Archaeol Anthropol Sci (2018) 10:1207–1223 DOI 10.1007/s12520-016-0450-9

ORIGINAL PAPER

The Servilia tomb: an architecturally and pictorially important Roman building

S. E. Jorge-Villar1,2 & I. Rodríguez Temiño3 & H. G. M. Edwards4 & A. Jiménez Hernández3 & J. I. Ruiz Cecilia3 & I. Miralles5,6

Received: 13 October 2016 /Accepted: 5 December 2016 /Published online: 26 December 2016 # Springer-Verlag Berlin Heidelberg 2016

Abstract One hundred and eleven samples from the impor- periods, or that the frescoes have been subjected to unrecorded tant Servilia Roman tomb have been analysed for the first time restoration. We conclude that Raman spectroscopy is a valu- by Raman spectroscopy, resulting in a complete characterisa- able analytical technique for the unambiguous identification tion of the palette used for its remarkable wall paint- of mixtures of both organic and inorganic compounds, to ings: 73 different pigment mixtures have been identified for study the degree of mineral crystallinity and for identifying the composition of its 11 colours and their tonalities. Dyer’s treatment. These data are relevant for the holistic interpreta- weld, an ancient organic pigment, which was de- tion of the artwork in its historical, economical and social scribed by Vitruvius, has been identified and characterised context. for the first time in Roman wall paintings. Distinctive Raman spectroscopic signals which differentiate between hae- Keywords Roman Necropolis of Carmona . Pigment matite and caput mortuum (a colour from haematite treatment . Dyer’s weld . Lazurite . Caput mortuum . Raman which has been subjected to thermal treatment) are also re- spectroscopy ported. The use of the very expensive lazurite for a balance relates the importance of this otherwise ordinary instrument with psychostasia (the human soul weighing process) and is Introduction not found elsewhere in the tomb. The distribution of minerals alone or in admixture is not related to any particular The Necrópolis Romana de Carmona (Roman Necropolis of colouring pigment or figure; this possibly indicates that there Carmona), Sevilla (Spain), which dates from the first century was no specific use for each white mineral and that several BC to the second century AD, is a funerary complex which craftsmen worked on the paintings, perhaps in different was discovered in 1868–1869 and first opened to the public as an archaeological site in 1885. This archaeological site is characterised by a type of burial which consisted of cremation * S. E. Jorge-Villar ashes kept in urns and placed inside family-unit hypogeal [email protected]; [email protected] chambers which could be accessed through a rectangular door-like opening. Alternative tomb constructions are also found in the necropolis with more complex floor plans in 1 Área de Geodinámica Interna, Facultad de Educación, Universidad de Burgos, C/ Villadiego s/n 09001, Burgos, Spain which the rectangular door-like openings leading to the hypo- geal chambers were replaced by large patios dug into sur- 2 CENIEH, Paseo Sierra de Atapuerca, 09002 Burgos, Spain rounding rock, such as those found in the Elefante, Postumio 3 Conjunto Arqueológico de Carmona, Sevilla, Carmona, Spain and Servilia tombs (Rodríguez Temiño et al. 2012). 4 Division of Chemical and Forensic Sciences, Faculty of Life This typological division of contemporaneous tombs is as- Sciences, University of Bradford, Bradford BD7 1DP, UK sociated with the presence in the municipium of Carmo of a 5 Experimental Station of Arid Zones (CSIC), Almería, Spain wealthy minority that maintained social and cultural ties with 6 Earth and Life Institute, Université Catholique de Louvain, the Italic elites to whom they were presumably related Louvain-La-Neuve, Belgium (Caballos Rufino 2007). Although already highly 1208 Archaeol Anthropol Sci (2018) 10:1207–1223

Romanised, the native population lacked this cultural connec- 2013; Gutman et al. 2016; Mazzocchin et al. 2004, 2010; tion with the Italian peninsula. The connection was particular- Paradisi et al. 2012). In the study presented here, we were ly apparent in the copying of motifs in wall paintings unable to use portable instruments for in situ analyses and (Mostalac Carrillo 1999). The largest tomb at the archaeolog- were permitted only minimal sampling, for which micro- ical complex is the Servilia tomb, named for the sculpture and Raman spectroscopy was the selected technique for analyses. pedestal found in it bearing the inscription Serviliae L(vcio) Furthermore, the fact that Raman spectroscopy gives specific f(iliae) (CILA-02-03, 00870). Dating to the first century AD, molecular information and is able to differentiate between it was the mausoleum of the wealthy Servilii family. The tomb polymorphs (such as calcite and aragonite), isomorphs (calcite is thought to have been built by LvcioServilioPollio(CIL II and dolomite) and mixtures containing both organic and inor- 5120), a prosperous oil merchant who held several local mag- ganic components made this technique the preferred choice. istracies and enjoyed the favour of the imperial nobilitas The primary objective of this work is to study the materials (Caballos Rufino 2007). The tomb is an outstanding building used as in the wall paintings of the very important in terms of its architectural features and wall paintings, Roman tomb of Servilia in order to determine the different consisting of a 24 by 17.6 m atrium carved into the rock and compounds present and the combinations that were used to surrounded by columns. In the centre of this atrium, there is a configure the colour palette. During this study, we have dis- small impluvium measuring 2.95 by 1.75 m. There is a corri- covered the use of a novel organic pigment which to our dor carved into the rock along the northwest wall, with open- knowledge has not been described hitherto in wall paintings ings to the patio through doors and windows; the corridor but which has been mentioned by Vitruvius in De architectura connects with two funerary chambers sited on the southwest libri decem (B The Ten Books of Architecture^; Vitr. 7.14.2) as side, the larger one possibly designed to harbour sarcophagi a commonly used dyestuff for other purposes. and the second one possibly designed for funerary urns. To access this area, there is a large lounge, also carved into the rock, topped with a 4.2-m dome, connected with the patio by three cavities that could originally have been windows or per- Experimental haps doors (Abad Casal and Bendala Galán 1975;Rodríguez Hidalgo 2001; Ruiz Cecilia et al. 2011). Materials The chamber walls and patio of this remarkable building have schematic drawings with flowers, birds and garlands, but Samples were collected from the Servilia tomb (Figs. 1 and 2). it is in the corridor leading to the funeral chamber where a rare The sampled paintings are located in the funerary chamber painted scene was found. Although most of this stretch of wall and in the northwest corridor, located on the right side of the has unfortunately been lost, it is still possible to discern a funerary chambers. The wall paintings, which are deteriorat- scene depicting a kneeling woman weighing something in a ed, are still in their original underground position under a libra (balance) held in the hand of a figure that today is almost primitive ceiling, and since they are not isolated from an at- entirely gone. The woman is being fanned with a palm leaf by mospheric environment, most of them showed evidence of a servant (Abad Casal and Bendala Galán 1975). bacterial colonisation, which facilitated the detachment of An analytical study of the Servilia tomb pictures will pro- the painting layer from the substrate mortar. vide a better understanding of the iconographic models used by the higher social classes of the Roman municipium of Carmo and their relationships with their Italian equivalents, particularly those from Campania, as well as highlight a Hellenistic influence which can be perceived in this tomb. Furthermore, understanding this funerary building and its pic- tures is vital for the general comprehension of Roman funer- ary paintings and the relevance of using exotic pigments, as well as the symbolism of their hierarchical usage in specific images. Several different analytical techniques have been used to study the elemental and molecular composition of the mate- rials used in Roman wall paintings, such as FTIR spectrosco- py, Raman spectroscopy, XRD, SEM-EDX, synchrotron radi- ation spectroscopy, chromatography, optical microscopy and reflectance spectroscopy (Apostolaki et al. 2006; Baraldi et al. Fig. 1 Panoramic view of the Servilia tomb at the Necrópolis Romana de 2006, 2007; Duran et al. 2010; Edreira et al. 2003; Fermo et al. Carmona (Sevilla, Spain) Archaeol Anthropol Sci (2018) 10:1207–1223 1209

