In situ Raman and pXRF spectroscopic study on the wall paintings of Etruscan Tarquinia tombs

Accepted Manuscript Mixture of pigments to obtain particular hues was a common practice for Archaic Etruscan painters in situ Raman and pXRF spectroscopic study on the mural paintings of Etruscan Tarquinia tombs G. Barone, P. Mazzoleni, A. Cecchini, A. Russo PII:

S0143-7208(17)31987-3

DOI:

10.1016/j.dyepig.2017.12.008

Reference:

DYPI 6414

To appear in:

Dyes and Pigments

Received Date: 19 September 2017 Revised Date:

18 November 2017

Accepted Date: 2 December 2017

Please cite this article as: Barone G, Mazzoleni P, Cecchini A, Russo A, Mixture of pigments to obtain particular hues was a common practice for Archaic Etruscan painters in situ Raman and pXRF spectroscopic study on the mural paintings of Etruscan Tarquinia tombs, Dyes and Pigments (2018), doi: 10.1016/j.dyepig.2017.12.008. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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In situ Raman and pXRF spectroscopic study on the mural paintings of Etruscan Tarquinia Tombs. Barone(1) G., Mazzoleni(1) P., Cecchini(2) A., Russo(3) A.

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1 - Department of Biological, Geological and Environmental Sciences -University of Catania, C.so Italia, 57, 95129 Catania (Italy). [email protected]; [email protected];

2- Associazione Amici delle Tombe di Tarquinia. [email protected]

3 - Soprintendenza Archeologica belle arti e paesaggio per l'area metropolitana di Roma, la provincia di Viterbo e

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l'Etruria Meridionale. [email protected]

ABSTRACT

The decorated graves of Tarquinia are among the more important pre-Roman records of classical painting

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in the Mediterranean. Their monumental series of funereal paintings, dated between the seventh and second century B.C., faithfully reflect the Etruscan civilization, of which they form a unique source of knowledge. They also represent indirect evidence of Greek paintings almost completely lost. The main goal of this research is the identification of pigments in order to clarify the unknown aspects of the materials used and, therefore, to furnish fundamental information to plan suitable restoration and

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conservation. With this aim in mind, complementary non-destructive and in situ handheld X ray fluorescence and Raman spectrometry were carried out on the wall paintings of eight of the more important Tarquinia graves, allowing us to highlight the use, together with common pigments such as hematite, carbon, goethite and calcite, of the more precious malachite, Egyptian blue, lazurite and cinnabar

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in some of the more notable tombs probably commissioned by rich nobleman. Furthermore, the research evidenced that the routine of mixture of pigments to obtain particular hues was a common practice for Archaic Etruscan painters. In this context the use of lazurite and probably of Tyran purple added to others

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pigments in symbolic details, opens new questions. On the whole, the value of these pigments gives additional importance to the Etruscan Necropolis. Moreover, the results of this study will be useful for future restoration and conservation strategies.

KEYWORDS: pigments; mural paintings; Etruscan; portable XRF; portable Raman spectroscopy

INTRODUCTION The most famous expressions of Etruscan paintings are the funerary decorations discovered in the necropolis of Cerveteri, Chiusi, Veio, Vulci and Tarquinia. The funerary paintings form a unique source of

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ACCEPTED MANUSCRIPT knowledge regarding the Etruscan civilization and represent indirect evidence of Greek paintings, almost completely lost [1–3]. The Tarquinia necropolis is one of the most beautiful and richest, considering the extension (over a wide hill territory of 750 ha) consisting of more than 200 decorated tombs built from the 7th to the 2nd century B.C. The importance of the site is attested also by the numerous studies on the subterranean chambers finalized

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towards archaeological and art history topics [4–7] and the preservation and/or restoration problems (Cecchini, 2012 and bibliography therein). Since 1827, several reports have shown the causes of degradation, many of these are strictly correlated to the opening of the graves since the first degradation cause was the variation of the microclimate and artificial lighting with a consequent increase of biological activity. Other causes, determining the damage of wall paintings, are the rise of capillary water, vandalism,

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and vibration caused by the use of agricultural machinery. Moreover, some incorrect restoration practices such as the wide dehumidification of the ambient or sometimes the application of untested protective

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products were responsible for a greater deterioration in some important tombs (Cecchini, 2012 and bibliography therein).

Another widely studied topic of the Tarquinia necropolis is the painting technique used for the decoration of the wall. Great importance was attributed to the preparatory layer, because it is considered the distinguishing element of Etruscan wall paintings. Even if there is not always a close correlation between technology and period, on the whole the more ancient tombs were painted directly onto smoothed rock

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while in the more recent ones, the bedrock was coated with one or more preparatory layers [6]. In particular, the substrate of the VI-V centuries B.C. tombs was coated with a white thin layer consisting of a mixture of powdered fossil limestone sometimes enriched with white clay, which improved the combining properties and appearance. In other cases, preparatory layers, formed by gray clay can be found probably

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with the aim to bring greater brilliance to the colors. Finally, the use of plasters preparatory layer was introduced only in the second half of the IV- III B.C.

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These differences give rise to numerous interpretations of the Tarquinia paintings technique too. In fact, some authors [8] argued that they are frescos based on their research in more recent tombs. On the contrary, others suggested there was the use of a tempera method in the older tombs according the egg binder found by [9] in the Etruscan Agro Chiusino tomb. Alternatively, the use of organic binders, is reported by Santamaria and Morresi (2012) who suggested the agglutination feature of the microfossiliferous limestone. In this scenario, one of the less studied questions concerns the identification of the pigments utilized in the Etruscan wall paintings [9–12]. Even if some information is reported in texts of ancient authors [13][14], an increasing interest emerged in the more recent scientific literature in the identification of wall painting pigments by means of nondestructive and in situ analytical methods. These last may discriminate the inorganic pigments thanks to characteristic key-elements determinate for example by portable X ray 2

ACCEPTED MANUSCRIPT fluorescence [15]. Regarding the mineralogical investigation, one of the principal techniques is Raman spectroscopy since it combines the required attributes of reliability and sensitivity, with those of being nondestructive [16,17]. This paper aims to study pigments used in the wall paintings of eight of the more impressive painted tombs of Archaic period applying combined handheld X-ray fluorescence and Raman spectroscopy. Furthermore,

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this research highlighted the potentiality in the use of these two micro-analytical techniques since they are applicable on site and have very good spatial resolution giving complementary information.

DESCRIPTION OF THE STUDIED TOMBS

In this paper we report the data obtained about the paintings of eight archaic Tarquinia necropolis graves.

