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Anal Bioanal Chem

DOI 10.1007/s00216-008-1945-8

ORIGINAL PAPER

Compositional analysis of Tuscan glass samples:


in search of raw material fingerprints
S. Cagno & K. Janssens & M. Mendera

Received: 31 October 2007 / Revised: 31 January 2008 / Accepted: 6 February 2008


# Springer-Verlag 2008

Abstract SEM-EDX quantitative analyses were performed tradition in glass manufacture. While Venice was undoubtedly
on 91 samples of vessel glass originating from a number of the most important center of glass production, the remains of
sites throughout Tuscany. A comparison with Venetian glass glass workshops have been uncovered by archaeologists in
data is made in order to evaluate differences in glassmaking other areas of Italy too, such as Tuscany, demonstrating that
materials. The compositions of the samples provide clues there were workshops in which all of the phases of the
about the different raw materials used in relation to recipes production chain were executed. A number of glass produc-
that changed slightly during the period covering the late tion sites located in the municipality of Gambassi Terme were
Middle Ages to early Renaissance. Two kinds of ash used as the focus of a study where attention was mainly devoted to
a fluxing agent were identified, one of which is of east raw materials, production indicators and the final glass
Mediterranean origin while the other is likely to be Spanish. fragments that had been excavated [1–4].
Two types of silica sources were also found. One of these The aim of this work was to determine whether it is
was recognized as being quartziferous river pebbles, while possible to identify the raw materials used in glass
the other is proposed to be local sand. production by considering the major elemental composi-
tions of a set of glass fragments excavated at these sites.
Keywords Archaeometry/fine arts . Glass . Tuscany . Ninety-one samples of glass fragments from different sites
Venice . Electron microprobe . X-ray spectroscopy (EDX) . located in Tuscany were analyzed via scanning electron
SEM-EDX microscope–energy dispersive X-ray analysis (SEM-EDX)
in order to (a) compare the glass compositions encountered
at the Tuscan production sites to those of the other sites and
Introduction (b) compare Tuscan and Venetian glass compositions.
Samples of finished glass vessels from Tuscan production
Glass in Italy in the medieval–Renaissance period was a sites were analyzed together with glass originating from
luxury product that spread throughout the entire peninsula, other Tuscan locations, while comparisons were also made
starting from a limited number of locations with an established with data on Venetian products.

Raw materials used for glassmaking


S. Cagno (*) : K. Janssens
MITAC 4, Department of Chemistry, Since the fluxing agents used for glass production in Italy
University of Antwerp (UA),
of the Middle Age were imported ashes, trade in and the
Universiteitsplein 1,
2610 Antwerp, Belgium transport of raw materials had an important impact on the
e-mail: simone.cagno@ua.ac.be development of the glass industry, and on the resulting
glass composition. It is reported that in Italy coastal plant
M. Mendera
ashes were imported from the Eastern Mediterranean
Department of Archeology, Università di Siena,
Via Roma 56, (Levantine ash) [5] or from Spain, from the region of
53100 Siena, Italy Alicante [6]. These two types of ash resulted in different
Anal Bioanal Chem

