Micro-Raman on Roman glass mosaic tesserae

Invernizzi C.1,2, Basso E.1,3, Malagodi M.1,4, Bersani D.2, Lottici P.P.2, La Russa M.F.5
Laboratorio Arvedi, CISRiC, Universit degli Studi di Pavia, via Ferrata 1, Pavia 27100, Italy 2 Dipartimento di Fisica e Scienze della Terra, Universit degli Studi di Parma, Parco Areas delle Scienze 7/a, 43100 Parma, Italy 3 Dipartimento di Scienze della Terra e dellAmbiente, Universit degli Studi di Pavia, via Ferrata 1, Pavia 27100, Italy 4 Dipartimento di Chimica, Universit degli Studi di Pavia, via Taramelli 12, 27100 Pavia, Italy 5 Dipartimento di Scienze della Terra, Universit della Calabria, via Bucci, Arcavacata di Rende (CS) 87036, Italy
1

Introduction
The Villa dei Quintili (1) was the biggest and magnificent estate of the Roman suburbia, set along the Via Appia Antica. The original nucleus was built during the Age of Traiano-Adriano (first half of the second century A.D.) by the rich family of Quintili and it was widened when Commodo made it become an imperial property, enriching it of functional facilities and decorations. The central area (2) includes different spaces: a curvilinear building/ludus, the areas of private residence and representation, the arcaded gardens and the thermal baths (frigidarium, tepidarium and calidarium). The archeological excavations have unearthed a lot of materials: ceramic and vitreous artifacts, marbles, mosaics, mural paintings ecc.. In particular, hundreds of glass mosaic tesserae were retrieved in the thermal baths, where they probably decorated the vaults. Object of this study are twenty-one glass mosaic tesserae (5), mostly opaque and covering the majority of colour palette of that time, collected in the calidarium (3,4) under the supervision of the Soprintendenza Speciale dei Beni Archeologici (Rome). The aim of the detailed spectroscopic, microstructural and chemical characterization of both the glass matrix and the crystalline inclusions was to identify the raw materials, the colouring agents and the opacifiers as well as the production technology used during the Roman Imperial Age.
2 1 3 5

Analytical techniques
-Raman FESEM-EDS LA-ICP-MS XRPD

Glass matrix
PbO wt%

Vitrifying agent
MgO wt%

Flux agent
4.5
Plant ash-based glass

Stabilizing agent
CaO wt%
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5

1) Soda-lime-silica glass

natron as flux

30.0

5.0

25.0

2) Lead-alkali mixed composition glass plant-ash as flux PbO contents are natron-plant ash as flux related to
colouring/opacifying agent (Pb-Sn antimonate)

20.0

15.0

10.0

5.0

orange light blue white blue yellow colourless red green

4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5

Mixed natron-plant ash based glass (Andreescu -Treadgold and Henderson 2006)

orange light blue white blue yellow colourless red green

orange light blue white blue yellow colourless red green

0.0 30 35 40 45 50 55 60 65 70 75

Natron-based glass

0.0 0.0 1.0 2.0 3.0 4.0 5.0 6.0

4.0 300

400

500

600

700

800

900

Relatively high Sr concentrations and CaOSr positive correlation for the majority of natronbased glass samples CaO (oxide stabilizer) derives from the bioaccumulation of marine organisms coastal sand as source of silica

SiO2 wt%

K2O wt%

Sr ppm

Colouring and opacifying agents

Pb-Sn antimonates
Pb2Sb2-xSnxO7-x/2
(SO4)2-

Ca antimonates

Ca2Sb2O7

CaSb2O6 + Ca2Sb2O7

(SO4)2group of Nosean mineral Na8Al6Si6O24(SO4) (dark area in BSE image) formed by the reaction between raw materials used to make the opacifier and gangue minerals

CaSb2O6

Metallic copper
Cu0 nanocrystals homogeneously dispersed in glass matrix (BSE image)

Cuprite
Cu2O sub-micron crystals Homogeneously dispersed in glass matrix (BSE image)

Chromophore ions
Ion Glass colour Concentration Blue (purplish hue) 285-599 ppm 122-191 ppm Blue Light blue Tessera

Co2+

Cu2+

Blue (greenish hue)

1-3.1 wt% (CuO) Green 1628 ppm Light blue (one sample)

Conclusions
The majority of the tesserae show the characteristic composition of the natron glass, typical of Imperial age. As vitrifying agent a coastal sand was used, high-purity oxide stabilizers (CaO) being present in the sand for the phenomena of bio-accumulation of marine organisms. The red and orange tesserae represent two outliers, because of their lead-alkali mixed composition: for the red glass plant ash was likely used as flux, while the orange glass displays an intermediate composition between natron and plant ash glass. The colour and the opacity were obtained by the combination of chromophore ions and/or opacifying and colouring crystals: Pb-Sn antimonates (yellow), Ca-antimonates (white), a mixture of Sn-Pb antimonates and Cu2+ ions (emerald green), a mixture of Ca antimonates and Co2+ (blue and light blue) or Cu2+ (blue-green) ions, Cu0 metal nanoparticles (red) and Cu2O sub-micron crystals (orange).