of green its scarcity paint layer in the was region. attributed According to green to Lal, earth there (celadonite) is no in- dicationthrough vibrationalof the usage features, of copper differentiating compounds from such glauconite as azurite spectra.for blue, and malachite for green in Ajanta caves [21,87]. Terra verte, also known as glauconite, is a green ferrous sili- cate complex that is formed as a by-product of basalt formation. There existed no evidence regarding the scientific study of pigment samples from Ajanta and Ellora until the recent researches by Singh, which aided in identifying the pigments at Ajanta as yellow ochre, red ochre, green earth, carbon black, lapis lazuli, and kaolin/shell lime [36,70]whereas hematite, cinnabar, green ochre, orpiment, and lime as pigments at Ellora (Figure 4) [71]. Aditya Prakash Kanth identified the 16th century C.E. Orchaha fort’s (Figure 5) pigments as yellow ochre for yellow, copper-based pigment for green, lapis lazuli for blue, and mixtures of lead carbonate, calcite, and gypsum for white [58]. Cinnabar and

Heritage2021, 4 FOR PEER REVIEWHeritage 2021 , 4 198521

Figure 4. MuralFigure fromNataraj, 4. Mural fromNataraj, Kailashnath Kailashnath temple temple (cave (cave no-16),no-16), Ellora, Ellora, Maharashtra. Maharashtra.

Heritage 2021, 4 1986 Heritage2021, 4 FOR PEER REVIEW 22

Figure 5. Wall paintings inside the Orchha fort complex, Madhya Pradesh.

Table 3. Chronological development of pigment used in Indian mural painting with techniques.

Analytical S.No. Date Location Pigments Painting Techniques References Technique Used White: Whewellite, lime and Bhimbetka, Bhopal gypsum Transparent/opaque Portable-Raman 1. 8000 B.C.E. [84] (Madhya Pradesh) Red: Hematite color EDX Yellow: Goethite Red: Red ochre Colorimetry Yellow: Yellow ochre Particle size Ajanta Black: Carbon analyzer 2. 2nd B.C.E.–6th C.E. Tempera [75] (Maharashtra) White: Lime and gypsum XRF Green: Terre verte FTIR Blue: Lapis lazuli SEM-EDX Sitabenji Paintings Red: Red ochre 3. 4–6th C.E. Keonjhar District Yellow: Yellow ochre Data not available [90] (Odisha) White: Lime

Heritage 2021, 4 1987

Table 3. Cont.

Analytical S.No. Date Location Pigments Painting Techniques References Technique Used Red: Red ochre Yellow: Yellow ochre Rock cut temple, Micro-chemical spot 4. 6–7th C.E. White: Lime Tempera [65] Badami (Karnataka) analysis * Green: Terre verte Black: Carbon Red: Red ochre Yellow: Yellow ochre Bagh Caves Green: Terre verte Micro-chemical spot 5. 7th C.E. Tempera [60] (Madhya Pradesh) Blue: Lapis lazuli analysis Black: Carbon White: Lime Red: Hematite + Cinnabar micro-XRF Ellora Green: Green ochre XRD 6. 7th C.E. Tempera [71] (Maharashtra), Yellow: Orpiment FTIR White: Lime Raman Pallava Painting, Yellow: Yellow ochre Kailasanatha Red: Red ochre Vaikunthaperumal Micro-chemical spot 7. 7–9th C.E. Green: Terre verte Lime (secco) [66] temple analysis Black: Carbon Conjeevaram (Tamil White: Lime Nadu) Yellow: Yellow ochre Red: Red ochre Kanchipuram Micro-chemical spot 8. Late 7th C.E. Black: Carbon Lime (secco) [90] (Tamil Nadu) analysis Green: Terre verte Blue: Ultramarine Pale red: Red ochre Vishnu Temple, Dark red: Hematite Micro-chemical spot 9. 6–9th C.E. Thodikodiyanum, Data not available [90] Pale green: Malachite analysis Kottayam (Kerala) Dark green: Terre verte Yellow: Yellow ochre Red: Red ochre Sittannavasal (Tamil Micro-chemical spot 10. 9th C.E. Black: Carbon Lime (Secco) [90] Nadu) analysis Green: Terre verte Blue: Ultramarine Yellow: Yellow ochre Red: Red ochre Thanjavur (Tamil Black: Lamp black Micro-chemical spot 11. 11th C.E. Lime (Secco) [68] Nadu) Green: Terre verte analysis Blue: Ultramarine White: Lime Ramdwara Shining red: Cinnabar Galiakot, Dark red: Hematite Micro-chemical spot 12. 11th C.E. Rajasthani [90] Dungarpur Dark green: Malachite analysis (Rajasthan) Shining blue: Azurite Dark red: Hematite Sankaranarayana Dark green: Terre-verte 13. 12th C.E. temple, Peruvanam, Data not available [90] Pale yellow: Yellow ochre Trichur (Kerala) Dark black: Carbon black Dark green: Malachite + iron oxide + silica, azurite, calcite and phloghite. Red: Cinnabar + gypsum + quartz + muscovite Lakhang-Gongma Dark blue: Azurite + gypsum + 14. 12th C.E. Monastery, Nako quartz Tempera XRD [91] (Himachal Pradesh) Greenish black blue: Azurite + malachite + goethite + gypsum + quartz Reddish dark: Karpatite + iron oxide, cinnabar, calcite, quartz and kaoline Shining red: Cinnabar Dark red: Hematite Dark green: Malachite JunaMahal, Pale green: Terre-verte 15. 13th C.E. Dungarpur Violet blue: Ultramarine Rajasthani [90] (Rajasthan) Off white: Lime Shining red: Cinnabar Pale yellow: Yellow ochre Pale blue: Ultramarine Heritage 2021, 4 1988