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The studied tombs (named Fior di Loto, Leonesse, Cacciatore, Barone, Bartoccini, Tori, Giocolieri and Caccia e Pesca) are among the more beautiful and richly decorated of Etruscan art and are located near the

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actual Tarquinia village. All the tombs in the site are carved out of a very porous and brittle yellowish limestone locally named Macco, attributed to the Middle-Upper Pliocene [18]. The Fior di Loto Tomb (VI century b.C.) was discovered in 1962, it has a rectangular room with a pitched ceiling, decorated with flowers. The paintings are well preserved, especially those on the back wall, showing a lion and a panther separated by an upside down lotus flower on the gable pediments. Both of these animal figures have been painted with bright, cheerful colours. The coloured bands in the high parts

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of the walls were painted directly onto a grey clayey preparatory layer, probably to give intensity to the colours while the figures are overlaying on white background. The Leonesse Tomb (VI century b.C.) discovered in 1874, has a room with a pitched ceiling and is accessible by a stepped dromos. The roof has a checkerboard pattern, while the back wall is decorated with two

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lionesses on the pediment and two musicians and dancers. Lying banqueters are painted on the side walls above a decorated frieze with dolphins. The main colours are red, white, black, green and blue; painted on

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a white layer.

The Cacciatore tomb (VI-V century b.C.) was discovered in 1962. The decoration in this tomb represents a hunting lodge with other decorative elements: a succession of riders, bulls, lions, deer, warriors coloured with red, brownish red and blue on a thin, white layer overlaying on the grey preparatory level. The Barone tomb (VI century b.C.) discovered in 1827. The more important paintings show a few symmetrically distributed people and horses, separated by trees, representing the division between earthly life and the underworld, on a white background. The figures seem to be painted directly onto a grey layer. The style of the paintings shows links with the Greek-oriental artistic expressions and it is considered a unicum. The Bartoccini tomb (VI century b.C.) discovered in 1959, is famous because it was chosen by the Templars as a place for secret initiation rites of the Order of Chivalry. It is a burial chamber with three cells and a 3

ACCEPTED MANUSCRIPT pitched ceiling. The more ornate is the central room with a squared motif and banqueting scene on the gable pediment. The predominant colours are red, white and blue on a preparatory grey layer. The Tori tomb (second half of the VI century b.C.) was discovered in 1892. It is composed by a central room and two funerary cells. On the main pediment there are some erotic sketches, probably the more famous of the Etruscan paintings, while on the front wall there is a mythological episode. The paintings were done

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on lime plaster and Macco refined with a white clay preparatory layer. The pictorial decoration was created by marking the drawing with strings. The engraving and contours were performed first in red and then in black.

The Caccia e Pesca tomb (520-510 a.C.) was discovered in 1873. It has two rooms, the first shows, on the pediment of the frontal wall, a hunting scene, while, on the lateral walls, there are characters that are

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dancing and playing among the trees. In the second room, on the frontal wall, there is married couple on a triclinium with the servants. On the lateral wall there is fishing scene and on the left, the famous depiction

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of a boy diving off a rock, into the sea. The paintings were done on lime plaster and Macco, prepared before painting, with a white clay preparatory layer. The pictorial decoration was created by marking the drawing

with

strings.

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The Giocolieri tomb (VI B.C) found in 1961, has one single room. On the pediment of the frontal wall, below a red lion and a blue panther, there is an old man sitting on a stool, probably the deceased, watching the

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juggling games. On the right side wall there is a dance scene while, on the left wall, there is an elderly man with a beard and a scene with apotropaic value. The paintings were done on lime plaster and Macco, prepared before painting, with a white clay preparatory layer. The pictorial decoration was created by

METHODS

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marking the drawing with strings. The contours were done first with red and then with black.

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Portable non-destructive x-ray fluorescence (pXRF) were performed with a Bruker Tracer IV-SD system endowed with an x ray tube with Rh target (and Pd slits) source and a 10 mm2 Silicon Drift Detectors (SDD). The instrumental setups used for this study are: i) 15 kV, 35 mA, no filter and vacuum condition for elements from Na to Ca; ii) 40 kV, 17 mA, Ti-Al filter for the heavier elements. Each measure was carried out with 60 sec of accumulation. The measurement instrumentation was mounted on a tripod with an extending arm allowing us to place the window mask of the Tracer very close to the analyzing surface. The identification of the elements peaks was acquired directly on the laptop connected to the instrumentation by means of the software S1PXRF. Quantitative data were obtained using PyMCA software [19] based on fundamental parameter calculations. The configuration files were designed considering the Tracer IV-SD specification and the measurement setup. The attenuation was calculated considering a matrix composition formulated on the basis of qualitative XRF data and Raman spectroscopy. The method was 4

ACCEPTED MANUSCRIPT tested on 42 international standards giving good results. Even if this calculation is affected by errors due to fact that the thickness of the pigmented layer is not infinite and that the surface is not regular, the data allow us to constrain the chemical composition of pigments and to highlight their differences in the studied tombs. Raman spectra were collected by means of the portable “i-Raman Plus” spectrometer (B&W Tek, Inc), with

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two available excitation wavelengths (785 and 532 nm) and using a high quantum efficiency CCD array detector with deeper cooling and high dynamic range. The system was equipped with a Raman probe which includes a fiber optic interface for convenient sampling. The spot size is 85 μm at a working distance of 5.90 mm.

Micro-raman measurements were carried out with an objective apparatus mounted on a tripod with an

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extending arm and an optical camera for positioning the laser spot to the investigation point. The Raman instrument is controlled remotely via a USB cable connected laptop. All the measurements were collected

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after automatic dark subtraction.

PORTABLE AND NON-DESTRUCTIVE ANALYSIS FOR PIGMENTS STUDIES

In the last two decades, the development of technical solutions and the miniaturization of the apparatus components allow us to have portable instruments capable to furnish data directly on the object. These portable systems were used in many research field thanks to their rapidity, simplicity and in many case the

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low cost. One of the more promising application is the in situ study of Cultural Heritage were the object are frequently unmovable and sampling is not possible. However, even if the advantages in the use of portable and non-destructive instrumentation are in many cases evident, some limitation are due to [20]: i) the composition complexity of many artwork; ii) the 3D structure characterized frequently by overlaid layers

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with different composition; iii) the presence of altered surface due to the burial processes or the use of protective or consolidants products during restoration works.