glass compositions: Spanish ash yields glass with a was active from the end of the thirteenth century to the
concentration of K2O that is around half of that of Na2O middle of the fourteenth; five furnaces were discovered,
(typically 8% K2O and 16% Na2O), while Levantine ash is with a number of glass samples in close proximity [1]. The
more sodic (typically leading to glass containing 3% K2O Gambassi (Piazza del Castello) workshop was active during
and 14% Na2O). On the other hand, potassic ash, produced a later period (middle of the sixteenth century) and was
by burning local wood, was normally produced and used equipped with a circular furnace [1]. Indicators of both
for glassmaking in Northern Europe. The ash could also be fritting and re-melting of glass were found at both sites,
purified by treating it with boiling water: the salts that suggesting that all of the steps involved in glassmaking
precipitated from the resulting solution were used as a were carried out there [7].
fluxing agent, and this process allowed much of (the less The San Vettore glassmaking site is reported to have been
soluble) calcium and magnesium salts originally present in active by the end of the thirteenth to the beginning of the
the ash to be eliminated. fourteenth century. The Orcia glass workshop was located in
Silica was obtained from sand quarries located close to the the municipality of Montaione, again in the Elsa Valley, and
glass workshop, but it should be noted that the presence of was active in the same time as the San Vettore workshop [8].
iron minerals dispersed in the sand is an important issue, as San Gimignano, an important town located in the Elsa
relatively small percentages of Fe2O3 (0.5–1%) in glass can Valley, ruled a wider territory comprising Gambassi and
cause an undesirable greenish hue in finished glass objects. Montaione; here glass workshops were active between the
When the desired product was a high-quality colorless fourteenth and the sixteenth centuries [8]. In San Giovanni
glass, local sands were not really suitable. One option to Valdarno, a town located in the province of Arezzo, a glass
achieve such glass was to add manganese, commonly found workshop was active from the fifteenth century; the
in the form of the mineral pyrolusite (MnO2), to the molten analyzed samples were found in cesspits of the Arnolfo
glass batch in order to decolorize the glass. The manganese Palace and have been dated to the sixteenth century [9].
ore oxidizes the iron present, yielding glass with hues from Rocca di Campiglia was a strategic castle in the province of
yellow to colourless, as the slight purple colour developed Livorno; it is reported to have been peopled from the
neutralizes the yellow tint. Also, adding more manganese eleventh to the sixteenth century; the glass samples
than needed to oxidize the iron produces purple glass. The considered here were dated to the 13–14th centuries [10].
other possibility was to use a purer silica source—one Finally, Poggio Imperiale is an important archaeological
containing almost all silica. For example, the quartziferous site located in the municipality of Poggibonsi, not far from
pebbles found in the beds of alpine rivers were used in Gambassi; this was a wealthy town founded in 1155 and
Venice for this purpose [5].

Samples and sites of provenance

A series of 91 samples of vessel glass were analyzed for their


major elemental compositions; the hues of the glass fragments
were principally greenish or yellow, while some specimens
were colorless. The fragments analyzed date from the ninth to
the sixteenth centuries (with most of the fragments created
between the fourteenth and sixteenth centuries), and two
different types of sites of provenance can be distinguished:
some of the glass fragments (33 samples) originate from
previously ascertained production sites, with the samples
found in the workshop layers (Gambassi, San Vettore,
Germagnana, Orcia); while many more (58 samples) were
found during archaeological excavations at different sites
throughout Tuscany (Poggio Imperiale, Rocca di Campiglia,
San Gimignano, San Giovanni Valdarno). The locations of the
archaeological sites are shown in Fig. 1.
The Gambassi, Germagnana and San Vettore sites are
located a few kilometers away from each other in the same
municipality of Gambassi Terme in the Elsa Valley, some
35 km away from Florence; glass workshops were active in
different periods in this area. The Germagnana glass factory Fig. 1 Locations of the archaeological sites in Tuscany
Anal Bioanal Chem

Fig. 2 K2O versus CaO 14.0


concentrations in the Tuscan
samples (% wt)

Unpurified Ash
12.0

10.0

CaO (% wt)
8.0

6.0
Purified Ash

4.0
A
B
2.0 C

0.0
0.0 2.0 4.0 6.0 8.0 10.0 12.0

Levantine Ash K2O (% wt) Barilla Ash

then destroyed in 1270; reconstruction work was begun for the quantitative analysis of glass without incurring
twice, in the year 1313 and by the end of the fifteenth significant diffusion of sodium during the irradiation [12].
century, but it was never actually completed. The glass The net intensities were calculated with the program AXIL
samples from Poggio Imperiale come partly from a tank (Analysis of X-rays by Iterative Least squares) and
filled during the construction work in 1313 (these are quantified using a standardless ZAF-program [13].
therefore confidently dated), and partly from other archae- The concentrations of Na2O, MgO, Al2O3, SiO2, P2O5,
ological layers [4]. SO3, Cl, K2O, CaO, MnO and Fe2O3 were quantitatively
determined.

