The fresco wall painting techniques in the Mediterranean area from Antiquity to the present: A review

Journal of Cultural Heritage 66 (2024) 166–186 Contents lists available at ScienceDirect Journal of Cultural Heritage journal homepage: www.elsevier.com/locate/culher Review The fresco wall painting techniques in the Mediterranean area from Antiquity to the present: A review D. Jiménez-Desmond a , ∗,J.S. Pozo-Antonio a ,A. Arizzi b a CINTECX, GESSMin group. Dpt. of Natural Resources and Environmental Engineering, Mining and Energy Engineering School, University of Vigo, 36310 Vigo, Spain b Dpt. of Mineralogy and Petrology, Faculty of Science, University of Granada, 18071 Granada, Spain a r t i c l e i n f o Article history: Received 10 July 2023 Accepted 20 November 2023 Keywords: Wall painting Fresco technique Lime mortar Pigment Compatibility Conservation of architectural heritage a b s t r a c t Fresco wall paintings are one of the oldest artforms in our cultural heritage, dating back to the second millennium BC. In this work, we carry out a thorough review on the evolution of the fresco wall painting technique from Antiquity to the present day. Focused on the Mediterranean area, the aim is to gather in-depth information on different technological aspects of this decorative artform such as execution procedure, materials used and pictorial palette. Considering that the recognition of the pictorial technique ( a fresco, a secco, or a mezzo fresco ) is often difficult since the identification of organic binders can be a challenging issue, the assignment of well-known non-alkaline-resistant pigments to the fresco technique might not always be precise. With this in mind, this review aims to highlight the contradictions found between the bibliographical sources on the fresco technique and recent scientific studies in relation to the preparation of materials, the execution on the wall and the incompatibility of certain pigments with the alkaline environment created by this pictorial technique. ©2023 The Author(s). Published by Elsevier Masson SAS on behalf of Consiglio Nazionale delle Ricerche (CNR). This is an open access article under the CC BY-NC-ND license ( http://creativecommons.org/licenses/by-nc-nd/4.0/ ) Introduction and research aim Wall paintings are understood as any kind of pictorial decoration executed on a wall (i.e., cave or masonry), and as such are considered one of the oldest forms of artistic and historical heritage which must be preserved in situ [1] . Apart from their unquestionable aesthetic worth, wall paintings are also of high historical and artistic value in that they act as a historical document that offers insights into the history, architecture, and customs of the time. This explains why in recent decades there has been increasing interest in frescoes within the field of conservation and restoration of architectural heritage. Over the course of the long history of wall painting, a wide range of different techniques have been used. The first examples were cave paintings dating back to the Upper Palaeolithic Age, and more specifically to the Aurignacian period (30,0 0 0 BCE), although this artform reached its zenith during the Magdalenian period around 15,0 0 0 BCE e.g., Altamira and Lascaux caves [2–4] . The first wall paintings associated with buildings appeared later, dur- ∗Corresponding author. E-mail address: [email protected] (D. Jiménez-Desmond) . ing the Neolithic (50 0 0 BCE). These were painted on walls covered with blocks of raw earth rendered with mud or clay [5 , 6] . However, it was not until Antiquity that the first traditional wall paintings appeared: i.e., murals painted on specially prepared surfaces made of traditional mortars, such as lime or gypsum-based ones [7 , 8] . The walls to which the layers of mortar were applied were made of varied masonry materials, including natural stone and artificial materials such as adobe, rammed earth and fired bricks [5 , 6] . Before proceeding, we must distinguish between the terms mortars, stucco and plaster when it comes to wall paintings. The European Standard UNE-EN 16572 (2015) [9] defines the term mortar as a material composed of a mixture of one or more binders, aggregates, water, and possible additives used as a bedding, jointing, and surface coatings which subsequently sets and forms a rigid material; stucco is more precisely defined as a mortar used for decorative purposes used on facades and building interiors as opposed to plaster which is used exclusively in reference to internal coatings. As stucco is a broader term, authors will refer to it when describing wall painting mortar coatings. Throughout history and regardless of their specific role in the building, mortars and stuccoes have been mainly composed of: i) a binder, which binds the different com ponents together by means of chemical transformahttps://doi.org/10.1016/j.culher.2023.11.018 1296-2074/© 2023 The Author(s). Published by Elsevier Masson SAS on behalf of Consiglio Nazionale delle Ricerche (CNR). This is an open access articleundertheCC BY-NC-ND license ( http://creativecommons.org/licenses/by-nc-nd/4.0/ ) D. Jiménez-Desmond, J.S. Pozo-Antonio and A. Arizzi Journal of Cultural Heritage 66 (2024) 166–186 tions in their composition; ii) one or more aggregates with different grain sizes providing volumetric stability during the drying process and final mechanical strength; iii) (when applicable) additives and admixtures, i.e. materials added to the mortar in small quantities in order to improve existing properties or add new ones; and iv) water, to mix the different components into a fresh mix that can be applied to the masonry [5 , 10–13] . These components are also found in the mortars used in frescoes. The decoration or artwork was painted onto the last layer of mortar using a range of pigments, defined as a finely ground, coloured powder which is mixed with a binder to create paints that add colour to artworks [14–17] . The binders traditionally used in mortars were clay, lime, and gypsum, although this varied according to the historic period and the geographic area [12] . Lime and gypsum were the most used in ancient times (80 0 0–70 0 0 BCE) in the Middle East, although, it was not until the Greek-Roman period (10 0 0 BCE) that their use spread beyond this region [5 , 6 , 8 , 12] . However, lime was the chosen binder par excellence in the manufacture of mortars in Antiquity (in the Mesopotamian, Egyptian and Mediterranean regions) and in the Middle, Modern and Contemporary Ages until the arrival of Portland Cement in the nineteenth century [18] . As regards the wall painting techniques used, they can roughly be divided into fresco (from the Italian word affresco , derived from the adjective ‘fresh’) and secco (meaning ‘dry’). In the former, the pigments are painted onto the outer layer of mortar (traditionally made with an air-hardening lime of calcitic composition, i.e., fat lime ) when it is still wet. This enables the pigments to bond to the surface via a carbonation process, i.e., calcium hydroxide reacts with atmospheric CO2 to form calcium carbonate [19] . In secco , by contrast, the pigments are fixed by mixing them with an organic binder and then applied to the dry mortar surface. The mortars are not all lime-based, as mixed (made for example with a mixture of lime and gypsum) or gypsum mortars can also be used. We should also mention other variations such as mezzo fresco ( mezzo meaning ‘half’ in Italian) in which pigments, previously mixed with lime water, are applied onto a dry mortar, and fixed to the surface by the reactivation of the carbonation process [7 , 8 , 20] . In this paper we review the fresco technique, considered one of the oldest forms of painting and therefore of cultural heritage, since it first appeared in the second millennium BC until the present day. To this end, authors will examine the Mediterranean region. This area must be understood not only as the countries surrounded by the Mediterranean Sea but also those territories that make up Western and Eastern Mediterranean, the Adriatic-Ionian region and those countries influenced by the Mediterranean during history (i.e., Switzerland, Macedonia, Bulgaria and Romania) [21 , 22] . Whilst extensive research has been conducted into wall painting techniques, no specific review has been carried out of the fresco technique. In any case, identifying the pictorial technique ( a fresco, a secco, or a mezzo fresco ) often presents problems related to the identification of possible organic binders. In this way, it has been observed that the often-used assignment of some mural paintings to the fresco technique may not always be entirely justified, especially in the presence of unstable pigments (i.e., copper or lead-based). With this in mind, this review aims to: - Carry out a compilation of the bibliography on fresco wall painting in the Mediterranean area from a historical, technical, archaeological and archaeometric point of view without delving into stylistic aspects. The aim is to gather as much information as possible on this wall painting technique since it first appeared until the present day. To this end, we will be focusing on the traditional sources (painting treatises and art textbooks) which include numerous references to the execution technique and the materials used, comparing them with the archaeological evidence. This will enable us to identify common themes and discrepancies. - Gather information on the specific materials used in frescoes (binder, aggregates, and pigments) from recent studies, in this way helping to trace the evolution of the fresco over the course of history. In all, the authors will also be looking closely at the differing opinions in the sources and in recent scientific studies regarding the compatibility of certain pigments with the fresco technique. Evolution of the fresco technique In this section we examine the development of the fresco technique, as described initially in treatises on architecture and painting and later in art textbooks ( Table 1 ), discussing its evolution in terms of execution procedures and materials and comparing these findings with archaeological evidence. For this purpose, the review has been divided into five historic periods (Prehistory, Classical Antiquity, Middle Ages, Modern Age and Contemporary Age) where the evolution of the fresco technique is discussed throughout time and considering the different civilisations that have existed in the Mediterranean. The fact that some of the different cultures overlap in time, especially during Classical Antiquity (e.g., Greek and Phoenician), implies that a continuous timeline has not always be followed in this review. In view of the numerous contradictions identified regarding the use of pigments in frescoes, Table 2 lists the main pigments referred to in painting treatises and those found through archaeological evidence, with some notes on terminology. When possible, three real examples of the use of each pigment in fresco wall painting has been included, bearing in mind the difficulty in finding examples where 20th century pigments have been used (e.g., Guignet green and titanium white). In addition, it should also be noted that in some of the examples given, analyses that can rule out the presence of organic binders may have not been appropriately carried out. Therefore, the presence of some of the pigments (e.g., copper-based) should be seen with caution. Prehistory The use of lime-based mortars dates back to the 8th or 7th millennium BC, when they were widely used in the Near and Middle East [5] . Studies of the wall paintings in the Yarim-Lim Palace (Antakya, Turkey), found that the preliminary drawing was painted while the mortar was still damp, effectively creating what is thought to be the first fresco executed in the Mediterranean area [23 , 24] . There are also various examples of frescoes during the Bronze Age (3300 –1200 BCE) [25] . These were used to decorate the walls and the floors of the houses of the elite in the Mediterranean region, and often included scenes depicting power and authority [26] . The oldest surviving frescoes deliberately executed as such, exhibiting a high degree of technical skill [16] , date from around the second millennium BC. These examples of Cretan Minoan art can be found in the Palace of Knossos (Crete, Greece) [25 , 27–29] or Pylos (also in Greece) [30 , 31] . However, it must be considered that intercultural exchanges occurred at the time between the Aegean culture (i.e., Crete, the Cyclades, the Greek mainland south from Thessaly, including the Peloponnese, and Macedonia, Thrace, and western Anatolia) and other Mediterranean territories. For instance, based on stylistic comparisons, the wall paintings of Tell el-Dab’a (Avaris, Egypt) are considered as Minoan-style frescos [32] , regarded as a good example of the prevailing style at that time [33] . In relation with the materials used in these thought-to-be frescoes, calcite (CaCO3 ) appears as the main mineral in the lime plaster, with small amounts of dolomite (CaMg(CO3 )) and crushed shell [34 , 35] . Regarding the pigments 167 D. Jiménez-Desmond, J.S. Pozo-Antonio and A. Arizzi Journal of Cultural Heritage 66 (2024) 166–186 Table 1 Main references and guiding elements in treatises about plaster preparation techniques in the period under consideration. Historical period Author/work Binder Aggregates Slaking period