Fig. 2 Floor plan of the Servilia tomb showing the location of the panels

We analysed six different panels located in the corridor and in the tomb chambers, all of which exhibited deterioration:

Panel 1: a column located at the beginning of the corridor that is not protected from weathering by the overlying roof. The only pigment remaining is a colour at the base of the column. Panel 2: exhibits the most interesting and complex paint- Fig. 3 Panel 2 showing a woman weighing something on a balance and ing, depicting a woman weighing a non-visible object on being fanned with a palm leaf a balance (libra) held by a shadowy human figure (Figs. 2 and 3). Behind the woman, two hands can be seen hold- ing a palm leaf. On the left side of this scene, there is a A scalpel was used to excise the paint surface, either direct- piece of furniture similar to a table with a cushion on top ly from the walls or from the museum pieces, collecting just a (Fig. 2). few grains of the pigment in each case, which were then stored Panels 3 to 6 are all located inside the funerary chambers. in Eppendorf tubes or in tiny paper envelopes. Panel 3 shows remains of column drawings with garlands The colours sampled ranged from white, beige, yellow, and doves. The design is framed within a line. yellow ( and dark), (light and dark), , Panels 4, 5 and 6 show remains of botanical motifs such , red (light and dark), violet, green (light and dark) and as branches and leaves, sometimes in the form of a wreath . A factual colour scale was not used because the light and at other times forming a cross or a simple straight level inside the tomb was different from that in the museum line. office where the fragment samples were sampled, which af- fects colour perception. Interestingly, no yellow ochre or pink colours were observed on the samples taken directly from the From the large number of fragments stored and preserved tomb’swallpaintings. in the site’s museum, 16 pieces were chosen for our analyses Altogether, 111 samples were taken and all but one white in accordance with the following criteria: state of preservation, specimen were successfully analysed using Raman spectrosco- range of colours and tonalities and the use of different design py. Table 1 lists the colours and their occurrence. As will be patterns. Surprisingly, one of the fragments showed a mould- discussed later, the presence of white colour in a sample could ing that was not found in any in situ tomb panel. Although all be ascribed to its use as a pigment alone or in admixture with fragments were collected when the archaeological excavation another pigment to lighten the colour or alternatively arising was carried out and most likely belong to walls or ceilings from as part of the wall mortar substrate; pigments applied from the tomb, it is not possible to assess where in the using the wet fresco technique impregnate the substrata and Servilia tomb the fragments originated. Other samples were therefore both, pigment colour and wall substrate, are analysed taken directly from the wall paintings still in place in the tomb simultaneously. Hence, in Table 1, we have recognised the and their precise location was recorded (Fig. 2). presence of these white minerals and have distinguished 1210 Archaeol Anthropol Sci (2018) 10:1207–1223

Table 1 Summary of all compositional combinations Sample colour White pigments Colouring pigments Specimens found in the colour palette on Servilia tomb with the number of White – 1 specimens in which each different White Calcite 2 combination was found White Calcite and dolomite 2 White Calcite and feldspar 1 White Calcite, gypsum and quartz 2 White Calcite and quartz Carbon 1 White Calcite and quartz Goethite 1 White Calcite and quartz Goethite and unknown compound 1 White Calcite, quartz and aragonite – 1 Beige Calcite Goethite 1 Beige Calcite and dolomite Goethite 1 Beige Calcite and gypsum Goethite and carbon 1 Beige Calcite and dolomite – 1 Black Calcite Carbon 3 Black Dolomite Carbon 1 Black Quartz Carbon 1 Black Calcite and gypsum Carbon 1 Black Calcite and aragonite Carbon 1 Black Calcite and quartz Carbon 1 Black Dolomite and quartz Carbon 1 Black Calcite, dolomite and quartz Carbon 1 Black Calcite Haematite and carbon 1 Black Calcite and quartz Haematite and carbon 1 Pink Calcite and dolomite – 1 Pink Calcite and dolomite Cinnabar and carbon 1 Light red Calcite Haematite 7 Light red Calcite and gypsum Haematite 2 Light red Calcite and dolomite Haematite 1 Light red Calcite Haematite, goethite and carbon 2 Dark red Calcite Haematite and carbon 1 Dark red Calcite Haematite and goethite 1 Dark red Calcite Haematite, goethite and carbon 1 Dark red Calcite and dolomite Haematite 1 Violet – Haematite 2 Violet Calcite Haematite 2 Violet Calcite Haematite, goethite, Egyptian 1 blue and carbon Violet Calcite and quartz Haematite 1 Violet Calcite Haematite and Egyptian blue 1 Violet Calcite Haematite and carbon 2 Yellow Calcite and dolomite Goethite 1 Yellow Calcite and aragonite Goethite 1 Yellow Gypsum Goethite 1 Yellow Calcite Haematite 1 Yellow Calcite, dolomite and gypsum Goethite 1 Yellow Calcite and gypsum Haematite and goethite 1 Yellowish ochre Calcite Goethite 1 Yellowish ochre Calcite and dolomite Goethite 2 Yellowish ochre Calcite Goethite and cinnabar 2 Light brown Calcite Haematite and goethite 2 Archaeol Anthropol Sci (2018) 10:1207–1223 1211