SEM-EDX analysis Fluxing agent

The glass samples were embedded into acrylic resin. The Based on the major elemental composition, all of the samples
resin blocks were then mechanically ground with silicon appear to have been produced using vegetable ash as the
carbide paper and polished with diamond paste of up to 1 fluxing agent, since the amount of K2O was always higher
μm in order to obtain a smooth surface of unaltered glass than 2% wt. The alkaline and alkaline-earth compositions of
(up to ~5 mm per side) on which SEM-EDX measurements the samples and the results of hierarchical cluster analysis
could be performed without interference from the corroded indicated that three clusters can be distinguished, as shown in
surface layers of the glass fragments. Fig. 2. In this plot, the three groups can be separated from
SEM-EDX measurements were performed with a JEOL each other by their contents of K2O and CaO.
(Tokyo, Japan) 6300 scanning electron microscope The first group (A) mainly comprises glass vessels
equipped with an energy dispersive X-ray detector [11]. originating from Gambassi (production site) as well as
Four spectra, taken at different spots on each sample, were samples from San Gimignano and San Giovanni Valdarno.
collected for 100 s using a 2 nA electron beam current, an The composition is that of a mixed alkali glass, as
accelerating voltage of 20 kV and a microscope magnifica- characterized by around 14% Na2O, 3% MgO, 6% K2O
tion of 500×. These parameters were found to be suitable and 10% CaO (see Table 1), and this can be considered a

Table 1 Average concentrations and standard deviations of A, B and C clusters (% wt)

Na2O MgO Al2O3 SiO2 P2O5 SO3 Cl K2O CaO MnO Fe2O3

A “Barilla” 38 samples 13.6±1.9 3.0±0.8 4.4±1.0 60.1±2.6 0.5±0.2 0.2±0.1 0.5±0.1 6.3±1.2 9.3±1.2 1.1±0.4 0.7±0.3
B “Levantine” 39 samples 13.9±1.5 3.6±1.2 3.3±1.2 64.0±3.5 0.5±0.2 0.2±0.1 0.6±0.2 3.1±0.9 9.0±1.2 0.9±0.5 0.7±0.3
C “Purified 14 samples 17.6±1.5 2.3±0.7 3.1±0.8 65.0±2.4 0.5±0.1 0.1±0.02 0.9±0.1 2.6±0.6 5.3±1.3 0.9±0.4 1.4±0.6
Levantine”
Anal Bioanal Chem

Table 2 Average concentration and standard deviations of Venetian glass types (% wt) [5]

Na2O MgO Al2O3 SiO2 P2O5 SO3 Cl K2O CaO MnO Fe2O3

Common glass 8 samples 13.5±0.9 3.1±0.3 1.7±0.2 64.7±0.7 0.3±0.1 0.2±0.04 0.7±0.1 3.3±0.6 10.1±0.6 1.3±0.3 0.8±0.1
Vitrum Blanchum 33 samples 13.6±1.4 3.4±0.7 1.0±0.4 66.9±1.7 0.3±0.1 0.2±0.1 0.9±0.1 3.0±1.2 9.8±1.2 0.5±0.2 0.4±0.1
Cristallo glass 16 samples 17.2±1.5 1.8±0.4 0.7±0.1 70.5±1.3 0.2±0.04 0.3±0.1 1.0±0.1 2.9±0.4 4.9±0.7 0.3±0.1 0.2±0.1