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In the case of paintings, many efforts have been made in the attempt to identify pigments directly in museums or in archaeological site. Most of researches point to the identification of cromophorous chemical elements by mean of handled XRF [21]. Recently the development of software based on fundamental parameter allowed researchers to obtain quantitative analysis despite the difficulties due to the matrix correction and the multilayer structure [22]. On the whole, XRF analysis even if very important can not permit the univocal identification of the pigments especially if light elements are present. In order to give a more reliable description of the pigments, the portable Raman spectroscopy was frequently used [17]. Indeed, this technique possesses high potentiality in the recognition of pigments compounds although the portable instruments do not have the performance of laboratory spectrometers [23]. In this scenario, the combination of techniques such as XRF and Raman spectroscopy is a good approach thanks to the complementary information that they assure [24]. 5

ACCEPTED MANUSCRIPT In spite of the potentiality of the in situ investigation and the importance of the painted Etruscan tombs, the XRF and Raman in situ analysis are lacking in the scientific literature. The only XRF and Raman in situ data are relative to one tomb of the 4th century B.C. [25] and are largely insufficient to describe the use of pigments in the Etruscan tombs especially considering the more ancient ones (VI – V century B.C). This shortage of information, moreover, concerns also the Greek and Roman Archaic wall paintings [26] while

RESULTS

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more studies have been carried out on more recent paintings [27–29].

The points on which the analysis were carried out are shown in the figures reported for each tomb and the

assigned to each color on the basis of its analytical results.

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Fior di Loto Tomb

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qualitative XRF and Raman results obtained are listed in the tables. An identification pigment (IP) is

In this tomb (fig.1; tab.1), the acquisition of Raman spectra were, in many cases, difficult due to the use of highly fluorescent Paraloid in previous restoration works.

The dominant color of the tomb is white that in the roof assumes a pearly luster (FL1 and FL6). The Raman analysis (fig. 2a) permitted us to attribute the pigment to the use of calcite thanks to the intense 1086 cm−1 band attributable to the symmetric stretch (ν1) of the CO32− ion and to the 714 cm-1 assigned to the

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asymmetric stretching (v3) mode [30,31]. This result is confirmed by the XRF spectra characterized by high Ca peak and minor Si, K and Fe signals imputable to the substrate contribution. The analysis of the red pigment (FL4) indicated the presence of hematite (red ochre) as attested by Raman peaks (fig.2b; 223, 290, 407 and 610 cm-1) [32,29] and by the pronounced Fe peak together with lower Mn,

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Cu and As signals in the XRF.

In the blue portion (FLX3), pXRF investigations evidenced the use of a Cu bearing pigment with minor

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amounts of Pb and Sn. Raman spectrum (fig.2c) obtained on it showed the 430, 466 and 1084 cm-1 peaks of the Egyptian blue (cuprorivaite CaCuSi4O10) [33,34]. Finally, pXRF measurements on green color (FL7), allowed us to establish that the used pigments were based on Cu rich compounds. The Raman spectra (fig.2d) indicate the presence of malachite (156, 170, 181, 220, 271, 351, 435,534, 1085 cm-1)[35].

The Leonesse tomb The in situ examination indicated the use of two different red pigments. In the front wall of the tomb (fig.3; tab.2; LEO1-5-9) cinnabar was used as showed by Raman spectra (fig.4a; 254 cm−1, 344 cm-1) [33] and by the presence of Hg in XRF spectra (fig.4b). In particular, cinnabar was detected in the bright red on the border of the dancer’s dress. 6

ACCEPTED MANUSCRIPT On the contrary, the red pigments used in the side walls (LEO2-4) are red ochre as revealed by Raman (hematite: 226, 292, 410 cm-1) and XRF. Regarding the green pigment, XRF revealed the presence of Cu and Ca together with less pronounced Fe and Zn peaks. However, the identification of the Cu rich pigment by Raman analysis was not possible due to high fluorescence perhaps caused by the use of protective products in the previous restoration works.

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Blue pigment is composed mainly by Cu but unlike the green pigment, Sn and Pb were detected as in the Fior di Loto tomb. Also in this case, it was not possible to identify the pigment due to the high Raman fluorescence but the close compositional similarities with the Fior di Loto blue suggest that it is Egyptian blue. The analytical results obtained on the white portion of the painting (LEO6) confirm the use of calcite

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as pigment.

The Cacciatore tomb

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In this tomb (fig.5; tab.3), a dark red hue is juxtapose to the red already seen in the previous tomb (ID R1). Both pigments have pXRF and Raman spectra characteristic of red ochre but the dark red one is distinguishable due to the Raman signal of carbon (fig.6; large bands at 1300 and 1600 cm-1) [36]. This pigment is also characterized by remarkable presence of As. However, a mixing of red ochre with As bearing phase (i.e. realgar - As2S2) is improbable since the Raman spectra does not evidence the presence of realgar.

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The XRF spectra, performed on the light blue pigment, have the Cu peaks associated like in the pigment of the Fior di Loto tomb with weak peaks of Pb and Sn.

In XRF spectra obtained from the white area (CA1, 4), the Ca peak is always the more relevant and related to calcite while Fe, Si, K peaks are probably associated to the mineralogical composition of the painting

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The Barone tomb

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substrate (grey preparatory layer; CA2, 3, 5, 8) in which these elements are more relevant.

This tomb (fig.7; tab.4) is characterized by variegated paintings. Among the red pigment, it is possible distinguish three hues: i) the branch of the tree (BA1) and the cloak of the woman (BA6) in the frontal wall (BA1) have Raman and XRF spectra typical of red ochre pigment; ii) the branch of the tree on the right wall (BA9) has a darker hue than the previous one and is characterized by the XRF spectrum with the As peak similar to that of the dark red of the Cacciatore tomb; iii) the brilliant red of the calf of the defunct (BA5) reveals the presence of Hg with trace of Fe due to the use of cinnabar as evidenced by Raman spectrum. Noteworthy, it is the presence in this tomb of the violet color used in some important details such as the shoes of the defunct (BA4) and the border of his wife’s dress (BA7). The measurements gave unexpected results since the XRF analysis shows the presence of As, Fe and Cu while micro-Raman spectra (fig.8) evidenced the peaks of hematite, carbon and lazurite (fig.9; 253, 245, 798, 1094, 1641 cm-1) [37] on red, 7

ACCEPTED MANUSCRIPT black and blue particles respectively. The latter is a tectosilicate Na6Ca2(Al6Si6O24)(SO4,S,S2, S3,Cl,OH)2 present together other minerals in lapis lazuli. Green color is used in the leaves (BA2, BA2a and BA10) and in the shoes (BA8) of a person painted on the right wall. Furthermore, a darker green hue is observable in the hair of the defunct (BA3). PXRF measurements allow us to establish that the used pigments were based on Cu compounds but significant Si

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peaks are observable too. Furthermore, pXRF spectra showed the presence of minor amount of Hg. The micro-Raman spectra indicate the use of malachite with the addition of cinnabar, green earth (celadonite K(Mg,Fe2+)Fe3+(Si4O10)(OH)2), and in the dark green carbon. XRF measurements were obtained on the

grey preparatory layer and on the plaster; both are characterized by high Ca but the first has a higher Si

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signal.