Number of layers L:S∗ Arriccio Intonaco Classical Antiquity (IV BC –I BC) Pliny the Elder Lime Sand; Marble powder Three years Five 3 layers –1:3 2 layers –1:2 Marcus Vitruvius Lime Coarse sand; Crushed brick; Pozzolans; Marble powder Three years Seven 4 layers –1:3 3 layers –1:2 Medieval Age (V –XV) Anonymous, Mappae Clavícula Lime River sand; Crushed brick; Marble powder Not mentioned Not mentioned 1:3 ( + 1/3 crushed brick + 1/6 straw + 2/6 pig fat) 1:2 ( + 1 olive oil + 1 chopped tow) Cennino Cennini Lean Lime Coarse sand; River sand; Marble powder; Crushed brick Not mentioned Three 2 layers - 1:2 1:2 Leon Batista Alberti Lime (mixed with gypsum in dry places) River sand; Crushed brick; Marble powder > Three months Three 1 layer Not mentioned 2 layers Not mentioned Modern Age (XV – XVIII) Giorgio Vasari Lime Marble powder; Pozzolanic sand Not mentioned Not mentioned Not mentioned 1:2 Andrea Pozzo Lime River sand 6–12 months Two 1:3 1:2 Antonio Palomino Lime Good quality and free-clay sand 4–6 months Three Not mentioned Not mentioned Contemporary Age (XVIII –present) Max Doerner Air-hardening lime River sand without micas; Marble, limestone and quartz sands > Two years Four 2 layers - 1:3 2 layers –1:2 and 1:1 James Ward Air-hardening lime Gritty sand; Well-washed river sand One year Two 1:2 1:3 Ralph Mayer Slaked lime paste Coarse sand; Marble powder 3–6 months Three 2 layers - 1:3 and 1:2 1:1 Antoni Pedrola Air-hardening lime ( < 5 % MgO) Coarse and fine quartz aggregate; Marble powder > Nine months Two 1:2 1:1 Josep Minguell Cardenyes Air-hardening lime River sand without micas; Marble powder > Three months Four 2 layers - 1:3 and 1:4 2 layers - 1:2 and 1:2 L:S∗: lime-to-sand ratio according to the number of layers. 168 D. Jiménez-Desmond, J.S. Pozo-Antonio and A. Arizzi Journal of Cultural Heritage 66 (2024) 166–186 Table 2 Main pigments found on fresco paintings in the Mediterranean area. Evidence of their apparent use in the fresco technique are included. Colour Pigment Nature Pigment composition Approx. period of use Evidence Red Red ochre; Red earth Inorganic Natural Hematite, Fe2 O3 + impurities (e.g., quartz, clays, anatase/rutile) Ancient Age – Present - Saint Jeremiah Monastery (4th c.)(∗) (Saqqara, Egypt) [181] - Roman wall paintings from Castulo (Jaen, Spain) [182] - Frescoes in the tablinum of the House of the Bicentenary at the archaeological site of Herculaneum (Pompei, Naples, Italy) [183] Lead red; Minium a Inorganic Synthetic Minium, Pb3 O4 Ancient Rome (500 BCE) – Modern Age - St. Alexander catacombs (2nd - 5th c.) (Rome, Italy) [184] - Twelve Byzantine churches (10th–15th c.) (Mani Peninsula, Greece) [185] -RomanwallpaintingsfromCastulo (Jaen, Spain) [186] Cinnabar b Inorganic Natural Cinnabar, HgS, + impurities (e.g., quartz, dolomite, pyrite) Ancient Greece (1600 BCE) –20th century - Etruscan Tarquinia wall painted tombs (Tuscia, Italy) [61] - Wall paintings at the Domus of Octavius Quartio (Pompei, Naples, Italy) [187] - San Isidoro del Campo Monastery (15th c.) (Seville, Spain) [188] Vermillion b Inorganic Synthetic Cinnabar, HgS Medieval Age – 20th century - Wall paintings in Saint Orso Priory palace (15th c.) (Aosta, Italy) [105] - Wall paintings in Aosta Valley (mid-15th c.) (Aosta, Italy) [107] - Wall paintings in Santa María de Lemoiz (Basque Country, Spain) [189] Litharge c Inorganic Synthetic Litharge, PbO Ancient Age – 1800 - Roman wall paintings from Monte d’Oro (Rome, Italy) [190] - Medieval wall paintings from the Monastery of Saint Baudelio (Soria, Spain) [191] - Wall paintings in Saint Orso Priory palace (15th c.) (Aosta, Italy) [105] Green Green earth d Inorganic Natural Fe-containing clay minerals: celadonite or glauconite + minerals of the smectite and chlorite group Ancient Age – Present - Fresco wall painting of Mariano de Cossío (Canary Islands, Spain) [192] - Church of the Anunciation of Mary (13th – 15th c.) (Crngrob, Slovenia) [193] - Frescoes in the tablinum of the House of the Bicentenary at the archaeological site of Herculaneum (Pompei, Naples, Italy) [183] Malachite e Inorganic Natural Malachite, Cu(CO3 )(OH)2 Natural: Ancient Age (2600 BCE) – 19th century Synthetic: 17th century –Present - Saint Jeremiah Monastery (4th c.) in Saqqara, Egypt [112] - Wall paintings at the Domus Valeriorum (Rome, Italy) [194] - Roman site of Cambre (La Coruña, Spain) [111] Chrysocolla e Inorganic Natural Chrysocolla, (Cu,Al)4 H4 (OH)8 Si4 O10 ·nH2 O Ancient Age – Present - 2nd m.(∗) BC frescoes from the Mycenaen Palace of Pylos [195] - 12th c. frescoes from Novalesa Abbey (Turin, Italy) [121] - 13th c. frescoes beneath Siena cathedral (Italy) [173] Verdigris Inorganic Synthetic Hoganite, Cu(CH3 –COO)2 ·2Cu(OH)2 Ancient Greece and Rome – 19th century - Madonna and Child enthroned with Saints wall painting in St. Augustine church (Siena, Italy) (14th c.) [196] - Medieval frescoes from Saint Baudelio Monastery (Soria, Spain) [191] Viridian f Inorganic Synthetic Cr2 O3 ·2H2 O Beginning of 19th century - Present - The Crucifix Chapel of Aci Sant’Antonio (Sicily, Italy) [148] - Different paintings by Henrique Pousao (1859–1884) (Portugal) [197] Guignet green f Inorganic Synthetic Cr3 BO6 1838/1859 – Present - 20th c. Gino Severini (1833–1966) wall paintings (Semsales, Switzerland) [166] Chromium green Inorganic Synthetic Skolaite, Cr2 O3 1860 –Present - Vincenzo Pasqualonis (1820–1880) wall paintings in Saint Nicola (Carcere, Rome, Italy) [161] - Juan Miguel Sánchezs wall Paintings in the Carmen Chapel (Seville, Spain) [198] ( continued on next page ) 169 D. Jiménez-Desmond, J.S. Pozo-Antonio and A. Arizzi Journal of Cultural Heritage 66 (2024) 166–186 Table 2 ( continued ) Colour Pigment Nature Pigment composition Approx. period of use Evidence Blue Egyptian blue g Inorganic Synthetic Cuprorivaite, CaCuSi4 O10 Ancient Age – Medieval Age (13th century) - Knossos Palace (Crete, Greece) [199] - Wall paintings at the Domus of Octavius Quartio (Pompei, Naples, Italy) [187] - Wall paintings at the Domus Valeriorum (Rome, Italy) [194] Natural ultramarine h Inorganic Natural Lazurite, 3Na2 O ·3Al2 O3 ·6SiO2 ·2Na2 S, + impurities Ancient Age –end of the 18th century - Santa Maria di Cerrate abbey (12th-13th c.) (Lecce, Italy) [200] - Byzantine frescoes at Chora Church (Istanbul, Turkey) [201] - Servilia Roman tomb (Carmona, Seville, Spain) [202] Azurite e Inorganic Natural Azurite, Cu(CO3 )2 (OH)2 Natural: Ancient Age (2600 BCE) – 18th century Synthetic: 17th century –Present - Assumption of the Virgin Mary (1526–1530) dome (Cathedral of Parma, Italy) [158] - Byzantine wall paintings in the Protaton Church (Mount Athos, Greece) [203] - Regina Martirium dome in the Pilar Basilica (Zaragoza, Spain) [204] Smalt