typical product of the Gambassi and also the San Giovanni contents of aluminum, iron and manganese to those of
workshops. It is likely that relatively K-rich Spanish ash group B led us to hypothesize that this type of glass was
(Barilla) was used for its construction [14]. also produced using a local silica source, or was subjected
The second group (B) is made of samples of different to significant secondary processes, such as the re-melting of
origins, mainly from Poggio Imperiale and from the adjacent cullet (recycled glass). A significant percentage of MnO
production sites of Germagnana and Gambassi. Since its (averages from 0.9 to 1.1%) was also found in all the groups,
composition is characterized by a relatively low K2O content suggesting that a pyrolusite was added to the batch in order
(3%), it is likely that Levantine ash was used to produce it. to decolorize the glass, since the colour would otherwise
From Table 2, we can see that its composition is similar to have been affected by the high iron content.
the Venetian “Vitrum Blanchum” and “Common” glasses, From Fig. 2, it is possible to distinguish between the
with the principal difference between these groups being the three previously described groups by considering whether
MnO and Fe2O3 contents (which are higher in “Common” the CaO concentration is below or above 7% wt and
glass). The average concentrations of the abovementioned whether the K2O abundance is below or above 4.5% wt:
oxides in group B are closer to the higher values of glass with more than 4.5% of K2O was made using
“Common” glass. The high average contents of Al2O3 and European ash, while percentages of CaO of <7% indicate
Fe2O3 seem to indicate that this type of glass was made by that an ash purification process was used. In the samples
using local impure sand or clay as a raw material. from Gambassi, the potash content is generally higher than
The third group (C) comprises some samples from in those from Germagnana, which indicates that a different
Gambassi and San Giovanni Valdarno, while others are ash was used. It is likely that in Germagnana only sodic
from excavation sites. Their composition is consistent with Levantine ash was used. The San Vettore and Orcia samples
the hypothesis that sodic ash, purified before the fusion show both lower and higher potash contents. Glass from
process, was used, as indicated by its low calcium and San Giovanni Valdarno is similar in composition to that
magnesium contents. From Table 2, the alkaline and from Gambassi, while in Poggio Imperiale and Rocca di
alkaline-earth compositions of this group are close to that Campiglia lower magnesium, potassium and aluminum
of Venetian “Cristallo” glass, but the presence of similar concentrations are found.

Fig. 3 Al2O3 versus Fe2O3 8.0


contents in Tuscan samples,
and comparison with Venetian
7.0
groups from Verità and
Zecchin [5]
6.0
Tuscan production

5.0
Venice, 11-14th century
Al2O3 (% wt)

4.0

3.0 Venice, 11-16th century


Poggio Imperiale "Cristallo"

2.0
A
B
th
Venice, 13-17 century C
1.0

0.0
0.0 0.5 1.0 1.5 2.0 2.5
Fe2O3 (% wt)
Anal Bioanal Chem

Table 3 Compositional groups and average contents (% wt)

Na2O MgO Al2O3 SiO2 P2O5 SO3 Cl K2O CaO MnO Fe2O3

Tuscan Barilla 35 samples 13.8±1.7 3.1±0.7 4.6±0.7 59.6±1.7 0.5±0.2 0.2±0.04 0.5±0.1 6.2±1.1 9.3±1.1 1.2±0.4 0.7±0.3
Pebbles Barilla 3 samples 10.4±0.2 1.9±1.5 2.0±0.5 66.4±3.3 0.5±0.2 0.2±0.2 0.5±0.1 8.0±1.4 8.7±2.5 0.7±0.2 0.4±0.1
Tuscan V. B. 8 samples 13.8±1.5 3.7±0.7 4.2±0.2 62.2±1.2 0.4±0.1 0.2±0.1 0.5±0.04 4.0±0.5 8.9±1.3 1.1±0.5 0.6±0.1
Tuscan Common 13 samples 14.1±1.5 4.5±1.2 4.3±0.6 60.6±2.1 0.7±0.2 0.2±0.1 0.6±0.1 3.3±0.8 9.4±1.0 1.2±0.6 1.0±0.3
Pebbles V. B. 11 samples 13.0±0.9 3.1±0.9 2.0±0.6 67.4±1.9 0.4±0.1 0.2±0.1 0.6±0.2 2.6±0.7 9.3±1.2 0.6±0.4 0.4±0.1
Pebbles Common 7 samples 15.2±1.3 2.7±1.0 2.3±0.3 66.7±1.7 0.5±0.1 0.1±0.04 0.8±0.1 2.3±0.5 7.6±0.4 0.6±0.2 0.9±0.1
High Fe Cristallo 6 samples 16.5±0.8 2.3±0.7 2.3±0.3 66.9±1.3 0.5±0.1 0.1±0.01 0.8±0.1 2.3±0.4 6.0±0.8 0.9±0.3 1.0±0.2
T. Crist. 1 sample 19.4 2.8 4.6 59.9 0.4 0.1 0.8 4.0 6.8 0.7 0.6
P. Imp. Cristallo 7 samples 18.2±1.4 2.2±0.9 3.5±0.3 64.2±1.5 0.5±0.1 0.1±0.02 0.9±0.1 2.5±0.6 4.5±1.2 1.0±0.5 1.9±0.2

