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Journal of Archaeological Science xxx (2010) 15

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Journal of Archaeological Science

journal homepage: http://www.elsevier.com/locate/jas

The meals in a Tuscan building yard during the Middle Age. Characterization of
organic residues in ceramic potsherds
Gianluca Giorgi a, *, Laura Salvini b, Alessandra Pecci c
a

` di Siena, via Aldo Moro, 53100 Siena, Italy

Dipartimento di Chimica, Universita
` di Siena, via Aldo Moro 53100 Siena, Italy
Centro di Analisi e Determinazioni Strutturali, Universita
c
` di Siena, via Roma n. 5653100 Siena, Italy
Dipartimento di Archeologia e Storia delle Arti, Universita
b

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 15 July 2009
Received in revised form
27 December 2009
Accepted 4 January 2010

The characterization of organic residues found in ceramics objects coming from the Carmine Convent in
Siena (Central Italy), probably built in the second half of the 13th century, is described. The nine objects
analyzed in this study are pots, casseroles, and lids and they were used as lling material of the vault of
one room of the convent.
A gas chromatography-mass spectrometry approach has been used to analyze both the chloroform
methanol extracts as well as those obtained owing to alkaline hydrolysis.
On the basis of the compounds identied, the ceramic vessels were divided into three groups. One is
constituted by vessels that might have been used to cook different kinds of foodstuff (so called cauldron), including animals, and in particular ruminants. The second group is formed by a pot whose main
use might be as olive oil container. No traces of animal fats has been found in it. The third group is
formed by vessels mainly used for containing or boiling water or other substances not rich in fats. In
particular, one of them might have been used as a colander or to roast chestnuts, that were a common
food during the Middle Age.
These results, in conjunction with others obtained by different techniques, contribute to a better
understanding of the use of the ceramic vessels found in the Carmine Convent in Siena and on dietary,
uses and customs of people living there, and more generally in Tuscany, during the Middle Age.
2010 Elsevier Ltd. All rights reserved.

Keywords:
Archaeological ceramics
Gas chromatography (GC)
Mass spectrometry (MS)
Fatty acids

1. Introduction
Ceramic objects, such as pottery vessels, are the most common
class of objects found during archaeological excavations. They
might have had different functions: containers for storing food,
such as oil, wine, water, and for cooking and serving meals.
If their conservation during the centuries was not in drastic
conditions, their organic residues contain biomarkers produced by
biochemical transformations of their original content. In particular,
the characterization of the lipid fraction in archaeological material
(Rottlander, 1990) is of great importance to obtain information on
uses, custom and dietary of people who used this material (Dudd
and Evershed, 1999; Dudd et al., 1998; Evershed et al., 1995; Mottram et al., 1999; Raven et al., 1997; Evershed, 2008). In this frame,
the use of different mass spectrometry techniques and their

* Corresponding author at: Dipartimento di Chimica, Universita` degli Studi di

Siena, via Aldo Moro, 53100 Siena, Italy. Tel.: 39 0577 234241; fax: 39 0577
234233.
E-mail address: gianluca.giorgi@unisi.it (G. Giorgi).

coupling with separation methods, play a key role in identication,

structural characterization and quantitation of molecules present
in archaeological material (Agozzino et al., 2001; Salvini et al.,
2008).
Siena is a typical Medieval town, developed on a hilly
ground, located in Central Italy, in a region called Tuscany.
Among the numerous churches and convents present in the
town, the Carmine Convent belonged to the order of the Carmelitan monks and it was probably built in the second half of
the 13th century.
The church, the courtyard, a open space, an orchard and
a rectangular building in the south-eastern part of the courtyard,
probably a store house, known by the written documents as the
fondaco, formed the most ancient parts of the convent (Francovich
and Valenti, 2002). The Convent was restored and modied many
times between the 13th and 14th centuries. At the beginning of
the 14th century it overcame works to enlarge the structures of
the Convent. Among other rooms, a dormitory for the monks was
built on top of the fondaco (Francovich and Valenti, 2002). The
original rst oor of this building was made bigger and a new
oor with walls of stone and bricks replaced the original one that

0305-4403/$ see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jas.2010.01.005

Please cite this article in press as: Giorgi, G., et al., The meals in a Tuscan building yard during the Middle Age. Characterization of organic
residues in ceramic potsherds, J. Archaeol. Sci. (2010), doi:10.1016/j.jas.2010.01.005