Table 1 (continued) Sample colour White pigments Colouring pigments Specimens

Light brown Calcite and gypsum Haematite, goethite and carbon 1 Light brown Calcite, aragonite and quartz Goethite and carbon 1 Dark brown Calcite Haematite 1 Dark brown Calcite Haematite and goethite 1 Dark brown Calcite Goethite and carbon 1 Dark brown Calcite Haematite, goethite and carbon 1 Dark brown Calcite Haematite, goethite, lazurite and 1 unknown Dark brown Calcite and quartz Goethite and carbon 1 Blue – Egyptian blue 1 Blue Calcite Egyptian blue 4 Blue Quartz Egyptian blue 1 Blue Calcite Egyptian blue and carbon 1 Blue Gypsum, quartz Lazurite, goethite and carbon 1 Blue Calcite Carbon 1 Blue Calcite, quartz and hydrocerussite Carbon and unknown compound 1 (lead white) Light green Calcite Green earth 6 Light green Calcite Green earth and carbon 2 Light green Calcite Green earth and Egyptian blue 2 Light green Calcite Green earth, Egyptian blue and carbon 1 Light green Calcite Goethite, Egyptian blue and carbon 1 Light green Calcite Green earth, carbon and organic 1 compound Light green Calcite and gypsum Egyptian blue and carbon 1 Light green Calcite and gypsum Green earth and carbon 1 Light green Calcite and quartz Green earth 1 Light green Calcite and hydrocerussite Green earth 1 Light green Calcite, gypsum and quartz Green earth 1 Dark green Calcite Green earth and Egyptian blue 3 Dark green Calcite Goethite and carbon 1 Dark green Calcite Goethite, green earth, Egyptian blue 1 and carbon Dark green Calcite, quartz and anatase Green earth and carbon 1 Dark green Calcite Green earth and carbon 1

White pigments have been separated from the colouring pigments since they could be a proper ingredient of the pigment manufacturing or be related to wall preparation. For further explanations, see text different colouring compounds (minerals and organics) for a multi-particle analysis), ×50 and ×100 (for extreme small parti- better understanding of the Roman pigment mixtures. cles) microscope magnifications were utilised, the ×50 objective gave the best spectra with regard to signal-to-noise ratios, and the spectral footprint at this magnification was 5 μm in diameter. Analyses were performed with a DXR Thermo Fisher con- Methods focal Raman spectrometer with an Olympus optical micro- scope attachment. Samples were analysed in the Archaeometry Laboratory of the Centro Nacional de Investigación en Evolución Humana (CENIEH); 780 nm (near infrared) and 532 nm (green) laser excitations were used. Systematically, 10 s of exposure time Results and Discussion and between 40 and 60 spectral accumulations were used to achieve each co-added spectrum, using a maximum laser power From the 111 specimens, we have found 73 different admix- of 0,5 mW to avoid specimen degradation. Although ×10 (for tures of pigments (Tables 1 and 2). Of these 73 mixtures in the 1212 Archaeol Anthropol Sci (2018) 10:1207–1223