Silica source the production site. Three samples from group A appear to
have been made with a purer silica source (1.6–2.3% Al2O3).
In order to discriminate between the different sources of silica The samples of group B are spread across the Tuscan group
used for glassmaking, we can consider the contents of and the group produced with river pebbles. So, some of the
aluminum and iron, which are usually correlated elements. “Levantine” group was indeed produced with raw materials
As a matter of fact, colorless high-quality glass produced with similar to those used in Venice, and we can possibly
a selected silica supply tends to have low concentrations of distinguish between luxury (real “Vitrum Blanchum”) and
these elements, as iron would affect the final hue of the glass. ordinary glass on the basis of iron content. Another part of this
When Al2O3 is plotted versus Fe2O3 (Fig. 3), the samples group was produced locally with a Tuscan source and so we
are arranged in different lines. 13–17th century Venetian glass can now term these samples “Tuscan Vitrum Blanchum” or
[5], for example, usually follows the lower line, which “Tuscan Common,” where the last one has a higher iron
exhibits a direct relationship (low intercept), meaning that content.
almost all of the aluminum present was introduced into the One sample from group C, from Gambassi, was produced
glass in association with iron. This correlation could be used with the Tuscan silica source (and is termed “Tuscan
to identify the actual Ticino pebbles. Earlier Venetian glass Cristallo”), while other samples from group C, although
tends to have a higher intercept, which could be due to the they follow the lower line, have iron contents that are too
different kinds of pebbles or quartziferous sand used [5]. We high to be considered real “Cristallo” glass. Among these,
should also note that in Venetian productions Fe2O3 >0.6% is we can distinguish between two different groups: one is
typical of ordinary glass, while Fe2O3 <0.6 identifies luxury characterized by iron contents typical of Venetian common
glass (i.e., “Cristallo” and “Vitrum Blanchum”). Based on glass (0.6–1.2% Fe2O3), while the other has levels of iron
this, the following conclusions can be drawn. that are much too high to occur in Venetian productions
The samples of group A (mixed alkali, many of them (1.6–2.3% Fe2O3). This last group, which is quite homo-
coming from Gambassi) are mainly present in the group with geneous, only comprises samples originating from Poggio
the highest intercept; this group is not encountered for Imperiale. It is interesting to note that in these samples the
Venetian glass, and so it could identify a local Tuscan silica manganese content is also higher than in usual “Cristallo”
source with a peculiarly high aluminum content (higher than glass, and the quantity of MnO, around 1%, is similar to
3.5% Al2O3). This could be a sand which was extracted near those found in the other groups related to the Tuscan silica

Table 4 Distribution of compositional groups across the archaeological sites

Provenance Total # Tuscan Pebbles Tuscan Tuscan Pebbles Pebbles High Fe Tuscan P. Imp.
site Barilla Barilla V. B. Common V. B. Common Crist. Crist. Crist.