blue Inorganic Synthetic Blue potassium glass composed of SiO2 (65–72 %), K2 O (10–21 %), CoO (2–18 %) + impurities [160] 15th century – 18th century - Assumption of the Virgin Mary (1526–1530) dome (Cathedral of Parma, Italy) [158] -Wall paintings at Saint Girolamo Chapel (1560–1564) in the SS. Annunziata Church (Florence, Italy) [205] - Antonio Palominos (1655–1726) wall paintings in the Real Parroquia de los Santos Juanes (around 1697) (Valencia, Spain) [151] Synthetic ultramarine h Inorganic Synthetic Lazurite, 3Na2 O ·3Al2 O3 ·6SiO2 ·2Na2 S 1828 –Present - Vincenzo Pasqualonis (1820–1880) wall paintings in Saint Nicola (Carcere, Rome, Italy) [161] - Wall paintings on the Almada Negreiros building (Lisbon, Portugal) [178] - Fresco wall painting of Mariano de Cossío (Canary Islands, Spain) [192] Yellow Yellow ochre; Yellow earth Inorganic Natural or synthetic Limonite, FeO(OH) ·nH2 O (mixture of iron-containing oxo-hydroxides as e.g., goethiteFeO(OH), ferrihydrite Fe c + 10 O14 (OH)2 , jarositeKFe3 (OH)6 (SO4 )2 ) or goethite (with quartz and clay minerals) Natural: Ancient Age –Present Synthetic: 17th-18th century –Present - Knossos Palace (Crete, Greece) [199] - Roman wall paintings from Castulo (Jaen, Spain) [182] - Frescoes in the tablinum of the House of the Bicentenary at the archaeological site of Herculaneum (Pompei, Naples, Italy) [183] Naples yellow i Inorganic Synthetic Bindheimite, Pb2 Sb2 O7 Ancient Age – 19th century Industrially manufacture since 1850 - Wall paintings from a building complex (Caelian Hill, Rome, Italy) [89] - Frescoes painted by Antonio Palomino (1655–1726) (Valencia, Spain) [139] - Wall paintings in the Baños de Doña María de Padilla (1565–1579) (Royal Alcázar of Seville, Spain) [188] Orpiment Inorganic Natural or synthetic Orpiment, As2 S3 Ancient Age –8th century Synthetic: 17th century - Paestum archaeological site wall paintings (Capaccio, Salerno, Italy) [206] - Vincenzo Pasqualonis (1820–1880) wall paintings in Basilica of S. Nicola (Cercere, Rome, Italy) [161] - Medieval Islamic wall paintings of Al-B¯ ım¯ arist¯ an Al-Mu’ayyidi (Cairo, Egypt) [135] Massicot d Inorganic Synthetic Litharge, PbO Ancient Age – 19th century - Wall paintings (12th c.) from the Monastery of Santa Maria delle Cerrate (Puglia, Italy) [207] - Medieval wall paintings (10th-14th c.) of the Santi Stefani crypt at Vaste (Lecce, Italy) [208] - Wall paintings in Saint Orso Priory palace (15th c.) (Aosta, Italy) [105] Chrome yellow Inorganic Natural or synthetic Crocoite, PbCrO4 Middle Ages – Present Synthetic: 1778 - Vincenzo Pasqualonis (1820–1880) wall paintings in Saint Nicola (Carcere, Rome, Italy) [161] - 13th c. frescoes beneath Siena cathedral (Italy) [173] - 20th c. Pentecostes by Julio Resende (1917–2011) at the Church of Nossa Senhora da Boa Esperança (Canaviais, Portugal) [209] ( continued on next page ) 170 D. Jiménez-Desmond, J.S. Pozo-Antonio and A. Arizzi Journal of Cultural Heritage 66 (2024) 166–186 Table 2 ( continued ) Colour Pigment Nature Pigment composition Approx. period of use Evidence Brown Raw sienna Inorganic Natural Goethite, FeO(OH) + quartz + clays Ancient Age – Present - Saint Nicholas Anapafsas church (Meteora, Greece) [210] - Roman wall paintings in Villa della Piscina (Rome, Italy) [211] Burnt sienna j Inorganic Natural Hematite, Fe2 O3 + quartz + clays Ancient Age – Present - Saint Nicholas Anapafsas church (Meteora, Greece) [210] - Roman wall paintings from archaeological sites (Judea, Israel) [212] Raw umber Inorganic Natural Iron and manganese oxides + quartz + calcite + clays Ancient Age – Present - Saint Nicholas Anapafsas church (Meteora, Greece) [210] - Wall paintings (18th c.) from the Convent of Saint António dos Capuchos (Estremoz, Portugal) [213] Burnt umber j Inorganic Natural Iron and manganese oxides + quartz + calcite + clays Ancient Age – Present - Saint Nicholas Anapafsas church (Meteora, Greece) [210] - Wall paintings (18th c.) from the Convent of Saint António dos Cauchos (Estremoz, Portugal) [213] Purple Caput Mortuum k Inorganic Synthetic Hematite, Fe2 O3 + kaolinite, Al2 Si2 O5 (OH)4 Ancient Rome – Present Synthetic (Mars Violet): since 18th century - Byzantine wall paintings in the Protaton Church (Mount Athos, Greece) [203 , 210] - Servilia Roman tomb (Carmona, Seville, Spain) [202] White Lime white l Inorganic Natural Calcite/aragonite (CaCO3 ), dolomite (CaMg(CO3 )2 ), chalk (white clay), diatomite (SiO2 ·nH2 O) Ancient Age – Present - Roman wall paintings in Thamusida (Rabat, Morocco) [214] - Medieval frescoes from the Žiˇ ca monastery (Serbia) [102] - St. Alexander catacombs (2nd - 5th c.) (Rome, Italy) [184] Lead white Inorganic Synthetic Hydrocerussite, 2PbCO3 ·Pb(OH)2 Ancient Age – mid-19th century - Wall paintings (12th c.) from the Monastery of Santa Maria delle Cerrate (Puglia, Italy) [207] - Wall paintings in Saint Orso Priory palace (15th c.) (Aosta, Italy) [105] - 13th century frescoes beneath Siena cathedral (Italy) [173] Barium white Inorganic Synthetic Baryte, BaSO4 Around 1782 – Present - 20th c. Pentecostes by Julio Resende (1917–2011) at the Church of Nossa Senhora da Boa Esperança (Canaviais, Portugal) [209] -Crowning of the Virgin Mary from artist Vittorio Fagnano (18th c.) at Beata Vergine del Pilone (Piemonte, Italy) [215] Zinc white Inorganic Synthetic Zincite, ZnO 1834 –Present - 20th c. Gino Severini (1833–1966) wall paintings (Semsales, Switzerland) [166] - Rejoicing querubs from artist Vittorio Fagnano at Beata Vergine del Pilone (Piemonte, Italy) [215] - Vincenzo Pasqualonis (1820–1880) wall paintings in Saint Nicola (Carcere, Rome, Italy) [161] Titanium white Inorganic Synthetic Anatase, TiO2 1916 –Present - 20th c. Pentecostes by Julio Resende (1917–2011) at the Church of Nossa Senhora da Boa Esperança (Canaviais, Portugal) [209] Black Carbon black m Inorganic Synthetic Carbon (C) Ancient Age – Present - Knossos Palace (Crete, Greece) [199] - Wall paintings at the Domus of Octavius Quartio (Pompei, Naples, Italy) [187] - Roman wall paintings from Castulo (Jaen, Spain) [186] Lampblack m Inorganic Synthetic Carbon (C) Ancient Age – Present - Church of the Holy Mother of God Hodegetria in Pec Monastery (14th c.) (Peja, Serbia) [216] - Paestum archaeological site wall paintings (Capaccio, Salerno, Italy) [206] - Medieval wall paintings from the Peregrina Convent (Leon, Spain) [217] ( continued on next page ) 171 D. Jiménez-Desmond, J.S. Pozo-Antonio and A. Arizzi Journal of Cultural Heritage 66 (2024) 166–186 Table 2 ( continued ) Colour Pigment Nature Pigment composition Approx. period of use Evidence Ivory black Inorganic Synthetic Carbon (C) Ancient Age – Present - Paestum archaeological site wall paintings (Capaccio, Salerno, Italy) [206] - Wall