Table 2 Summary of the samples analysed of each colour obtaining the tonality desired by the artist. Although it can Colour Samples Total admixtures Colouring admixtures crystallise in nature from aqueous media (caves and hot springs), its occurrence in the shells of molluscs, corals, plank- White 12 8 3a ton etc. is a more common origin. The presence of aragonite Beige 4 4 2 from shells in wall paintings was much appreciated because of Black 12 10 2 its adherence (Bearat 1997). According to Bearat (1997), it is Pink 2 2 1 + 1b the pigment called by Pliny the Elder paraetonium (Plin. Nat. Red 16 6 4 5.6), although paraetonium has also been interpreted as the Violet 9 6 4 tripoli rock (Eastaugh et al. 2004). Aragonite has been de- Yellow 6 5 3 scribed as an expensive white pigment and is then found Yellowish ochre 5 3 2 mixed preferentially with other expensive colouring minerals Brown 10 8 5 + 1b (Bearat 1997). Aragonite was found on four occasions in our Blue 10 7 5 pigment samples (in white, yellow, brown and black) and in Green 25 14 7 + 2b each case seemed not to be associated with other costly Total 111 73 38–42 minerals. Dolomite is a calcium and magnesium carbonate that has The number of Btotal admixtures^ take into account the colouring pig- been found in our samples and is characterised by its Raman B ment as well as all white minerals found in each specimen; colouring signatures at 1098, 725, 300 and 176 cm−1. The appearance of admixtures^ only consider pigmenting compounds found in each sample this mineral could be due to the substratum (as part of the a We do not consider here mixtures used for obtaining white colour but only when some colouring pigment was identified dolomitic marble dust applied on the mortar layers) or alter- b On these cases, the first cipher indicates the number of samples with natively to the pigment itself, being added as a white mineral pigments leading to obtaining the described colour or any of it; the (Eastaugh et al. 2004). Although dolomite has been pointed second number indicates number of specimens where no colouring min- out as the carbonate mineral most preferred for the dilution of eral was detected or where the admixture did not lead to the described blue pigments in wall paintings (Bearat 1997), in our samples, colour dolomite was detected in white, beige, yellow and yellowish ochre, black, red and pink pigments, but not in blue, brown, colour palette described in this work, calcite (with Raman violet or green ones. bands at 1086, 713, 281 and 156 cm−1) was identified in 66 Quartz (Raman bands at 464, 205 and 127 cm−1) was used (90.41%) specimens. Although calcite can be used as a white as a part of the mortar composition in the form of fine sand but mineral added to the pigment to obtain a desired tonality, the has also been described as an additive for improving the pig- fresco painting technique itself results in calcite crystallisation ment grinding process (Villar and Edwards 2005). Quartz is an once the wall preparation and the colour application have inert mineral that does not react with limewash, atmosphere or dried. For the wall preparation, several layers of mortar (sand water when applied as mortar or pigment. Tripoli, a rock made or marble), each becoming increasingly smoother and thinner, from the shells of diatom, comprises amorphous fine-grained are brushed over a wall together with limewash (Ca(OH)2), silica and has been described as a white pigment, the so-called which reacts with atmospheric CO2 and leads to the calcite paraetonium pigment described by Pliny the Elder (Plin. Nat. precipitation inside the mortar pores. According to Vitruvius 5.6) (Eastaugh et al. 2004). It is not possible to distinguish by (Vitr. 7.2.1.) (Millar 2015), the set of layers is called a Raman spectroscopy when α-quartz was used as a mortar tectorium and usually comprised three layers of sand mortar component or when it has been added as a white component and three more of marble dust, applied with limewash. Fresco of a pigment colour. colours were water based and were often applied using Gypsum (identified by the Raman bands at 1139, 1008, limewash to improve their adherence (Abad Casal 1982). 619, 492, 415, 210 and 179 cm−1) has been described as a Calcite crystals could therefore originate from the fresco tech- white pigment, but there are not many references alluding to nique itself or as a part of the mineral mixture used to obtain a this (Eastaugh et al. 2004). Its use as a plaster component in specific colour, and it is not possible to discriminate between the wall preparation for Roman frescoes and in admixture with these by Raman spectroscopy. expensive and valuable pigments, such as lazurite and pure It has been proposed that, since high temperatures can be and well-crystallised haematite (Edwards et al. 2009), has reached during the calcium oxide slaking process to make been described. Among our 111 samples, gypsum appeared limewash, the precipitation of aragonite (Raman bands at in only two of the red samples, as well as in the two samples 1086, 708, 204 and 156 cm−1), a calcium carbonate poly- where lazurite was identified; however, it has also been de- morph, is possible (Bläuer-Böhm and Jägers 1997). tected in two white specimens, one beige, three yellow, one However, the presence of aragonite crystals in a colour is blue (together with lazurite), one brown, one black and three perhaps more likely ascribed to its use as a white mineral for green (one mixed with lazurite) specimens (Table 1). The Archaeol Anthropol Sci (2018) 10:1207–1223 1213 presence of gypsum could also be ascribed to weathering pre- assigned. The weak and broad 392 cm−1 feature could be cipitation processes and be related to wall painting degrada- assigned to goethite, which would explain the yellow colour; tion through the reaction of calcium carbonate with sulphur however, this assignment is doubtful because other features containing atmospheric contamination. are missing. The signature at 1025 cm−1 could be assigned to Although the use of different white minerals with different bassanite, a hemihydrate form of calcium sulphate (Prieto- purposes on the same archaeological site has already been Taboada et al. 2014). reported (Béarat and Fuch 1996), we have not observed any relationship between white minerals and specific designs or Beige colours. Four samples were described as beige. Sample 3598 showed the presence of goethite plus calcite; in the Raman spectra of White sample 1149, only calcite and dolomite were discovered. Sample 1133 exhibited the signals for calcite, gypsum and White and beige colours were mainly used as background amorphous carbon, whereas in sample 3338, despite its clas- over which other patterns were drawn. Twelve samples were sification as beige, no colouring compound was found and described as white, but one of them did not give any Raman only the white minerals calcite and dolomite were identified. response, using either the 780 or 532 nm laser wavelengths; thus, no compound potentially used as pigment could be identified. Black Eight specimens showed evidence of solely white minerals (Table 1): calcite (two samples); calcite and dolomite (two Twelve black samples were analysed, two from the tomb and samples); calcite and microcline feldspar, identified by the ten from the museum fragments. The colouring pigment used Raman bands at 512, 475, 284 and 155 cm−1 (1 sample); for black was carbon; however, in two samples haematite, a calcite, quartz and gypsum (2 samples); and calcite quartz red iron oxide was also found. These pigments were mixed and aragonite (1 sample) (Fig. 4). with white minerals in different proportions. However, three white samples showed some kind of Carbon is well characterised by Raman spectroscopy be- coloured pigments, even if they appeared in low proportion: cause of the presence of two broad signatures centred around sample 3577 exhibited Raman bands from calcite, quartz and 1595 cm−1 (G band) and 1330 cm−1 (D band); the stronger and goethite, whereas the white sample from the 3328 fragment sharper the D band, the higher the degree of crystallinity of the showed calcite and weak Raman signals of carbon with a low carbon (Deldicque et al. 2016;Cuestaetal.1994). Most of the degree of graphitisation. In the white sample from fragment carbon detected in our samples showed a high degree of 3333, calcite with amorphous carbon were clearly identified, graphitisation (Fig. 5). Of the various ways to obtain carbon, although the strong Raman bands at 146, 235, 277 and charcoal, soot and bone black have been detected in Roman 1025 cm−1, together with very weak signals at 392 and paintings (Ling 1991). The absence of a Raman signature 346 cm−1, achieved on a yellow particle have not been around 965 cm−1 assigned to phosphate dismisses the use of

Fig. 4 Raman spectra of the main white minerals found in samples Calcite+gypsum from the Servilia tomb 800800

600600

Aragonite

400400 Calcite

200200 Dolomite Intensity (arbitrary units) (arbitrary Intensity

00

Microcline feldspar -200 Quartz

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Fig. 5 Raman spectra of black 180180 specimens showing a Raman spectrum of pure carbon with a b high degree of crystallinity, 160160 carbon with calcite and haematite, c carbon with calcite and d a amorphous carbon 140140

120120 b Intensity (arbitrary units)