The Bartoccini tomb

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Also in this tomb (fig.11; tab.5) different red hues are visible: i) the prevalent red color has the same hue as most of the other tombs and is formed by red ochre, as shown by the analysis of the bands in the left room (BART7b); ii) the light orange of the lion in the gable of the right room (BART1) is probably obtained using a different ochre richer in Fe- hydroxides, mixed with calcite as evidenced by XRF analysis; iii) Fe and As are distinctive of the dark red measured in the gable (BART2) and in the goat (BART3) of the right room, in the

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shoes (BART4) and in the dress (BART5) of the principal room and in the dark band of the left room. Worth noting is the presence of Cu in the BART2, BART3 and BART4 spectra. The blue color outlining the goat is formed by a Cu rich pigment in which there is a lead contribution. Also in this case the white is calcite, while the Raman spectra of the black shows only the carbon bands. The measurements carried out on the white

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pigment (BART11, 12, 13) and on the grey preparatory layer (BART10) exhibit high Ca peaks while Si is more pronounced on the grey layer.

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The Tori tomb

In this tomb (fig.12; tab.6) there is the same red palette observable in the previous tombs. The analytical results showed that chemical and Raman data are very closely related to those already reported (table 6). However, the blue pigment under the bull (TOR5) has only the Cu peak without Sn and Pb signals while more peculiar is the green measured in the shoes in which Hg and Pb are present in addition to Cu. The white pigment (TO11, 12, 13) of this tomb has the chemical composition qualitatively close to the other analysed white colors. Finally, it was investigated the Macco bedrock that shows a XRF spectra dominated by the Ca peak.

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ACCEPTED MANUSCRIPT The Giocolieri tomb The painting of the frontal wall of the tomb (fig.13; tab.7) shows the use of different nuances of red: i) the orange hue (GIO1-3) has the XRF spectra in which Fe and Ca are the more strong peaks like in the orange of the Bartoccini tomb; ii) the pink color (GIO4) is distinguishable by the weak Fe peak and higher Ca signal and was probably the result of a mixing of red ochre with calcite; iii) the dark red (GIO5) is comparable to

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the same color of the other tombs with XRF spectra in which are observable As in addition to Fe. The blue color (GIO7) is similar to all the blue analysed in the other studied tombs, with Cu and weak peaks of Sn and Pb. Finally, the color black is obtained with carbon as shown by Raman spectra.

The Caccia e pesca tomb

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The orange color of the man’s complexion in this tomb (fig.14; tab.8) has a chemical composition dominated by Fe and Ca with weak Cu peak while the dark red pigments (CP3, 4, 7), as in the other tombs,

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are Fe and As rich. However, CP3 is characterized by a relevant Cu peak whereas in the CP4 and, to a lesser extent in the CP3, it is noteworthy a weak Br signal (fig.15). This last element is detectable also in the violet color of the woman’s dress (CP6) together with Fe and Ca, this suggests the use of a pigment obtained with the adding of Tyrian purple [26] even if this use must be verified by further analysis. Finally, the triclinium violet (CP5), does not present bromine but it is based on Fe and Cu compounds. Green and blue colors (CP8, 9 and CP10, 12 respectively) are obtained by Cu-based pigments with XRF

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spectra similar to those of the other studied tombs.

DISCUSSION

The chemical data and the results of Raman mineralogical analysis show a remarkable variety of pigments

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utilized in the eight studied tombs (tab.9). With the aim of giving a more detailed description of the chemical composition of the pigments, the quantitative elemental results of selected pXRF analysis

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performed by PyMca software [19] are reported in table 10 .

Red and violet pigments

The chemical data suggest that most of red and violet colors are based on Fe rich pigments. However, some differences may be recognized by chemical and mineralogical analysis. In all the studied tombs, hematite is the principal coloring phase giving the typical red ochre hue. The light red or pink nuance was obtained by mixing this pigment with calcite as testify by the measured high CaO abundance (tab. 9). The same features are shown by XRF spectra of orange but the yellowish hue is probably due to a different ochre, rich in hydroxides, even if this suggestion is not supported by Raman analysis. The dark red and the violet pigments are distinguishable in all the tombs by the high As (fig. 16). Furthermore, the Raman spectroscopy revealed that these colors are due to the presence of hematite and 9

ACCEPTED MANUSCRIPT carbon while the analytical results excluded a relevant quantity of As-minerals. Therefore, the arsenic high abundance may be interpreted as due to the composition of a red ochre such as that used in some Pompeian wall paintings [28]. High As abundance was detected in red ochre of Mt. Amiata district (Tuscany) due to the adsorption on iron (hydr)oxide nanoparticles. In this perspective, it is plausible the use in the Tarquinia wall paintings of red ochre coming from nearby region.

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Worth noting is that, in the Caccia e Pesca tomb, the red and the violet used in the clothes of both the dead man and woman show meaningful Br abundances suggesting the use of precious Tyrian purple [26] mixed with ochre. This hypothesis, although it needs confirmation, may be interpreted as the desire to reproduce, also symbolically, the richest of the defunct clothes.

The peculiarity in the composition of the violet pigments are testified also by the Raman analysis of the

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woman’s dress on the frontal wall and of those belonging to the young man on the right wall of the Barone tomb. In these cases the micro-Raman evidenced the use together with hematite and carbon, of lazurite

highlighted in the Archaic Etruscan tombs.

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known as Caeruleum Scythicum pigment in the Roman age [13,14]. This latter was for the first time

The only exception to the prevalent use of hematite - with other pigments for the red and violet colors- is represented in the Leonesse and Barone tombs in which some decorative details, such as the calf and the shoes of important figures in both the tombs, are obtained with the cinnabar, up to now, found only in the wall paintings starting from the V century B.C. [38] and in the pottery decoration of the IV-III century B.C.

Green pigments

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[39].

In all the tombs the green colors are obtained by the use of Cu compounds. Raman spectra allows us to

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identify the malachite as the main green coloring phase in the Fior di Loto and Barone tombs. Moreover, in the Barone tomb, malachite is associated with celadonite while cinnabar was detected thanks

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to micro-Raman analysis of red particles present in some portions painted with dark green hues. The chemical composition confirms the peculiarity of the Barone green pigments that have a higher Si abundance than those observed in the other tombs (fig. 17a). Furthermore, Hg contents of the Barone greens support the use of cinnabar. This latter may be assumed on the basis of the composition as well as for the Tori tomb green color of which however there is no Raman data. Finally, the dark green hues observable in the Barone tomb were obtained with the addition of carbon as suggested by Raman spectrometry. In this context, the presence of arsenic in the dark green color may support the use of conichalcite CaCuAsO4 (OH), a pigment reported in Late Classical and Hellenistic painting [40]. However, this mineral was not detected by Raman analysis.

