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
1

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

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

Analytical techniques

-Raman
4

FESEM-EDS
LA-ICP-MS
XRPD

natron as flux

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)

Flux agent

30.0

25.0

orange
light blue
white
blue
yellow
colourless
red
green

20.0

15.0

10.0

5.0

MgO wt%

1) Soda-lime-silica glass

PbO wt%

Vitrifying agent

Stabilizing agent

5.0
4.5
Plant ash-based glass

4.0

orange
light blue
white
blue
yellow
colourless
red
green

3.5
3.0
2.5
2.0
Mixed natron-plant ash based glass
(Andreescu -Treadgold and Henderson
2006)

1.5
1.0

CaO wt%

Glass matrix

8.0
7.5

orange
light blue
white
blue
yellow
colourless
red
green

7.0
6.5
6.0
5.5
5.0
4.5

0.5
Natron-based glass

0.0
30

35

40

45

50

55

60

65

70

75

SiO2 wt%

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

Sr ppm

K2O wt%

Colouring and opacifying agents

Pb-Sn antimonates

Ca antimonates

Pb2Sb2-xSnxO7-x/2

Cu0 nanocrystals
homogeneously
dispersed in
glass matrix
(BSE image)

CaSb2O6 +
Ca2Sb2O7

(SO4)2-

(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

Metallic copper

Ca2Sb2O7

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

CaSb2O6

Chromophore ions
Ion Glass colour Concentration

Co2+

Cu2+

Blue
(purplish hue)

Blue
(greenish
hue)

Tessera

285-599 ppm

Blue

122-191 ppm

Light blue

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).