Table 3. Cont.

Analytical S.No. Date Location Pigments Painting Techniques References Technique Used White: Lime Black: Wood charcoal. Vijayalaya Yellow: Yellow ochre Cholisvaram, Micro-chemical spot 16. 14–15th C.E. Red: Red ochre Tempera [64] Pudukkottai state analysis Yellow: Yellow ochre (Tamil Nadu) Bluish green: Terre verte + ultramarine Yellow: Yellow ochre Lepakshi (Andhra Red: Red ochre Micro-chemical spot 17. 16th C.E. Lime (Secco) [90] Pradesh) Black: Carbon analysis White: Lime Shining red: Cinnabar Charryyapali Dark red: Terre verte Micro-chemical spot 18. 16th C.E. Church, Kottayam Data not available [90] Pale green: Malachite analysis (Kerala) Dark green: Terre verte Red: Red ochre Optical microscopy Green: Terre verte with polarizing Moghul Gateway, Yellow: Yellow ochre 19. 16th C.E. Rajasthani microscopy [92] Bairat, (Rajasthan) White: Chalk Micro-chemical spot Black: Carbon black analysis Blue: Ultramarine Dark red: Cinnabar Brilliant red: Cinnabar + red lead Pink: Cinnabar + chalk Brownish red: Red ochre White: Chalk micro-Raman Raja Mahal, Orchha Bright yellow: Orpiment 20. 16th C.E. Tempera FTIR [58] (Madhya Pradesh) Brownish yellow: Yellow ochre SEM-EDX Warm green: Malachite Cold green: Terre verte Dark blue: Prussian blue Medium blue: Ultramarine or azurite Silver: Silver XRD St. Mary Church of Red: Cinnabar/hematite XRF (Unpublished 21. 16th C.E. Cheriapally, Tempera Green: Malachite FTIR work) Kottyam (Kerala) Raman Reddish brown: Raw umber Red: Burnt umber Yellowish brown: Raw sienna Golden temple (Sri Reddish brown: Burnt sienna Harmandar Red: Red ochre Microscopic 22. 16th C.E. Tempera [93] SahebJi), Amritsar Blue: Ultramarine blue Analysis (Punjab) Yellow: Yellow ochre Green: Green earth Black: Carbon black White: Lime Sri Ranganathaswamy temple, Srirangam, Dark green: Malachite Tiruchira-palli Pale yellow: Yellow ochre 23. 16–17th C.E. Data not available [90] Thiruvannali Pale blue: Ultramarine Prakalam Vishnu Deep blue: Carbon black Temple (Tamil Nadu) Red: Cinnabar + hematite XRD Adiyamankottai Yellow: Orpiment XRF [(unpublished 24. 16–17th C.E. Temple (Tamil Tempera Gray: Lime+ manganese oxide FTIR work) Nadu), Figure6 Black: Lamp black Raman Gold: Gold White: White lead. Servent Chapel of Black: Carbon black Micro-chemical spot 25. 17th C.E. St. Monica Church Tempera [94] Red: Red ochre/Red lead analysis and Convent (Goa) Blue: Prussian blue/malachite Green: Terre verte High Red: Red ochre+ cinnabar Chatta Chowk, Red resolution-XRD 26. 16–17th CE +cadmium sulfide [57] Fort, Delhi FTIR Green: celadonite Portable-Raman Heritage 2021, 4 1989

Table 3. Cont.