Blue pigments 10

ACCEPTED MANUSCRIPT In respect to the other elements the blue hue shows a relative homogeneity. The Raman spectra in Fior di Loto and Bartoccini tombs allow us to identify cuprorivaite as the main pigment in these paintings. In the other tombs it is possible to suppose the same phases since the ratio Si/Cu is similar and close to the cuprorivaite one (fig.17a). The presence also of Sn and Pb (fig.17b) in Giocolieri, Caccia e Pesca, Leonesse and Fior di Loto tombs suggests that the Egyptian Blue was synthesized probably with copper alloy with

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traces of other metals [41].

White and black pigments

In all the tombs the white pigments are calcite, as detected by Raman analysis and confirmed by the high CaO abundance (tab. 8). The low MgO and SiO2 abundances suggest a quite pure limestone or marble with

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low dolomite contents as raw material.

The black pigment used is always obtained by amorphous carbon [42]. The low arsenic abundance strongly

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contrasts with the hypothesis that this element is controlled in the dark red and green pigment by using carbon.

The Limestone substrate, plasters and grey preparatory layer

The local outcropping limestone, named Macco, and the plasters of the Toro tomb, formed principally by calcite with a low silicoclastic component, is envisaged by SiO2 and Al2O3 abundances obtained by XRF

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(tab.8). The ratio CaO/MgO and Sr/CaO are very similar suggesting that the plasters were produced starting with Macco as a raw material. Finally, the gray substrate shows the chemical composition of a calcareous

CONCLUSION

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marl with SiO2, Al2O3 and K2O due to the clay minerals component.

Our approach, with new non-destructive instrumentation, gives us an opportunity to reexamine the above

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mentioned questions and provide a new perspective regarding the use of color in Etruscan scenario. Thanks to the comparison between the results obtained from the different color pigments, it is possible to conclude that precious pigments have been used extensively in the analyzed tombs. Particularly interesting is the presence of cinnabar as a red pigment of some symbolically relevant details. Until now, this mineral was observed in the more recent (IV century) Orco tomb [25]. Among the violet and dark red pigments, the presence of As, suggest probably the use of a ochre caved in the Mt Amiata (Tuscany) region. The addition of lazurite to hematite and carbon to obtain a violet hue in the Barone tomb, raises other problems since this mineral, until now, was not identified in the Etruscan paintings even if it was erroneously reported as blue pigment in the Bighe tomb [6].

11

ACCEPTED MANUSCRIPT The presence of Br in the pigments used to paint the dress of the defunct, in the Caccia e Pesca tombs, allow us to hypothesise the use of Tyran purple, until now never reported, suggesting the symbolic use of the colors. Blue was obtained using the synthetic Egyptian blue, in which the presence of Sn suggests that in preparing the pigment, copper and also bronze alloys have been used together. Previously, this pigment was reported

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in the Leonesse (Santamaria U. et al. 2012) and Tori tombs (Borrelli 2003; Brecoulaki 2001), in the Demoni tomb (Santamaria U. et al. 2012) and in the Chiusi and Sarteano tombs (Colombini et al., 2003).

Regarding the color green, it is always a copper bearing pigment that, in some cases, may be identified as malachite. This data is in contrast with the common opinion that in the archaic paintings the green colors were obtained by using green earth [10,12].

SC

On the whole, the results evidenced the Etruscan artist pictorial research of new hues through the use of pigments mixing with the aim to give a naturalistic view [38]. Furthermore, interesting is the presence of

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precious pigments in the richer tombs and in the more important representation suggesting the linkage between the importance of the defunct and the relevance of the painting.

Acknowledgement

The authors are grateful to Valentina Vasta and Elisa Le Pira for the participation to the analysis

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campaign and Arlen Heginbotham for the help in the PyMca configuration setup.

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15

ACCEPTED MANUSCRIPT

Distinctive elements Fe + Mn + Cu + As Cu + Sn + Pb Cu Ca Ca + Si

Mineralogical composition Hematite + carbon Egyptian blue Calcite

RI PT

colour Dark Red Blue Green White Grey

ID DR1 B1 G1 W GR

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Point of analysis FL4 FL3, 11 FL7, 10 FL2, 6 FL8, 9

Colour Red Red Light blue Blue Green White

Distinctive elements Hg Fe Cu + Ba Cu + Sn + Pb + Zn Cu Ca

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Point of analysis LEO1, 5, 9 LEO2, 4 LEO3 LEO7 LEO8 LEO6

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Table 1 - Qualitative pXRF and Raman spectroscopy results for the analysed pigments and preparatory layer (grey) in the Fiore di Loto tomb. Mineralogical composition Cinnabar Hematite

ID R3 R1 B2 B1 G1 W

Table 2 - Qualitative pXRF and Raman spectroscopy results for the analysed pigments in the Leonesse tomb. Distinctive elements Fe + Cu + As Fe + Cu(-) Cu+ Sn+Pb Ca Ca+Si

Mineralogical composition Hematite + Carbon Hematite

EP

Colour Dark Red Red Light blue White Grey

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Point of analysis CA6 CA7 CA9 CA1, 4 CA2, 3, 5, 8

ID DR2 R2 B1 W GR

Table 3 - Qualitative pXRF and Raman spectroscopy results for the analysed pigments and preparatory layer (grey) in the Cacciatore tomb. Point of analysis BA1,6 BA5 BA9 BA4, 7 BA2, 2a, 3, 8, 10 BA12 BA13

Color Red Red Dark Red Violet Dark green Grey Plaster

Distinctive elements Fe Hg + Fe(-) Fe(++) + As Fe + As Cu + Hg Ca + Si Ca

Mineralogical composition Hematite Cinnabar Hematite + Lazurite + Carbon Malachite + Cinnabar +/- Carbon Calcite

ID R1 R3 DR3 V1 DG GR PL

Table 4 - Qualitative pXRF and Raman spectroscopy results for the analysed pigments, preparatory layer (grey) and plaster in the Barone tomb. 16

ACCEPTED MANUSCRIPT Color Orange Red Dark red Dark Red Blue Black White Grey

Distinctive elements Fe(-) Fe Fe + As + Cu Fe + As Cu + Pb Ca Ca + Si

Mineralogical composition Hematite + Calcite Hematite Hematite + Carbon Hematite + Carbon Carbon Calcite

RI PT

Point of analysis BART1 BART7b BART3, 4 BART2, 5, 6, 7 BART8 BART9 BART11, 12, 13 BART10, 14

ID O1 R1 DR2 DR3 B3 BL W GR

Color Dark Red Red Blue Green White Bedrock

Distinctive elements Fe + Cu + As Fe Cu Cu + Hg + Pb Ca Ca

Mineralogical composition Hematite + Carbon Hematite

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Point of analysis TO1 TO2-4-6-7-9 TO5 TO10, 8 TO3, 11, 12, 13 Macco

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Table 5 - Qualitative pXRF and Raman spectroscopy results for the analysed pigments in the Bartoccini tomb.