paintings from the Roman archaeological site of Cuma (Campania, Italy) [218] - Roman wall paintings from Castulo (Jaen, Spain) [182] ∗c.: century; m.: millenia. a Minium secundarium in Latin. b Minium in Latin. Cinnabar is the natural pigment whilst vermilion is the synthetically obtained. It should be noted that the term vermilion has been used in some studies without prior analysis to differentiate whether it is the natural or artificial variant (e.g., the presence of impurities). Therefore, the examples given should be treated with caution. c Litharge (reddish orange) and massicot (yellow), both lead oxide, are often confused or used synonymously in literature. Both are obtained from lead white (litharge around 330 °C and massicot 600 °C) although they are also found as minerals. d Also known as Verona green. Creta viridis in Latin. e Green malachite was known as Chrysocolla in Greek and Latin. However, chrysocolla is an independent pigment of copper silicate hydroxide hydrate. Synthetic malachite is known as green verditer, as well as synthetic azurite in known as blue verditer. f Guignet green is sometimes improperly confused with Viridian or Emerald green. g During ancient times it had different nomenclatures: c aeruleum aegyptium; vestorianum; puteolanum in Latin. h Caeruleum scythicum in Latin. Known as ultramarine during the Middle Ages, it was obtained from the mineral lapis lazuli. In the present we differentiate between natural and artificial ultramarine. i It must be pointed out that even though Naples yellow was synthetically obtained in 1850, it was already artificially prepared in Antiquity. j The so-called “burnt” pigments are obtained from calcination of their raw counterparts, i.e., burnt sienna from raw sienna and burnt umber from raw umber. k Usta purpurissimum in Latin. l Bianco sangiovanni in Italian, a calcium carbonate that can appear in the form of calcite, vaterite or aragonite. Nowadays, calcite is mainly used as an inert pigment, mixed with other mineral pigments [15 , 203] . m Both carbon black and lampblack are obtained from burning fuels (gas, fats, asphalt, etc.). However, lampblack is obtained specifically by burning oil in a lamp. used during the Bronze Age, red and yellow ochres (i.e., hematiteFe2 O3 -, goethiteFeO(OH)- or limoniteFeO ·nH2 O-), carbon black and Egyptian blue (CaCuSi4 O10 ) were used [28 , 34 , 36] , probably obtained from local sources [37] . Other compounds have been found to be used as blue pigments during this period such as iron-rich minerals (e.g., riebeckite-Na2 Fe2 + 3 Fe3 + 2 (Si8 O22 )(OH)2 -) [37] . Classical Antiquity The painting technique later spread throughout Ancient Greece (1200 – 323 BCE), as can be seen for example in Women at work at the Akrotiri archaeological site (Santorini, Greece) [38] . During the Hellenistic period (4th –3rd c. BC) there was a phenomenon of decorating tombs with fresco wall paintings such as the Tomba di Cavalieri (Ancient Apulia, southern Italy) [39] or several tombs from Ancient Thrace (southern Bulgaria). In the latter, up to three layers of plaster were encountered [40] . In short, archaeological evidence from this period shows the high quality of the rendering on the mortar surface during this period, as can be seen in the hunting scene frieze in the Tomb of Philip (Vergina, Greece), and in other frescoes from the Macedonian period [41] . In terms of fresco pigments, the main contributions made by the Greeks were lead white (2PbCO3 ·Pb(OH)2 ) and lead red (Pb3 O4 ), the latter known as minium after the River Minho in northern Spain [42] . Both were found in a Greek villa in the archaeological site of Tel Anafa (Galilee, Israel) together with exported pigments like Egyptian blue or yellow ochres, i.e., earth pigments from hydrated forms of iron oxide, which the Greeks called ochra [43] . Even though these pigments may have been exported to Greece, there is evidence that Egyptian blue was one of the main products manufactured during the Hellenistic period in the ancient town of Kos (Island of Kos, Greece) [44] together with other earth pigments such as hematite-based red earth (Fe2 O3 ), yellow ochres (goethite-FeO(OH)-, ferrihydrite-Fe3 + 10 O14 (OH)2 - and jarosite-KFe3 (SO4 )2 (OH)6 -) and green earth (Fe-containing clay minerals: celadonite-K(Mg,Fe2 + )Fe3 + (Si4 O10 )(OH)2 )- or glauconite- (Fe3 + ,Al,Mg)2 (Si,Al)4 O10 (OH)2 -, and minerals from the smectite and chlorite group) [44] . It must also be considered the use of local minerals as pigments during this period. Even though the wall paintings at the monumental cist tomb in Pella (Macedonia, Greece) are thought to be executed following a secco technique, the minerals vanadinite (Pb5 (VO4 )3 Cl) or conichalcite (CaCu(AsO4 )(OH)) were encountered mixed with lead white [45] . These two minerals were also found in tombs from Hellenistic Alexandria (Egypt) [46] . In addition, pigment manufacture is well documented during the Hellenistic period in Ancient Greece where Liber De Lapidibus , a treatise by Theophrastus (372 – 286 BCE), is of particular interest in that it summarizes the state of knowledge on stones, minerals, gems, and earths [47 , 48] . It describes the production of two ancient pigments, Egyptian blue ( egyptios kyanos ) and lead white ( psimythion ) [49] . Throughout the 9th and 8th centuries BC, people from the Mediterranean Levant settled in different territories bathed by the Mediterranean (Cyprus, the Maghreb, Sicily, Sardinia, Ibiza and the Iberian Peninsula) giving rise to the Phoenician culture [50] , known as Punic from the 5th century onwards. Carthage (actual Tunisia) became the major political power in the Mediterranean until Roman conquest (2nd century BC) [50] . Despite their influence in the Mediterranean, wall painting was rare in Phoenician contexts, surviving principally in tombs [51] . On the one hand, one of the few examples that can be related to this culture is the so-called Sidonian tomb at Maresha (Shfela, Israel), where the ornamental decoration can be related to Hellenistic and Phoenician styles [52] . On the other hand, the use of cinnabar was found in several burial chambers in the region of Kroumirie (Western Tunisia) [53] , known to be used together with hematite as a cosmetic powder during this period [54] . The Sidonian tomb decorative style and the use of cinnabar in Kroumirie are good evidence of the intercultural exchanges that were happening at the time. Probably, the most interesting contribution to posterior painting is the so-called Punic wax, invented by Carthaginians for their ships [55] . Its elaboration and use were described by Pliny and Vitruvius as a binder (painting technique known as ganosis ). Although it has been found as binder in Roman art [55] , beeswax has only been detected in ceramic vessel in Punic Sardinia [56] , but not in wall paintings. The fresco technique was later employed by the Etruscans (around 800 –300 BCE) also to decorate their tombs [57] , as in The Tomb of the Swimmer in the Paestum archaeological site (Salerno, 172 D. Jiménez-Desmond, J.S. Pozo-Antonio and A. Arizzi Journal of Cultural Heritage 66 (2024) 166–186 Italy) [58] . Due to the posterior Roman occupation, not many wall paintings remain from the Etruscan period. The few remnants that have survived are those preserved in burial sites, i.e., necropolis [59–61] . Tarquinia (Viterbo, Italy) is one of the most important due to its extension (up to 200 tombs), highlighting The tomb of Orcus where a mixture of cinnabar and red ochre (hematite) was encountered, as well as the presence of Egyptian blue or yellow ochre [60] . Regarding the preparation of the wall, Steingräber clearly distinguished between three periods [62] : i) the Orientalizing period (7th and 6th c. BC), of Asian and Corinthian influence, with the use of three basic colours (red, yellow and black) applied directly onto a stone wall; ii) the Archaic period (6th and 5th c. BC), with a pictorial palette enriched with green and blue pigments applied in a rudimentary form of a fresco onto a thin layer (1 –3 mm) made of clay, a non-specified stone powder and vegetable fibres, followed by a thin layer of lime paste; and iii) the Hellenistic period (4th and 3rd c. BC) with a thicker layer (up to 3 cm) composed of three layers i.e. the bottom of pozzolana, the second of limestone and siliceous sand, and the last of calcium carbonate. The technique was substantially improved during the Roman period (around 750 BCE – 476 AC) and spread throughout the Empire. Sometimes the frescoes were retouched a secco , using four clearly differentiated artistic styles known as the first, second, third and fourth Pompeian styles (the first inherited from Hellenistic Greeks [63] ). The tradition of combining fresco and secco was rather recurrent, as seen in the Roman city of Emona (actual Ljubljana, Slovenia) [64] . The most representative examples of fresco wall paintings due to their exceptional state of preservation are in the Pompeii [65 , 66] , Herculaneum [67] and Stabiae [68] archaeological sites (Naples, Italy), which are outstanding not only in terms of quantity, but also of quality [6] . Pliny the Elders (23 –79 CE) Natural History [69 , 70] is considered an essential source for those wishing to understand the role played by wall paintings in Roman society, described as expressions of the luxury and wealth of the dominus as seen in the Mt. Vesuvius area. He also mentions numerous distinguished Greek painters (i.e., Panaenus, Apollodorus or Apelles among others) [8 , 71] , although for our purposes the most valuable information appears in the last two chapters which deal with mineralogy and art [70] . Another important contribute into the knowledge of Roman mortars and stuccoes is Greco’s work [72] , where he compiles Latin bibliographical sources (from the 2nd c. BC until 5th c. AD) regarding this topic. Perhaps the most important bibliographical source on architecture in ancient times is Vitruvius (80–70 –15 BCE) and his De architectura [73 , 74] . Composed of ten books, the seventh (Vitr. arch. VII) contains information on the stucco technique and the preparation of the walls [8 , 74] . Vitruvius also specified that lime has three functions: a) as a bond between stones and bricks; b) for plastering (stucco) as a means of protecting and/or decorating surfaces; and c) as a base for mural painting, flooring, and mosaics [12] . According to Vitruvius, wall paintings should be composed of seven layers. However, only in Rome there are few surviving examples that seem to have followed this rule [75] . And whilst in various provinces of the Roman Empire (e.g., Ostia Antica in Italy, Carnuntum in Austria and Ephesus in Turkey) the Vitruvian rule of applying more than one layer of intonaco (explained further bellow) was followed [76] , this did not always occur in other provinces. For instance, a series of Roman wall paintings from Aquileia (Italy) which span a period of over six centuries have shown that they completely differ between one another regarding the number of mortar layers and their thickness [77] . Yet, the materials used were always the same and from local provenance [77] . As regards the constituent materials, during the Roman Empire it was easy to locate and extract suitable calcitic stone materials ( lapidem bonum or ‘good stone’). The method for obtaining the lime consisted of calcinating calcitic stone such as white stone ( albo saxo ), travertine ( tibertino ), etc., at a temperature of around 900 °C in order to obtain quicklime or calcium oxide (CaO). The person responsible for firing the stone was known as the calcarius [73 , 74 , 78] . This process is well described by the Roman author Marcus Porcius Cato (Cato the Elder: On agriculture, XXXVIII [5] ). To obtain a lime mortar, quicklime ( calx viva ) must be mixed with water in a slaking process to produce slaked lime (referred to as calx macerata by Vitruvius [74] ) or calcium hydroxide (Ca(OH)2 ) via an exothermic reaction. Different ancient sources generally recommend slaking the lime for between two and three years [6] to obtain a high-quality slaked lime. This process must be carried out to remove any lumps of calcium oxide that could damage the mortar due to later hydration [5 , 73] . The aggregates used during this period varied according to their geological area, as most came from local sources [79] . In Roman construction, caementa was understood as coarse aggregates [18] . It was also known that, if not properly and repeatedly washed, using sea sand ( harena marina ) as an aggregate caused the formation of saline efflorescence, which is why river sand ( harena fluvialis ), e.g., quartz-based sands, was preferred. However, other aggregates such as pozzolanic sands ( harena fossicia ) and crushed terracotta ( testae tunsae ), characteristic of the Roman period, can also be found in mortars [79] . According to Vitruvius, marble powder ( opus marmoratum ) could also be used in the final layers of stucco to provide a whiter, smoother, more lustrous appearance [73] . It should be noted that the use of marble powder can be traced back to the Mesopotamian period, as in the palace of Yarim-Lim in the archaeological site of Alalakh (Antakya, Turkey) [6 , 80] . However, no petrographic characterisation was carried out in these studies to precisely identify the type of aggregate based on the morphology, structure, and size of the