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d 8080

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bone black in our specimens; we did not find any Raman Pink bands characteristic of iron or manganese minerals, such as magnetite or pyrolusite, which have also been used as black Only two samples were catalogued as pink. Both presented pigments, or the presence of any organic signatures. signals for calcite and dolomite. In specimen 3333, the Raman Among the white minerals found in the black samples, signals at 343, 283 and 253 cm−1 indicate the presence of carbonates were the most frequent compounds. The main car- cinnabar (Fig. 6); neither cinnabar nor haematite was found bonate phase was calcite (1086, 713, 281 and 156 cm−1), but in the 2159 sample, despite this specimen possessing a beau- aragonite and dolomite were clearly identified in some of the tiful and unique moulding which could be indicative of some samples. Aragonite is a calcium carbonate, a calcite poly- special design, whereas the former specimen showed a simple morph, and is identifiable by the presence of a medium inten- straight pink line between black lines. Cinnabar was also sity lattice mode Raman band at 204 cm−1, instead of that at found as a part of the pigment mixture in a yellowish- 281 cm−1 characteristic of calcite or that at 300 cm−1 for do- reddish ochre colour from a broad, irregularly coloured circu- lomite. Although the ν4 in-plane bending Raman mode lar band that will be discussed in more detail in the yellow/ (713 cm−1 for calcite and 708 cm−1 for aragonite) could also ochre section. be used for characterisation, these bands are usually not visi- ble in degraded samples because as a result of their weak intensity, they are often hidden by fluorescence emission and Red noise. Dolomite, a calcium-magnesium carbonate with Raman signatures at 1098, 725, 300 and 176 cm−1, has also been We analysed 16 red specimens: 12 light red and 4 dark red. characterised here. Quartz (464, 205 and 127 cm−1) and gyp- With regard to the colouring minerals, light red was made sum were also found as white pigments. using only haematite (612, 500, 411, 293, 244 and Different admixtures of the five white minerals (calcite, 226 cm−1) in ten samples, while two light-red specimens aragonite, dolomite, quartz and gypsum) together with carbon showed, together with calcite and haematite, the presence and haematite gave ten different ways to obtain shades of of goethite and carbon. The four dark-red colours were black and greyish colours (Table 1). The addition of more or obtained using four different admixtures of colouring min- less carbon to a white mineral is enough to obtain a wide range erals; only haematite; haematite and carbon; haematite and of shades (from very light to very dark), but we have not goethite; and, finally, haematite, goethite and carbon described grey in our specimens and, furthermore, there is no (Table 1). Calcite was detected in all samples, while dolo- apparent reason to use five different white minerals in admix- mite was identified in the specimen with haematite as the ture with carbon for pigment tonality. Only the addition of sole colouring pigment. The identification of goethite in haematite, a red mineral, could change the tonality of black four specimens leads us to conclude that it was probably here. There is no ostensible relationship between the white added on purpose, sometimes together with carbon, for minerals used in these pictures for obtaining obtaining the desired hue. There is no evidence of a hier- with design, figure hierarchy or sample site. archical use of gypsum or dolomite in our paintings. Archaeol Anthropol Sci (2018) 10:1207–1223 1215

Fig. 6 Raman spectra achieved on the pink specimen from fragment 3333, showing a calcite 300300 and dolomite, b cinnabar plus calcite and c pure cinnabar

250250

200200 Intensity (arbitrary units) a

150150 b

c

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Nine light-red and three dark-red specimens showed only used as the only pigment in five samples; two specimens showed calcite as the white mineral; two light showed calcite and haematite and carbon; the admixture of haematite with Egyptian gypsum whereas calcite and dolomite were detected in one blue (one specimen); and of haematite with Egyptian blue, car- light-red and one dark-red specimen. Although some degrad- bon and goethite (one specimen) have also been characterised. ed specimens on the panels showed a gypsum efflorescence, Egyptian blue, also known as caeruleus (Suet. 25 Aug.), is a under the microscope gypsum appeared integrated with the synthetic variety of the mineral cuprorivaite, a calcium and cop- pigment suggesting that in these specimens, it was added as per silicate, which is very scarce in nature but relatively easily an integral component of the colour preparation or possibly obtained by heating silica, calcium oxide and oxide (Ling present as a smoothing topcoat on the panel. 1991;Eastaughetal.2004). This compound gives a good Four red samples, two light and two dark, exhibited signals Raman spectrum with signatures at 1087, 568, 430, 354 and for carbon. It appears that the darker tonalities were obtained 116 cm−1 that leads to an unambiguous identification. Some by using a higher ratio of the haematite to white minerals references in the literature show that this was also a common aided by the addition of carbon. It is interesting to note that way to obtain the colour violet in Roman wall painting two reds (light and dark) were analysed in fragment number (Mazzocchin et al. 2010; Bearat 1997). 1133 and only the dark one showed dolomite particles, as if Although differences in tonalities and involving hae- this mineral had been added on purpose. Carbonates are easily matite could also be related to crystal size (de Oliveira et al. and unambiguously characterised by Raman spectroscopy, 2002;Bikiarisetal.1999) and shape (de Oliveira et al. 2002), and there is no doubt about their presence or absence in our the use of haematite to obtain violet has also been related to samples. Both calcite and dolomite are white minerals used as the use of the expensive Roman pigment called caput diluents for lightening pigment colours and their presence mortuum, which was obtained naturally or by heating haema- could reflect a painter’s preference or it could be related to tite (Eastaugh et al. 2004;deOliveiraetal.2002). The pres- secondary repainting, a contemporary restoration process of ence of the Raman bands at 243 and 660 cm−1 has been related the wall paintings, or the presence of different masters in to a thermal treatment of haematite (de Oliveira et al. 2002). In charge of different parts of the final designs. our spectra (Fig. 7), the Raman signature at 243 cm−1 clearly appeared in most of the spectra of haematite in red (either light Violet or dark) and violet samples but the band at 660 cm−1 was stronger in the violet specimens. In summary, we confirm that The colour violet was found in nine samples. Six pigment ad- in the Servilia tomb paintings some violet colours were ob- mixtures were used in the Servilia tomb for obtaining this colour. tained by mixing blue (Egyptian blue) and red (haematite), With regard to the white components of the mixtures, two sam- while others were probably achieved by a thermal treatment ples did not show the presence of any white mineral at all, of haematite. We can discount a laser-induced haematite ther- whereas calcite was found in the remaining seven specimens, mal transformation because of laser heating when analysing in one case mixed with quartz. Four different coloured pigments our samples, since the use of a maximum power of 0.5 mW were used in the mixtures for obtaining violet: haematite was negates this effect (de Faria et al. 1997;Hanesch2009). 1216 Archaeol Anthropol Sci (2018) 10:1207–1223

Fig. 7 Raman spectra of 10001000 haematite from the red and violet specimens. Bands at 243 cm−1 −1 and particularly at 660 cm , 800800 related to artificial heating processes, are more evident in the violet specimens (four spectra 600600 from bottom) than in the reds (three spectra from top) 400400

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00

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1600 1400 1200 1000 800 600 400 200

Wavenumber (cm-1)