Gambassi 23 18 – – 3 – – 1 1 –
Germagnana 4 – – – 3 1 – – – –
S. Vettore 2 – 1 – 1 – – – – –
Orcia 4 1 – – 1 2 – – – –
P. Imperiale 27 1 – – 4 7 4 4 – 7
R. Campiglia 5 – – 1 – 1 3 – – –
S.G. Valdarno 17 12 1 2 1 – – 1 – –
S Gimignano 9 3 1 5 – – – – – –
Anal Bioanal Chem

Fig. 4 Na2O versus SiO2 levels 18.0


in the “V. Blanchum” and
“Common” groups as a function 16.0
of the silica source used
14.0

12.0

Na2O (% wt)
10.0

8.0

6.0

4.0
Tuscan silica
river pebbles
2.0

0.0
56.0 58.0 60.0 62.0 64.0 66.0 68.0 70.0
SiO2 (% wt)

source. This suggests that the Mn was added in order to higher contents of K2O and MgO are present in the samples
decolorize the glass. produced with the Tuscan sand. Therefore, considering the
In Table 3, a summary of the compositions of the SiO2 and Na2O contents of these samples (Fig. 4), it is
samples is presented, with all the groups distinguished on apparent that the two groups are well separated, and that they
the basis of SEM-EDX measurements, while Table 4 shows are both characterized by a roughly anticorrelated relation-
the distributions of the compositional groups across the ship between the silicon and sodium contents. Now,
archaeological sites. considering that the sodium content is not remarkably
We can see that most of the “Tuscan Barilla” group different in the two groups, we can assume that a similar
originates from Gambassi and San Giovanni Valdarno, and silica flux ratio was used to produce all of the samples
these could be centers of production for this type of glass. considered, and the differences in the silica contents of glass
“Tuscan Vitrum Blanchum” and “Tuscan Common” are spread are simply due to the higher amount of quartz supplied by
across all sites, while “Pebbles Vitrum Blanchum” and “Pebbles the river pebbles.
Common” mainly come from Poggio Imperiale, like the two Table 5 shows the results of XRF analyses of sands
bigger groups of “Cristallo,” while the only sample of “Tuscan collected in quarries near Gambassi (performed by Bianchin
Cristallo” was found in Gambassi. It is interesting to note that et al.) [2]. The silicon, aluminum and iron contents are
no sample of “Tuscan Barilla” was found in the Germagnana compatible with those found in finished glass objects, while
site, while glass with a recipe closer to that of Venice was the percentage of K2O (presumably due to feldspar) in the
produced; these samples fall into the Tuscan and the Pebbles sand could have given rise to the higher content of this
“Vitrum Blanchum” group and into “Pebbles Common.” oxide found in the “Tuscan Vitrum Blanchum” group.
However, only four samples from Germagnana were analyzed.
We then focused on “Vitrum Blanchum” and “Common
glass” produced with the Tuscan sand and with river pebbles, Conclusions
in order to see whether, besides the change of silica source,
there was any other modification to the glass recipe. In light of the SEM-EDX analyses performed, a number of
Looking at the compositions in Table 3, it is clear that, glass recipes have been identified as a function of the
besides the higher amounts of Al2O3 and Fe2O3, somewhat different raw materials used for glassmaking. The Tuscan

Table 5 Compositions of sands collected from quarries near Gambassi (% wt) [2]

Na2O MgO Al2O3 SiO2 P2O5 K2O CaO MnO Fe2O3

La Casina 2.0 0.2 7.7 84.0 0.02 1.8 0.7 nd 0.6


La Casina. La Cava 1.7 0.2 6.2 85.5 0.03 1.6 0.1 nd 1.6

ND = not detected
Anal Bioanal Chem

glass workshop appears to have produced various types of These results mean that we are close to identifying the
glass in the period of time extending from the ninth to the different fluxing agents and silica sources used in Tuscan
sixteenth century, and some of the samples analyzed here glassmaking during the Middle Ages–Renaissance period;
show a close similarity to contemporary Venetian glasses. in order to gain a better understanding of the supplies of
The first type of glass described was found in Germag- quartz, sand or clay utilized, a trace element quantification
nana, Orcia (centers of production) and Poggio Imperiale of these samples is being prepared. Moreover, new samples
and Rocca di Campiglia, and the samples dated from the from Tuscan sites will be investigated in the future.
ninth to the fourteenth century. This kind of glass was made
with Levantine ash as fluxing agent and quartziferous
pebbles as the silica source, and had a final composition in
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