crystals, and therefore the exact lithotype cannot be asserted. The execution procedure of a wall painting was perfected during the Roman era where stuccoes were referred as opus tectorium, opus albarium or gypsum depending on material composition, workmanship and utility (i.e., inside or outside of the architectural building) [81] . In relation to wall paintings, the master builder ( redemptor ) was accompanied by specialized craftsmen ( tectors ), who applied successive layers of mortar ( opus tectorium ) to smoothen the rough surface of the wall (i.e., stucco). The mixture of binder and aggregates was known as calx harenata (‘sanded lime’). According to Vitruvius, the procedure was as follows: first the arriccio ( harenatus ), composed of several layers of mortar, was applied to smooth the rough surface of the base wall. This was followed by several more layers of intonaco to homogenise the surface and, lastly, the intonachino or painting layer. The layers were applied with an increasingly fine-grained aggregate from the innermost to the outermost layer [6 , 16 , 81] . Some authors, such as Vitruvius and Faventinus, also refer to an additional final stage in which the final layer was polished ( politiones ) to make it more resistant [73] . The outlines of the decorations were drawn by wall painters ( pictores parietarii ) and then a figure painter ( pictor imaginarius ) carried out the more complex artwork [8 , 73] . The fresco painting itself was created with pigments (from the Latin pigmentum ) that had previously been mixed with water. These were applied with a brush onto the fresh fine-grained limebased plaster (calcium hydroxide, Ca(OH)2 ) or intonaco . The pigment particles became bonded to the surface when the calcium hydroxide reacted with atmospheric carbon dioxide (CO2 ), so creating a compact, resistant film of calcium carbonate (CaCO3 ) that protected the pigment [7 , 8 , 82] , so making the paints more durable [8 , 14] or ‘permanent’ according to Vitruvius [6] . Ever since ancient times, inorganic pigments (minerals) have been preferred to organic pigments in fresco painting because they can withstand the alkaline environment of lime mortars [7] . Inorganic pigments are either native earths or calcined native earths, obtained from me173 D. Jiménez-Desmond, J.S. Pozo-Antonio and A. Arizzi Journal of Cultural Heritage 66 (2024) 166–186 chanical processing and separation. There were also inorganic synthetic colours obtained artificially from chemical reactions between different raw materials [16 , 83] . Most of the traditional pigments used since ancient times are still a common feature of the painters palette today, although some have fallen into disuse [84] . Romans used the same pigments as the Egyptians and Greeks i.e., Egyptian blue, named by the Romans as Alexandrian blue, among other terminologies, or green-earth pigments, the latter were obtained by the Etruscans from glauconite, celadonite and chlorite [85 , 86] . It is thought that the earliest Roman frescoes were painted with pure pigments such as yellow and red ochres, carbon blacks, and whites such as calcite/aragonite (CaCO3 ), dolomite (CaMg(CO3 )2 ), chalk (white clay), diatomite (SiO2 ·nH2 O) and lead white as mentioned by Pliny and Vitruvius [85 , 87] . One of the most important pigments was cinnabar (HgS) ( cinnabaris in Latin), which according to authors like Vitruvius was obtained from mines in Almaden (Ciudad Real, Spain) [42 , 85 , 88] , and has been found in numerous wealthy Roman houses such as in a domus on the Caelian Hill (Rome, Italy) [89] , all around Mount Vesuvius [90] and in other places in the Roman Empire such as King Herods Palace in Jericho (Jerusalem, Israel) [91] . Also, in a fresco fragment preserved at the National Archaeological Museum of Naples (Italy), small particles of lazurite (from the mineral lapis lazuli) were promptly identified [90] , as in the pigment named by Pliny [69] Caeruleum Scythicum . The name derives from the Scythian traders (region located in the northern coasts of the Black Sea) who exported to the Mediterranean [48 , 92] , another clear reference of the commercial trade that happened at the time. As for the production of synthetic pigments, the conversion of magnetite to hematite by calcination was described by Dioscorides (40 –90 BCE) in De materia medica [93] . It therefore seems likely that the Romans obtained various ochres from iron metal [94] , as also happened in Ancient Greece [44] . Many examples of the use of such ochres are drawn out on Table 2 . Vitruvius [74] also explained the reaction whereby acetic acid (vinegar) was poured onto copper sheets so as to obtain copper green, also known as verdigris (Cu(CH3 –COO)2 ·2Cu(OH)2 ) ( aeruca in Latin), considered as a partially organic pigment and therefore theoretically not suitable in alkaline environments [95] . However, it has been found to be part of the pictorial palette of an extensive collection of fresco fragments from several roman villas in Burgos (N Spain) [96] . The purple pigment known as caput mortuum was also identified as part of the palette [96] , a pigment obtained from iron oxides and hydroxides with a high presence of clays (above 80 %) [97] . However, although this pigment was not mentioned by Pliny nor Vitruvius, Pliny does mention the production of a purple pigment called usta, ostrum or usta purpurissimum [69] obtained by heating hematite with acetic acid, covering a wide range of colours (from red to deep violet) [98] . This pigment was indeed encountered, although on RomanoBritish wall paintings, presenting a similar composition to caput mortuum [98] . Finally, Vitruvius [74] also described the production of lead white following a similar procedure to verdigris but with lead sheets [74] , found in wall paintings from the Vesuvian area [90] . Mediaeval age The literature of the Middle Ages often consisted of a compendium of texts reviewing previous ancient works, including technical treatises, recipe books and iconographic catalogues. New considerations were also included, together with theological reflections in that art was regarded as a way of praising God, and colours were used with symbolic meanings [7] . Compared to the Roman tradition of seven layers of mortar, in the early Middle Ages (5th-10th centuries), fewer preparatory layers (normally just two) were applied [7] . Straw could also be used as an admixture, added to the arriccio to facilitate carbonation [99] . This is recurrent during the Byzantine period (312–1453) [100 , 101] and in the Mediterranean [7] , observed in medieval frescoes such as those in the Žiˇ ca monastery (Serbia) [102] . During the long period of the Byzantine Empire the wall painting