No Raman signatures characteristic of kaolinite were found been found. No signals of cinnabar were detected on the cor- in the samples containing caput mortuum, despite that its pres- ridor panels, where human figures are clearly preserved and in ence has already been reported in Roman wall paintings to which lazurite was identified. It is also noteworthy that, de- increase the pigment adherence (Edwards et al. 2002). spite the bright tonality that cinnabar brings to the coloured pigments, no red colour, light or dark, showed cinnabar Yellow and yellowish ochre Raman signatures. As already noted, this was a very expen- sive pigment in Roman times and its use for and yel- Six samples were described as yellow, all of them collected lowish in geometrical designs is therefore surprising, from the Museum fragments, except for one which was collect- especially where the link with hierarchical use is not clear. ed from panel 3. Calcite, aragonite, dolomite and gypsum were However, as the precise fragment location from the tomb is all characterised as white minerals, but each sample showed not known, further exploration of the use of cinnabar for spe- different compositions in the mixtures; calcite appeared in five cific designs or figure hierarchy may not be possible. of the six specimens but only once as the unique white mineral. Although most authors describe goethite as the mineral used One yellow specimen had gypsum but did not show Raman for obtaining a yellow colour in Roman wall paintings, there are bands of any carbonate. For a yellow colouration, we found references in the literature to the use of limonite for this purpose three different admixtures (Table 1): goethite was unambigu- (Apostolaki et al. 2006; Mazzocchin et al. 2003, 2004; Villar ously identified in five samples (in four of them as the unique and Edwards 2005; Edwards et al. 2003). Limonite yellow pigment), haematite was also identified in admixture (FeO(OH)∙nH2O) is not considered a true mineral since it is with goethite in the yellow sample from panel 3. One of the an amorphous phase of iron oxide/hydroxide which normally specimens only showed Raman peaks for the red haematite, appears mixed with other iron oxides/hydroxides. Goethite and no yellow pigment was evident. (FeO(OH)), however, is the crystallised phase. There is some We identified five yellowish ochre samples. Three showed confusion in the literature with regard to the Raman spectral only calcite as a white mineral, whereas two specimens assignments of the bands observed at 550, 478, 386, 299, 245 showed calcite and dolomite. Goethite was detected as the and 204 cm−1, which are sometimes assigned to limonite only pigment in two ochres and neither haematite nor carbon (Bikiaris et al. 1999) and sometimes to goethite (de Faria et al. was found. Surprisingly, cinnabar was unambiguously identi- 1997; Bouchard and Smith 2003; Legodi and de Waal 2007). fied in the irregularly coloured wide ribbon from fragments Because an amorphous compound does not usually give sharp 1099 and 1133 by its characteristic Raman signatures at 343, Raman bands but rather broad signatures, such as those of glass 284 and 254 cm−1; although both samples exhibit different or carbon, the presence of clear sharp Raman peaks should be designs, the black patterns on top of these wide yellowish related to a type of crystallised mineral; therefore, the identified ochre ribbons suggest that they may have formed a part of Raman signatures in our spectra should be assigned to goethite. the same circular band (Fig. 2). It is interesting to notice that Nevertheless, the degree of crystallisation of this mineral could this yellowish ochre sample and the pink band from fragment be linked to the shifts and increased breadth of the Raman 3333 are the only specimens where this costly pigment has bands; this effect is observable as the main Raman peak at Archaeol Anthropol Sci (2018) 10:1207–1223 1217

385 cm−1 shifts to higher wavenumber positions (Bouchard and to play the main role in the scene, since, as will be seen below, Smith 2003) when the crystallinity decreases and, in the case of it could represent the instrument where souls were weighed pigments, could be related to the presence of a higher amount of upon death. This idea is further supported by the use of the limonite amorphous phase in the mixture. In our samples, lazurite to paint it (see blue pigments). Furthermore, a brown we have observed a range of wavenumber positions of this colour is not usually made by mixing a blue pigment, as is spectral signature from 384 to 396 cm−1, and it is clearly ob- commonly found in or violets for changing the hue. A servable that when this band appears at higher wavenumber possible contamination as sometimes happens when one col- positions, it is also significantly broader (Fig. 8). our is superficially applied to another has been considered when explaining the use of lazurite on the hand of the second- Brown ary figure, but in this case, the balance and the secondary figure’s arm are quite distant from each other, so this possible Four light-brown and five dark-brown samples were collected explanation has been rejected. Because of the methodology from panel 2; one dark-brown specimen comes from fragment used when collecting the samples, we can discount sampling 1133. With regard to the white minerals, calcite was identified in contamination. Occasionally, colours do exhibit composition- all samples, usually alone except in three specimens: once with al differences related to the hierarchical importance of the gypsum, once with quartz and once in admixture with aragonite figure (Edwards et al. 1999), but we have not found any evi- and quartz. For the coloured pigments, all , whether light dence of this in the use of pigments in the Servilia tomb, either or dark, showed Raman bands from goethite except the dark- on panel 2 or on the Museum samples. The reason for the use brown pigment used on the palm leaf, which only exhibited of lazurite in this figure is therefore still a mystery. signatures from haematite. When goethite was the only colouring pigment, it was always mixed with carbon. Other admixtures were haematite plus goethite, and haematite, goethite and carbon. Blue One of the Raman spectra achieved on the dark-brown specimen, collected from the hand of the secondary figure Ten blue samples were analysed, six from panels 2, 3 and 6 holding a palm leaf, exhibited a strong band at 547 cm−1 that, and four from the fragments. All samples collected from the together with the two broad and weak shoulders, centred at museum fragments and those from panels 3 and 6 showed 354 and 381 cm−1, could be assigned to lazurite. The assign- only two pigments: calcite and Egyptian blue (Fig. 9), identi- ment of lazurite in the spectrum of this secondary figure, al- fied by the Raman bands at 1087, 570, 431, 230, 193 and − though quite clear, is intriguing because the very expensive 119 cm 1, although on one of these spectra, from fragment blue pigment does not match the importance of the figure in 1133, quartz was also identified. the panel composition. This figure (Fig. 3) clearly plays a However, each of the four blue samples from panel 2 secondary role to the principal female figure who is weighing displayed different pigment admixtures. For the cloak of the something (not visible) in a balance held by a third figure: the figure holding the balance only calcite and carbon were iden- secondary figure hence appears to be the female figure’sser- tified, whereas for the cloak of the female figure, apart from vant. In this panel (number 2), it is the libra itself which looks calcite and carbon, Egyptian blue was clearly characterised.