Calcite Calcite

ID DR2 R1 B4 G2 W BR

Table 6 - Qualitative pXRF and Raman spectroscopy results for the analysed pigments and the bedrock in the Tori tomb. Distinctive elements Fe

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Color Orange Pink Dark Red Blue Black White

Fe + As Cu + Sn + Pb

EP

Point of analysis GIO1, 2, 3 GIO4 GIO5 GIO7 GIO8 GIO9

Ca

Mineralogical composition Hematite + Calcite Hematite + Calcite Hematite + Carbon Carbon Calcite

ID O1 P DR3 B1 BL W

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Table 7 - Qualitative pXRF and Raman spectroscopy results for the analysed pigments in the Giocolieri tomb.

Point of analysis CP1, 2 CP3, 4 CP7 CP5 CP6 CP8, 9 CP10, 11 CP12 CP13

color Orange Dark Red Dark Red Violet Violet Green Blue Blue White

Distinctive elements Fe + Cu Fe + Cu + As + Br Fe + Cu + As Fe + Cu Fe + Cu + Br Cu Cu + Sn + Pb Cu + Pb Ca

Mineralogical composition Hematite + Calcite Hematite + Carbon

Calcite

ID O2 DR4 DR3 V2 V3 G1 B1 B3 W

17

ACCEPTED MANUSCRIPT

Fior di Loto Leonesse Cacciatore Barone Bartoccini Tori

X

P X

O1

X

O2 X

R1

X X

X X

DR2

X

X

DR3 DR4

X

V1 V2 X

X

G2 X

X

X

X X X X X

X

B4

X

AC C

X X

X

EP

B3

GR

X X

B2

BL

e

X

DG

W

Caccia pesca

X

X

TE D

V3

B1

X

M AN U

X

R3

G1

X

X

R2 DR1

Giocolieri

SC

ID

RI PT

Table 8 - Qualitative pXRF and Raman spectroscopy results for the analysed pigments in the Caccia e pesca tomb.

X X

X X

X

X X

X

X

X

X

X

X

X

X

Table 9 – Distribution of the identified pigments in the studied tombs. The characteristics of the ID are reported in the tables 1 - 8