technique did not change much, except for a more accurate preparation of the wall [7] . One of the oldest and most relevant early mediaeval treatises were Mappae Clavícula (8th century, with its 12th century version known as Phillipps manuscript ), which contains recipes for materials of art and craftsmanship [101 , 103] , and Compositiones variae (late 8th century), also known as the Lucca manuscript [7] . The first describes in detail the preparation of different pigments (e.g., azurite, vermilion, white or red lead) and specifies the use of a lime obtained from the calcination of limestone, travertine or marble [103] . The second focuses on the fresco technique as no organic binder is mentioned in the application of the pigments, consisting of a collection of recipes with instructions on how to prepare and use pigments such as vermillion (HgS), i.e., artificial cinnabar, which was prepared by heating mercury and sulphur, although many of its recipes derive from the classical period [7 , 101 , 104] . This pigment was found in Saint Orso Priory palace in Aosta, Italy [105] . However, the authors make the assignment of the artificial variant on the basis of the absence of impurities (common in natural cinnabar). Therefore, other features should be analysed, such as pigment morphological appearance and particle grain size, being however difficult to differentiate between natural cinnabar and synthetic vermilion when the latter has been obtained by dry method (i.e., by sublimation) [106] . Additionally, the most used copper carbonate pigments used during the Medieval period, that is blue azurite (Cu(CO3 )2 (OH)2 ) and green malachite (Cu2 (CO3 )(OH)2 ), were found in the in the Saint-Maxime oratory (Aosta, Italy) [107] . Their synthetic analogues (manufactured in the 17th century) were known as mountain blue and mountain green respectively [108–110] . In fact, copper carbonate pigments have been used since Antiquity, for example in the Roman archaeological site of Cambre (La Coruña, Spain) [111] and in 4th century Coptic frescoes from Saint Jeremiah Monastery (Saqqara, Egypt) [112] . During the High Middle Ages (11th-13th centuries) and the Romanesque period a fresco, a secco and mezzo fresco techniques were used, although a fresco was by far the most widespread. During this period, wall paintings from different parts of the Mediterranean shared many features, leading some researchers to view fresco as the first international style [7 , 24] . Important art treatises included for example De coloribus et artibus Romanorum by Heraclius (around 11th century), who showed a keen interest in practical aspects of classical Roman art and offered detailed descriptions of pigment recipes [7] . De Diversis Artibus by Theophilus (early 12th century) also deserves a mention as the first treatise written by an artist. It was an important work of reference throughout the Middle Ages and included descriptions of the different methods and painting techniques used by mediaeval artists [113 , 114] . As well as offering instructions on to how to prepare colours, he also provided theological justifications for the use of certain pigments (for example the use of ultramarine to paint the clothes worn by the Virgin Mary) and described the creative process behind Romanesque art [115] . The Pyrenees has a remarkable collection of Romanesque buildings of very high quality, such as the Church of Santa Eulalia de Unha (Lerida, Spain), where vermilion was presumably found together with other red pigments (hematite and lead red) in fresco wall paintings [116] . The murals in the Abbey Church of Saint-Savin-sur-Gatempe (Saint-Savin, France) [117 , 118] are also of note. They were also painted on two layers of plaster with coarse sand of different colours due to the presence of iron compounds. Lastly, is interesting to point out the discovery of a rare silicate, from the pyroxene group, known as aerinite (from the Greek aerinos meaning blue-sky). This mineral was used as a 174 D. Jiménez-Desmond, J.S. Pozo-Antonio and A. Arizzi Journal of Cultural Heritage 66 (2024) 166–186 terials, and the individual artists, not always following what was stated in treatises and art manuals. Regarding pigments, the identification of mineral pigments different from those mentioned or found in the traditional pictorial palette has been seen as something recurrent (e.g., aerinite, riebeckite or crocoite) and is probably due to the accessibility of each local geographical area. It has also been highlighted here that the identification of the fresco technique in numerous studies is commonly not well supported by a complete analytical study. This is often the case of presumably recognised frescoes where pigments that are unstable under alkaline environment are identified. A common aspect of these studies is the lack of specific chemical analyses to detect possible organic binders remains, which would indicate, instead, a secco or a combined fresco-secco technique. Consent to participate The authors declare that they agreed to participate in the present review. Consent for publication The authors declare that they have read and agree to the publication of this paper. Author contributions Daniel Jiménez-Desmond: writing of the original version of this manuscript. José Santiago Pozo-Antonio and Anna Arizzi: revision and proofreading of the manuscript. Acknowledgements This study was funded by Research Projects PID2020-119838RAI00 and ED431F 2022/07 . Daniel Jiménez-Desmond was partially financed by the Xunta de Galicia project Limpeza sostible do patrimonio pictorico: optimizacion dos procesos de ablacion laser ( ED431F 2022/07 ) and the Spanish Science and Innovation Ministry project RYC2020-028902-I . J.S. Pozo-Antonio was supported by the Spanish Science and Innovation Ministry project RYC2020-028902-I . A. Arizzi was funded by State Research Agency (SRA ) and the Ministry of Science and Innovation under the Research Project PID2020-119838RA-I00 , within the Junta de Andalucía Research Group RNM179 . We also thank Nigel Washington for his review of the original English text. Funding for open access charge: Universidade de Vigo/CISUG. References [1] ICOMOS, Principles for the preservation, conservation and restoration of wall paintings14th ICOMOS General Assembly, 2003 Victoria Falls, Zimbabue . [2] P.G. Bahn, The Cambridge Illustrated History of Prehistoric Art, Cambridge University Press, 1998 . [3] O. Moro Abadía, M.R. González Morales, Paleolithic art: a cultural history, J. Archaeol. Res. 21 (2013) 269–306, doi: 10.1007/s1081401290638 . [4] P. Jezequel, G. Wille, C. Beny, F. Delorme, V. Jean-Prost, R. Cottier, J. Breton, F. Dure, J. 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