Fig. 8 Raman spectra of goethite showing how the shift to higher positions of the stronger Raman band is related to a broader signature 150

100 Intensity (arbitrary units)

50

800 700 600 500 400 300 200 100 Wavenumber (cm-1) 1218 Archaeol Anthropol Sci (2018) 10:1207–1223

Fig. 9 Raman spectra of blue pigments, from top to bottom: 600 Egyptian blue, lazurite from the Servilia tomb and lazurite from our database 580

560

540 Intensity (arbitrary units)

520

1000 800 600 400 200 Wavenumber (cm-1)

The sample collected on the line edging the table, situated detected using Raman spectroscopy; although the literature in- on the left area of this panel, showed calcite, quartz and car- dicates that it has also been detected elsewhere using other bon, with a signature at 1055 cm−1, which indicates the pres- techniques (Favaro et al. 2012; Salvadó et al. 2014; Cristache ence of lead white (hydrocerussite); one of the spectra also et al. 2013), it has never been detected on Roman frescoes. showed a Raman band at 425 cm−1 that is still without assign- Furthermore, it should be highlighted that on the occasions that ment, since it is located in a Raman wavenumber position that lazurite has been reported on wall paintings, it has always been is too low for being assigned to Egyptian blue. found in the distant provinces of the Empire, but never on wall The most interesting mixture of pigments is that used in the paintings in villas central to the Roman Empire. balance, for which gypsum, quartz, carbon and lazurite were The second interesting point centres on why this expensive identified. Lazurite was characterised using the green 532 nm and exclusive pigment was used on a libra, which at first laser wavelength, because of its signatures at 262, 547 and glance appears to be a very ordinary instrument. Because of 1091 cm−1 and overtones (such as 810, 1357, 1634 and the unique nature of this scene in Roman-era funerary art, its 2178 cm−1); it was also characterised using the near-infrared meaning has been extensively discussed (Guiral Pelegrín and laser (780 nm wavelength), because of the characteristic Mostalac Carrillo 2001; Guiral Pelegrín 2002; Fernández Díaz strong Raman band at 547 cm−1. Furthermore, one spectrum 2010). The most widely accepted interpretation to date was of this sample also exhibited a weak and broad band centred at that it depicted a scene from everyday life, related to oil pro- 384 cm−1, attributed to goethite. The admixture of a small duction, as LvcioServilioPolliowas involved in the lucrative amount of goethite with lazurite and carbon to obtain the blue oil trade. However, the presence of this expensive pigment in colour of the balance is peculiar, since lazurite is an expensive the libra can only be interpreted as a means of underscoring pigment whereas goethite was a very common pigment and the importance of this object, which would seem inconsistent together, blue and yellow, give a green tonality; therefore, this with a scene from the officina of a difussor olearii.Thisledto mix reflects a sophisticated way to achieve a specific blue a rethinking of the scene’ssymbolism,whichwaslinkedin- tonality verging towards a turquoise colour. stead to the classical soteriological universe. Indeed, despite Despite extensive studies carried out on the blue pigments the relative infrequency of such iconographic motifs, a scene used in the Roman Empire for wall paintings, only two works, depicting psychostasia (the weighing of souls) seems better to our knowledge, have hitherto reported the use of lazurite, a suited to the funerary context and to the painting’stopograph- very expensive blue mineral: in the Roman Villa of Baños de ical location within the tomb (in the narrow passageway used Valdearados (fourth to fifth centuries), in Burgos (Spain), it was to access the funeral chambers) (Rodríguez Temiño 2016). found related with a green colour (in admixture with limonite) (Villar and Edwards 2005) and as a pure blue colour in a villa Green belongingtoanearlyRomancolonyinColchester(UK) (Edwards et al. 2009). However, lapis-lazuli, the rock from Green colour was described in 25 samples and obtained from which lazurite is one of the main minerals, is often found in allpanels(1to6)aswellasfrom12fragments;ofthese,only jewellery, mosaics and other ornaments (Eastaugh et al. 2004). 7 can be described as dark green. All the samples showed It is interesting to note that, in both of these cases, lazurite was Raman signatures from calcite, whereas quartz was only Archaeol Anthropol Sci (2018) 10:1207–1223 1219 detected in four cases and gypsum in three; calcite, quartz and Both phyllosilicates are isostructural and give similar Raman gypsum were identified together in only one sample. spectra. Signatures from anatase were found only in one sample, along Interestingly, Egyptian blue (cuprorivaite) was detected in with calcite and quartz. The presence of hydrocerussite plus a total of seven specimens altogether with green earth (and calcite has been described in one specimen. We cannot find sometimes with carbon), possibly used to obtain a bluish- any relationship between the colouring pigments and the pres- green hue. In one of the samples, no green pigment was used ence of white minerals to assess whether or not there is any but Egyptian blue and goethite in admixture with carbon were connection between the use of quartz, gypsum, anatase or adopted for obtaining a light-green colour. Blue and yellow hydrocerussite with any particular pigment mixture. pigment admixture is known to give a green colour and may Carbon was found in five samples from the panels and in have been used here to achieve a specific tonality. four samples from the fragments; we cannot conclude that it Two samples revealed more sophisticated ways to obtain a was used for darkening purposes due to its use in four dark- green colour. One of these samples, a dark green from frag- green samples, but it was also detected in five of the light ment 3577, showed Raman signatures of green earth, green specimens. Carbon can also be found in wall paintings Egyptian blue and goethite together with carbon. The second that have been subjected to soot deposition from candles and sample, a light green from fragment 1147, showed, in addi- oil lamps used for . tion to the presence of green earth and carbon, Raman signa- Among all samples identified as green, 21 showed Raman tures of an organic compound, with bands at 1597, 1549, signatures identified as green earth, terre verte.Thispigment 1537, 1512, 1421, 1363, 1288, 1274, 1238, 1164, 1049, is a mixture of different minerals in which celadonite and/or 964, 916, 729, 635, 539 and 369 cm−1 (Fig. 11). The charac- glauconite (from the phyllosilicate group) are responsible for teristic Raman bands of verdigris, a copper acetate with var- the green colour. Discrimination between glauconite and iations in water molecule content, from our own database celadonite in our green samples is rather unclear (Fig. 10). (synthetic verdigris, Cu(CH3COO)2·[Cu(OH)2]3·2H2O) are Only one of our spectra, collected using a 532-nm laser wave- situated at 1441, 1417, 1361, 948, 703, 322, 185 and length, gave a really good Raman spectrum that matched the 106 cm−1. No significant differences in relative band intensi- published spectrum obtained for a celadonite standard ties were noted when spectra were achieved using 780 or (Ospitali et al. 2008; Aliatis et al. 2009), showing bands at 532 nm laser wavelengths and both are in agreement with 1132, 1087 (this peak can also be a contribution from associ- the published Raman wavenumber positions of verdigris ated calcium carbonate polymorphs), 1068, 959 (broad), 795, (San Andrés et al. 2010;delaRojaetal.2007). In all cases, 764, 701, 585 (broad), 547 (broad), 458, 396, 357, 320, 280 the characteristic and strongest signatures are those in the (shoulder), 271, 217, 176 and 87 cm−1.Insomecases,togeth- wavenumber regions at 936–949, 702–703 cm−1 and, in our er with some of the sharp signatures characteristic of analyses, also in the 322–323-cm−1 area; however, these celadonite (1132, 1087, 701, 458 and 273 cm−1), broad signa- bands were absent in the spectra acquired from the light- tures appeared centred around 633, 542 and 384 cm−1,and green specimen from the 1147 fragment. Consequently, we these could be assigned to either celadonite or glauconite. discounted the presence of verdigris here. In the work