18

ACCEPTED MANUSCRIPT

ID

TO2

R1

3.8

0.3

1.5

3.5

0.1

0.7 84.1

4.5

0.5

0.1

V

Cr

Co

Ni

Cu

Zn

As Br Rb

Y Zr

Sn

Ba

Hg

Pb

3

23

21

10

37

17

16

6 19 144 13 25

-

702

10

33

LEO2

R1

3.7

0.1

1.2

1.4

0.1

0.5 86.3

5.2

0.4

0.2

12 272

376 178

34

2

- 1260

91

24

CA7

R2

8.2

1.0

1.8

34.8

0.3

0.2 46.4

5.0

1.1

0.1

96 131

0

8

BA9

R2

16.4

1.2

3.8

21.7

0.1

0.4 48.5

4.6

1.9

0.3

1

72

18

12

110

32

16 12 26 275 15 33

-

175

0

32

637

32 140 14 21 204 15 19

-

192

22

34

BA5

R3

7.1

0.2

1.5

3.0

0.1

0.6 84.5

1.9

0.3

0.3

25

71

11

29

327

39

44

1 24 355 13 21

-

150

140

44

LEO1

R3

5.8

0.1

1.7

1.9

0.1

1.0 78.5

7.2

0.3

0.2

17

35

1

10

502 149

48

4

1

0 25

-

68 29279

1

63

0 18 214

37 172

SC

SiO2 TiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O K2O P2O5

RI PT

Sample

5

1

0

0

R3

2.7

0.1

0.9

1.5

0.1

0.3 89.6

3.3

0.4

0.3

16

38

2

0

490

9 22

-

100

3238

26

FL4

DR1

17.1

1.2

3.1

21.8

3.1

0.0 44.0

6.8

1.9

0.0

64

66

0

36

1628

41 119

8 32 199 10 33

-

185

2

32

BART2

DR2

10.6

0.4

2.1

9.5

0.1

0.2 73.7

1.8

0.7

0.2

42

68

6

26

1503

36 353 31 27 309 12 24

-

9

7

43

BART3

DR2

7.2

1.2

2.0

39.4

0.2

0.3 44.7

2.1

1.0

0.3 116

95

13

17

276

71 175 10 33 592 12 25

-

913

3

21

BART4

DR2

21.6

1.1

4.9

18.4

0.5

0.8 46.5

3.2

2.3

0.2

63

84

4

41

552

84 412 20 78 362 22 90

-

69

2

41

TO1

DR2

10.3

0.3

2.2

9.4

0.1

0.5 73.4

2.4

0.7

0.2

31

63

3

22

207

30 228

5 25 227 14 32

-

164

72

51

CA6

DR2

8.9

0.6

1.8

29.0

0.3

0.4 52.1

4.9

1.2

0.1

63 124

2

29

371

53 708

8 40 434 15 44

-

8

9

37

BART5

DR3

22.2

2.5

4.9

37.5

0.6

0.8 24.4

3.3

2.3

0.4 102 116

1

59

86

85 316 19 46 249 20 42

-

257

2

29

BART6

DR3

10.6

0.8

2.6

23.6

0.2

0.2 58.9

1.1

1.1

0.1 102 103

30

31

83

44 150 16 45 400 19 38

-

64

6

28

BART7

DR3

10.0

0.4

2.7

8.1

0.1

0.6 74.1

2.2

1.0

0.2

52

73

3

39

91

41

-

142

1

42

GIO5

DR3

4.5

0.2

1.3

9.2

0.1

0.4 81.1

2.3

0.4

0.1

28

59

6

34

81

35 474

6 21 370 13 22

-

17

31

38

CP7

DR3

2.9

0.1

1.0

3.7

0.0

0.2 87.3

3.1

0.2

0.8

14

31

27

26

30 154 11 28 377 11 22

CP3

DR4

0.2

0.2

1.5

11.8

0.3

1.9 77.0

6.7

0.3

0.1

42

23

21

2

CP4

DR4

1.4

0.1

1.1

3.3

0.0

0.4 91.4

1.3

0.2

0.1

48

40

17

6

BA4

V1

25.1

1.1

4.4

18.0

0.2

0.5 45.7

1.9

2.0

0.3

48

91

27

BA7

V1

13.4

1.0

3.3

18.4

0.2

0.4 56.4

3.5

0.3

24

60

3

CP5

V2

0.1

0.1

1.3

6.6

0.4

1.6 82.2

7.1

0.2

0.2

20

66

CP6

V3

1.1

0.1

1.0

1.8

0.0

0.4 92.3

1.8

0.2

0.1

4

25 20 47 418 15 33

-

9

10

45

98 37 24 422 10 24

-

1

13

38

321

38 185 83 28 472 17 33

-

182

11

39

24

573

52 200 23 32 295 14 18

-

333

9

45

36

196

50 205 27 25 243 15 21

-

394

2

42

6

19

347

31

81 13 28 458 13 21

-

106

8

47

39

2

9

2254

57

89 74 28 462 19 25

-

101

12

47

3070 112

1.8

BART1

O1

3.7

0.1

1.3

1.8

AC C

EP

TE D

M AN U

LEO5

330

37

2

Sr

0.1

0.4 89.3

2.3

0.3

0.3 111

62

46

12

119

16

3 12 28 339 14 27

-

239

17

53

GIO1

O1

0.3

0.2

1.3

8.6

0.1

2.5 82.2

3.8

0.4

0.3

51

54

17

23

60

40

19 15 20 346 13 15

-

35

9

37

GIO2

O1

6.4

0.2

1.8

3.7

0.1

0.4 84.3

2.1

0.4

0.2

13

35

1

14

57

20

9

5 24 324 13 16

-

113

13

30

GIO3

O1

2.3

0.1

1.2

3.3

0.1

0.3 89.5

2.3

0.3

0.1

23

69

0

13

82

22

30

8 17 293 14 20

-

202

13

41

CP1

O2

0.2

0.0

0.8

2.3

0.1

1.5 91.1

3.4

0.1

0.3

36

29

2

18

216

33

34

3 29 384 14 14

-

89

22

39

19

2.0

0.1

0.9

1.4

0.1

0.4 92.1

2.2

0.2

0.1

25

55

0

6

709

26

34 11 17 376 16 24

-

139

38

42

P

1.6

0.1

0.9

0.7

0.0

0.4 92.5

2.8

0.1

0.2

3

45

41

17

58

19

22 11 15 335 15

6

-

43

16

49

CP8

G1

2.2

0.1

1.0

5.1

0.2

0.5 73.2

2.4

0.3

0.2

59

58

5

3

30743 389

92 17 30 458 18 23

41

16

1

67

CP9

G1

1.2

0.1

0.7

3.9

0.3

0.3 79.2

2.4

0.2

0.2

76

74

61

9

36118 469

87 15 24 386 12 21

51

52

12

61

FL7

G1

9.1

0.4

2.2

9.9

0.2

0.3 42.2

5.0

0.6

0.1

69

65

1

12

76

81

14

44

LEO8

G1

3.8

0.2

0.9

2.1

0.1

0.4 55.3

3.7

0.4

0.1

68

89

61

49

8 20 117

75

6

79

TO10

G2

12.0

0.6

2.7

5.0

0.1

0.5 38.1

2.6

1.2

0.3

25

55

17

17 102941 548

68

9 21 316 21 15

36 1424

206 103

BA2

DG

17.7

0.6

2.7

6.1

0.1

0.5 16.1

1.3

1.3

0.1

78

66

2

65 144026 693

89

3 30 275 26 21

47

258

697

95

BA2a

DG

16.6

0.7

2.5

7.5

0.1

0.0 10.2

2.1

1.3

0.0

75 105 162

71 146843 727 133

1 36 325 23 24 137

496

746

96

BA3

DG

18.1

0.6

2.3

7.1

0.1

0.1

8.4

1.1

1.2

0.1 136 127

25

64 180630 812 122

0 39 288 26 34

54

552

856

85

BA10

DG

18.2

0.7

2.9

7.0

0.1

0.3 14.8

1.4

1.4

0.2

22

39 143980 702

89

6 43 296 25 22

45

347

463 111

CP10

B1

10.6

0.1

0.9

3.8

0.2

0.3 67.6

2.1

0.5

0.2

49

64

2

0

23024 104

30

6 30 566 10 31 106

113

4 350

CP11

B1

10.9

0.1

0.8

1.4

0.0

0.5 75.1

2.1

0.1

0.2

25

32

3

4

20702

83

22

8 25 612 14 18 173

130

21 470

GIO7

B1

16.9

0.2

0.8

2.7

0.1

0.4 59.3

1.9

0.3

0.2

18

36

34

12

33584

76

39 11 22 566 11 20 134

6

24 387

FL3

B1

27.3

0.8

2.3

15.5

0.7

0.3 25.6

6.2

1.1

0.0

40

56

16

23

15584

66

31 11 51 376 13 53 205

106

7 278

LEO7

B1

14.8

0.1

1.0

1.8

0.1

0.3 67.6

4.7

0.3

0.1

14

48

2

2

13793

34

LEO3

B2

7.4

0.1

1.1

1.4

0.1

0.4 74.9

4.0

0.3

0.2 121 192 651 186

22691 169

32 10

CP12

B3

10.9

0.2

1.0

2.3

0.1

0.5 71.0

2.6

0.3

0.3

11

53

46

14

17414

31

BART8

B3

21.0

0.2

0.8

5.9

0.1

0.3 51.2

2.0

0.1

0.1

55

55

63

13

38870 163

TO5

B4

18.2

0.2

1.1

2.4

0.2

0.3 65.9

3.3

0.4

0.2

51

39

16

11

9945

BART13

W

2.1

0.1

0.7

0.7

0.0

0.4 92.2

3.3

0.3

0.2 105 159

41

20

463

BART11

W

2.0

0.2

0.8

1.3

0.1

0.5 92.6

2.0

0.3

0.2

32

70

5

6

33135 199 90322 904

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47

1

3 19 273 16 16

25 10 14 314

8

3 22 419 13 25 285 8

1

2

0

7 27 529 14 19 138

97 11 28 524

2

0 1960

3 341 89

35

2

5 601 11 390

9 27

42

95

44 225

8 33 573 16 33

52

165

8

57

63

92

4 33 347 13 32

-

214

3

40

65

16

2

6 17 276 13

9

-

310

13

31

W

2.3

0.1

1.0

1.0

0.1

0.3 92.4

2.3

0.2

0.3

35

67

3

11

40

13

11

7 17 273 13 13

-

143

10

39

CA1

W

5.3

0.2

1.3

2.4

0.2

0.4 84.9

4.4

0.8

0.1

79 102

6

20

58

31

2

5 28 261 10 38

-

31

8

39