Analytical S.No. Date Location Pigments Painting Techniques References Technique Used Yellow: Yellow ochre Red: Red ochre 27. 17–18th C.E. Kerala Paintings Lime (Secco) [90] Black: Carbon Green: Terre verte Red: Red ochre Blue: Lapis lazuli Micro-Raman Yellow: Yellow ochre Indian Temple FTIR –ATR & 28. 18th C.E. Green: Green ochre Tempera [95] (New Delhi) FTIR-KBr Black: Carbon black SEM-EDX White: Lime or gypsum + kaoline Shining red: Cinnabar Dark red: Hematite Kushalgarh palace, Pale green/Dark green: Micro-chemical spot 29. 18th C.E. Dungarpur Rajasthani [90] Malachite analysis (Rajasthan) Pale yellow: Yellow ochre Off-white: Lime Shining red: Cinnabar Mansa Devi Temple, Dark red: Hematite Micro-chemical spot 30. 18th C.E. Panchkula Dark green: Terre verte Secco [90] analysis (Haryana) Pale yellow: Yellow ochre Off white: Lime Red: Red ochre Kusum Sarovar, Green: Terre Verte Micro-chemical spot 31. 18th C.E. Govardhan (Uttar Yellow: Yellow ochre Secco/Rajasthani [96] analysis Pradesh) Black: Lamp black White: Lime Orange Red: Red lead Brownish red: Red ochre Deep red: Cinnabar Sheesh Mahal, Blue pigment: Indigo Micro-chemical spot 32. 18–19th C.E. Rajasthani [97] Nagaur (Rajasthan) Green: Malachite analysis Yellow pigment: Orpiment White: Zinc white Golden yellow: Gold Yellow: Orpiment Red: Cinnabar, Vermilion Blue: Ultramarine Jhala Haveli, Kota 33. Late 18th and 19th C.E. Green: Terra-verte Rajasthani [90] (Rajasthan) Black: Animal Charcol Golden: Gold foil White: lime Dark red: Hematite Pale green: Malachite Shiva Temple, Dark green: Terre-verte 34. 19th C.E. Perumatrikovil, Data not available [90] Pale yellow: Yellow ochre Ernakulam (Kerala) Dark black: Carbon black Off white: Lime Tambekarwada Paintings Gold: Gold 35. 19th C.E. Data not available [90] Bhau Tambekar, Red: Vermillion Baroda (Gujarat) Red: Red lead & red ochre Blue: Ultramarine Optical microscopic Panchai Court, 36. 19–20th C.E. Green pigment: Malachite Tempera Micro-chemical spot [98] Imphal, (Manipur) Yellow: Orpiment analysis White: Lime * Micro-chemical spot analysis [99]. Heritage 2021, 4 1990 Heritage2021, 4 FOR PEER REVIEW 23

Figure 6. MuralMural paintings from Adhiyamankottai, Tamil Nadu.

5. Conclusions 5. ConclusionsThroughout the history of Indian wall paintings, artists’ palette were dominated by earthThroughout pigments, (iron) the history ochres, of green Indian earth, wall wads paintings, and white artists’ earth, palette and were palettes dominated were sim- by ilarlyearth pigments,limited to(iron) colors ochres, including green red, earth, yellow, wads andbrown, white green, earth, black, and palettes and white. were Explora- similarly tionslimited for to suitable colors includinghues were red,relentlessly yellow, brown,undertaken; green, quarries black, andwere white. established, Explorations and trade for insuitable their products hues were flourished. relentlessly White undertaken; was de quarriesrived from were kaolin, established, limestone and and trade gypsum; in their blackproducts from flourished. manganese White ochre; was green derived from from celadonite kaolin, and limestone glauconite, and gypsum; red from black hematite, from andmanganese yellow ochre;from goethite. green from The celadonite colors were and frequently glauconite, produced red from by hematite, the painters and yellowthem- selves,from goethite. using their The colorsown specific were frequently formulae. produced These pigments by the painters were themselves,carefully chosen, using theirthen groundown specific and blended, formulae. and These outstandingly pigments were the carefullytest of time chosen, has thenproven ground their and exceptional blended,

Heritage 2021, 4 1991

and outstandingly the test of time has proven their exceptional durability. Vivianite as a blue pigment hasnot been detected in Indian paintings, but its existence and usage cannot be unequivocally denied, since the absence of any discussion on these minerals in the literature is simply an absence of analysis rather than proof of the mineral’s non-existence or rarity. However, the evidence of historical pigments in Indian painting is not limited to earth pigments; there are other categories of pigments which are widely used in wall paintings (inorganic and organic) such as cinnabar, lapis lazuli, indigo, Indian yellow, malachite, carbon black or lamp black, lead white, madder, Prussian blue, orpiment, etc. The present review article is based on earth pigments explaining their existence and uses with regard to the Indian context.

Funding: This research received no external funding. Acknowledgments: The authors are thankful to the National Museum Institute, Janpath, and Na- tional Research Laboratory for Conservation of Cultural Property, Lucknow for providing us neces- sary facilities. We would like to provide our special thanks to Satyajith Ibn for revising the current manuscript. Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to publish the results.

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