Fig. 10 Raman spectra of greens. The bottom spectrum was characteristic of celadonite. The 30003000 three upper spectra could be related to glauconite, whereas the fourth and fifth spectra matched that of celadonite 28002800

26002600 Intensity (arbitrary units)

24002400

22002200

1200 1000 800 600 400 200 Wavenumber (cm-1) 1220 Archaeol Anthropol Sci (2018) 10:1207–1223

Fig. 11 a Raman spectrum of the a organic compound (probably 2600 dyer’s weld) found in a sample from fragment 1147; for 2500 comparison purposes, b Raman b spectrum of celadonite and c Raman spectrum of copper 2400 acetate

2300

2200 Intensity (arbitrary units)

2100 c

2000

2000 1800 1600 1400 1200 1000 800 600 400 200 Wavenumber (cm-1)

described here, the yellow particle is in a solid matrix and is the free CO and associated OH groups, which will lower not attributable therefore to a wax on the surface of the the CO wavenumber and assist in its coupling to the CC artwork. and aromatic CH vibrations, as observed here, and noted In his De architectura libri decem (BThe Ten Books of as a chelation between the CO and the C–OH in position Architecture^), Vitruvius (Vitr. 7.14.2) described the use of C5 in the colloidal absorption spectra. A similar effect dyer’s weld, a yellow organic pigment extracted from the was noted in the SERS spectra of the pure pigments since plant Reseda luteola (Eastaugh et al. 2004), in admixture the absorption of the molecules onto the colloid facilitated with blue, for obtaining a green colour. This plant is rich this interaction and decrease in intensity of the free CO in luteolin and apigenin (Gaspar et al. 2009), flavonoids mode. The weaker band at 1549 cm−1 in our spectrum similar in structure that show their main Raman signatures here is assignable to the CCH ring quadrant stretching in the 1587–1612-, 1224–1304- and 560–640-cm−1 wave- vibration of the pendant aromatic ring and the further number regions (Jurasekova et al. 2008;Corredoretal. bands between 1300 and 1540 cm−1 can similarly be 2009). The spectrum shown of the yellow particle in the assigned to the aromatic in-plane bending modes, namely light-green sample from fragment 1147 is assignable to a 1537, 1512, 1487 1422 and 1363 cm−1. All of these are mixture of apigenin (5,7,4′-trihydroxylflavone) and luteolin close to their congeners in the pure pigments but are also (5,7,3′,4′-tetrahydroxylflavone), which differ in molecular slightly shifted as expected because of the environmental structure by only a single phenolic hydroxyl group on influence of the natural material. The bands in the Raman the pendant aromatic ring of the parent flavonoid skeleton, spectrum in the wavenumber range 1100–1300 cm−1 are a two-ring fused system with a pendant phenyl ring. assignable to the aromatic CH bending modes in the fla- Comparison can be affected with standard Raman spectra vone skeleton of luteolin and apigenin. The band at and SERS-excited Raman spectra (Jurasekova et al. 2006; 1049 cm−1 is the C–OH stretching mode of the phenolic Corredor et al. 2009) from silver colloid-impregnated pig- hydroxyl groups. Weaker features between 350 and ment solutions of luteolin and apigenin backed up with 900 cm−1 are again attributable to both luteolin and DFT quantum mechanical calculations to determine the apigenin, being determined as mixed modes involving mode activities and potential energy distributions. The fol- CCC ring deformations, in-plane ring bending and C–OH lowing assignments can then be made: the strongest fea- in-plane bending modes. To our knowledge, there are no ture in the spectrum of the yellow particle is that at references to the detection of this organic pigment hitherto 1598 cm−1, which is assignable to a coupled skeletal on Roman wall paintings, and therefore the presence of mode of the flavone involving the aromatic semiquinone dyer’s weld in the Servilia tomb makes this particular group and the symmetric ring CC stretching mode. In tomb unique. luteolin and apigenin, this mode occurs at 1612 and Two samples did not show any green pigment or 1600 cm−1, respectively, but the absence of the CO mode admixtures which make green; one from panel 3, which near 1650 cm−1 must be noted in the putative weld spec- only showed Raman bands of Egyptian blue and carbon, trum. This can be attributed to hydrogen bonding between and a second from panel 2, with goethite and carbon. Archaeol Anthropol Sci (2018) 10:1207–1223 1221

Table 3 Comparison of the main Raman bands of Our spectrum Corredor et al. 2009 Jurasekova et al. 2008 Corredor et al. 2009 Jurasekova et al. 2008 the organic compound (780 nm) [46] [45] [46] [45] found in 1147 fragment luteolin (1064 nm) Luteolin (1064 nm) Apigenin (1064 nm) Apigeonin (1064 nm) and the published Raman bands of luteolin and 1660s 1658 apigenin 1612vs 1608 1606s 1588s 1587 1597s 1578s 1549 1541m 1556 1537 1512 1498 1497 1504m 1421 1399 1383 1355 1363m 1373m 1302 1313 1304m 1288m 1274s 1270m 1267 1266m 1267 1238m 1245s 1246 1224m 1221 1190 1164m 1183m 1180 1049m 1131 1002 983 964 916 908 842 832m 789 729 635 645 643m 642 603 590 539 580m 518 381 369m 358 –*355–* –*

Conclusions desired tonalities; when only the colouring pigments were considered, between 38 and 42 different mixtures were used One hundred and eleven specimens from the Roman Servilia (see Table 2). tomb have been analysed by Raman spectroscopy. Eleven The use of Egyptian blue is remarkable not only for the colours were described: white, beige, black, pink, red, violet, blue colours themselves but also for its presence in some vi- yellow, yellowish ochre, brown, blue and green. When white olets (mixed with haematite) and greens. Green hues were the minerals were considered a part of the colour preparation, 73 most variable colour with regard to mineral mixtures, where different pigment admixtures were used for obtaining the not only green minerals diluted with white or black were 1222 Archaeol Anthropol Sci (2018) 10:1207–1223 characterised, but yellow and blue pigments were also References identified. 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