CA4

W

3.6

0.2

0.9

1.6

0.1

0.4 88.6

3.9

0.6

0.2

72

55

0

11

62

21

4

7 24 265 11 30

-

48

7

30

CP13

W

1.3

0.1

0.7

0.8

0.1

0.5 94.1

2.2

0.1

0.1 279

29

10

6

45

17

5

5 22 236 11 17

-

696

11

26

LEO6

W

2.3

0.1

0.7

1.8

0.1

0.3 91.3

2.8

0.4

0.2

26

66

2

0

409

31

52

0 15 175

8 19

-

180

2656

21

TO11

W

5.0

0.3

1.6

1.9

0.1

0.5 87.9

1.9

0.6

0.2

39

84

14

22

49

27

16

9 31 239

9 28

-

109

10

61

TO12

W

5.1

0.3

1.5

1.9

0.2

0.3 88.5

1.4

0.7

0.2

59

80

2

27

161

30

36 10 27 209 12 19

-

18

12

45

TO13

W

5.6

0.3

1.4

1.7

0.1

0.3 87.8

1.9

0.7

0.2

97 118

3

23

44

20

0

8 29 210 12 26

204

16

38

BART9

BL

5.9

0.4

1.6

4.2

0.2

0.3 84.4

1.9

0.9

0.2

22 111

29

20

47

36

9

8 35 330 17 24

-

209

12

37

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CA8 BART10

GR GR GR

Limestone

BA14

1.1

2.4

8.5

0.2

0.7 69.8

4.4

2.0

0.3

9.9

0.6

2.0

6.6

0.3

0.5 74.8

3.8

1.4

0.1 147

10.8 1.4

Limestone BA13

10.6

PL PL

0.8 0.1

2.0 0.7

9.0 0.4

0.3 0.0

0.3 71.2 0.3 95.8

3.7 1.1

1.8 0.1

0.1 0.1

40 107 24 35

90 55 37

8

9

609

20

5

6 17 170 11 10

-

162

8

33

38

26

485

33

18

7 29 279 12 36

-

111

5

28

-

135

7

33

8

-

262

11

54

90

13

26

631

13

29

- 1012

11

41

9 12

0 4

4.2

0.1

1.1

1.5

0.0

0.3 88.8

3.1

0.7

0.2

4

91

0

9

1.5

0.2

0.7

0.5

0.1

0.3 94.8

1.5

0.2

0.1

33

52

0

12

4.4

0.2

1.1

2.1

0.1

0.2 90.5

0.7

0.5

0.2 398

65

7

82

4

41

22 36

19 13 18 227

8 28

1 12 12 187 11

46

19

2

5 16 330

9 22

-

40

13

0

7 16 269 11 10

-

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41

23

9 14 27 300 11 27

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Table 10 – Chemical composition of selected pXRF analysis. Major elements are reported in wt%, minor elements are in ppm. The major elements chemical data reported have been recalculated to 100%. The meaning of the ID codes was specified on the tables 1-8

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ACCEPTED MANUSCRIPT TABLE CAPTION Table 1 - Qualitative pXRF and Raman spectroscopy results for the analysed pigments and preparatory layer (grey) in the Fiore di Loto tomb. Table 2 - Qualitative pXRF and Raman spectroscopy results for the analysed pigments in the Leonesse tomb.

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Table 3 - Qualitative pXRF and Raman spectroscopy results for the analysed pigments and preparatory layer (grey) in the Cacciatore tomb. Table 4 - Qualitative pXRF and Raman spectroscopy results for the analysed pigments, preparatory layer (grey) and plaster in the Barone tomb.

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Table 5 - Qualitative pXRF and Raman spectroscopy results for the analysed pigments in the Bartoccini tomb.

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Table 6 - Qualitative pXRF and Raman spectroscopy results for the analysed pigments and the bedrock in the Tori tomb. Table 7 - Qualitative pXRF and Raman spectroscopy results for the analysed pigments in the Giocolieri tomb. Table 8 - Qualitative pXRF and Raman spectroscopy results for the analysed pigments in the Caccia e pesca tomb.

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Table 9 – distribution of the identified pigments in the studied tombs.

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Table 10 – Chemical composition of selected pXRF analysis. Major elements are reported in wt%, minor elements are in ppm. The major elements chemical data reported have been recalculated to 100%. The meaning of the ID codes was specified on the tables 1-8.

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FIGURE CAPTION Figure 1. Frontal wall of the Fior di Loto Tomb; the numbers indicate the points where analysis was performed. Fig. 2 Raman spectra of (a) white pigment of the roof (FL1), (b) blue pigment (FL3), (c) green pigment (FL7) and (d) red ochre (FL4). The spectra (a) and (b) were collected with 785 nm source while spectra (c) and (d) with 532 nm. Figure 3 – The Leonesse tomb; the numbers indicate the points where analysis was performed. Figure 4 – LEO1: a) Raman spectrum collected with 785 nm of red cinnabar and b) pXRF analysis of the same pigment with strong Hg peak Figure 5 - The Cacciatore tomb; the numbers indicate the points where analysis was performed.

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ACCEPTED MANUSCRIPT Figure 6 - Raman pectrum of Hematite and carbon acquired on dark red (CAC7) using 785 nm source Figure 7 - Barone tomb; the numbers indicate the points where analysis was performed. Figure 8 – XRF spectrum of dark green color of the Barone tomb (BA2).

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Figure 9 - Micro-Raman spectra of violet pigment collected with 532 nm: (a) red particles formed by hematite; (b) blue grains of lazurite and (c) black carbon component Figure 10 - Micro Raman spectra of dark green pigment (BA3) composed by green (a) and red (b) grains; the spectra were collected with 532 nm source. The black carbon spectrum it is not reported.

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Figure 11 - The Bartoccini tomb; the numbers indicate the points where analysis was performed. Figure 12 – The Tori tomb; the numbers indicate the points where analysis was performed.

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Figure 13 -The Giocolieri tomb; the numbers indicate the points where analysis was performed. Figure 14 – The Caccia e Pesca tomb; the numbers indicate the points where analysis was performed. Figure 15 – XRF spectrum of the dark red pigment (CP4)

Figure 16 – Fe2O3 – As diagram of the analysed red, orange, pink and violet pigments

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Figure 17 – Bivariate diagrams of blue and green pigments: a) SiO2 – Cu; b) (Sn + Pb) – Cu.

23

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ACCEPTED MANUSCRIPT Highlights The main goal of this research is the identification of pigments used in the Etruscan wall paintings Non-destructive and in situ handheld X ray fluorescence and Raman spectrometry were carried out on the wall paintings of eight of the more important Tarquinia graves

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Precious pigments such as malachite, Egyptian blue, lazurite and cinnabar were detected in some of the more notable tombs

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Mixture of pigments to obtain particular hues was a common practice for Archaic Etruscan painters