ARTICLE IN PRESS
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G. Giorgi et al. / Journal of Archaeological Science xxx (2010) 15

had earthen walls. It is supposed that this was done in order to

build a sleeping area for the monks, as some documents report
that in 1301 the town of Siena paid for this a large amount of
orini, the currency used at that time (Francovich and Valenti,
2002).
In order to build the upper oor, the ceiling of the rst oor
was provided with a vault, and the empty space between the
vault and the new oor was lled with ceramics by using
a technique that goes back to the Roman times and was used in
other buildings of that period, like in Assisi and Prato, two towns
in Central Italy. In fact, the lling between the vault and the oor
needed not to be too heavy, in order not to break down the
ceiling and walls of the lower oor: the ceramic materials fullled at all this aim, allowing to ll space without adding too
much weight (Fig. 1).
During the restoration works of the Convent started in 2001, the
vault was discovered, with the great number of ceramic objects that
were used as lling material of the vault. The portion of the vault
that has been investigated has dimensions 12  4 m. More than 360
intact ceramic vessels have been recovered. It has been estimated
that about 868 ceramics objects were present with 20002500
pieces of ceramics. Most of the ceramic objects are discarded
material obtained from the ceramic manufacturing in the
numerous workshops present in the town. Only a few of them are
characterized by a coarse mixture and show burnt traces. This
suggests that they were fragments of pots and pans probably used
by the workers in the building yard, or in the convent, for cooking
the meals of the monks.
The characterization of the organic residues therein contained
should allow to obtain information on the original content of the
vessels and on life and dietary in the Medieval Age. With this aim,
we wish to report here on a gas chromatography-mass spectrometry investigation of the organic residues absorbed in nine
potsherds taken from the ceramics recovered in the Carmine
Convent in Siena (Fig. 1, Table 1).

Table 1
Ceramic samples characterized in this study.
#

Object description

Part of the object analyzed

1
2
3
4
5
6
7
8
9

Pot
Pot
Pot
Pan
Lid
Pot
Pan
Pan with holes
Lid

Base
Body
Rim
Body
Body
Base with calcareous deposits
Base
Base
Base

2. Experimental
2.1. Materials and sampling
All solvents used were pesticides analysis grade and purchased
from Merck (Milan, Italy). n-Octacosane, used as internal standard,
N,O-bis(trimethylsilyl)triuoro-acetamide (BSTFA) and trimethylchlorosilane were purchased from Sigma Aldrich (Milan, Italy).
Nine ceramic vessels were sampled and analyzed. Samples were
obtained by drilling small holes in the ceramic body after having
cleaned smoothly the surface. About 2 g of powder were recovered
from each sample. In order to make comparative and differential
analyses, when possible, more than one sample for each manufact
was taken.
A weighted amount of ne powder of each potsherd sample was
transferred in a vial and it was extracted by chloroform/methanol
(2:1 v/v, 10 mL, 2  15 min ultrasonication). An aliquot of the total
extract was derivatized using BSTFA containing 1% v/v trimethylchlorosilane and maintained at 70  C for 40 min.
After solvent extraction, the residue was treated with 0.5 M
NaOH in MeOH/H2O (9:1 v/v, 10 mL). The mixture was heated at
70  C for 90 min in ultrasonic bath. After cooling, the saponied
mixture was centrifuged (2000 r.p.m., 20 min). 3 mL of the liquid
phase were acidied with 1 M HCl (20 drops) and extracted with
chloroform (2  3 mL). The solvent was evaporated under
a nitrogen gas stream. The residues were left overnight in a vacuum
desiccator. Trimethylsilylation was then performed as described
above.
2.2. Gas chromatography-mass spectrometry
Gas chromatography-mass spectrometry (GCMS) analyses
were performed using a gas chromatograph Varian 3800 (Varian,
Walnut Crick, CA) equipped with a 30 m  0.25 mm (i.d.) fused
silica capillary column coated with a DB5 stationary phase (lm
thickness 0.25 mm). Ultra pure helium was the carrier gas. The gas
chromatograph is coupled with a Saturn 2000 ion trap mass
spectrometer (Varian, Walnut Crick, CA).
The column temperature was held at 50  C for 1 min immediately after injection, then the temperature was increased to 300  C
at 5  C/min and held for 10 min.
The mass spectrometer operated in the electron ionization
mode (70 eV) in the 40650 m/z range with source temperature of
150  C. The injector and the transfer line temperatures were
maintained at 280 and 170  C, respectively.
3. Results and discussion

Fig. 1. View of the ceramics characterized in this study. Ceramic objects used as lling
material (top); particular of the pan with holes 8 (bottom).

The gas chromatograms obtained from the lipid extraction and

the alkaline treatment of the insoluble residues of the samples 19
show the presence of different classes of compounds, most of them

Please cite this article in press as: Giorgi, G., et al., The meals in a Tuscan building yard during the Middle Age. Characterization of organic
residues in ceramic potsherds, J. Archaeol. Sci. (2010), doi:10.1016/j.jas.2010.01.005

ARTICLE IN PRESS
G. Giorgi et al. / Journal of Archaeological Science xxx (2010) 15

being fatty acids. On the basis of their content, the samples have
been divided into three main groups.

3.1. Group 1. Samples 1,3,4,5,7

Samples 1,3,4,5,7 are characterized by high amounts of fatty
acids of different nature. The most abundant species are palmitic
(C16:0), stearic (C18:0) and C18:1 fatty acids (Fig. 2). While palmitic
acid is abundant in nature and it can be found in almost all
animal and vegetable species, stearic acid can be related to
degraded animal fats (Mottram et al., 1999). The presence of its
unsaturated derivative C18:1 can be related to the original content
of vegetable oils in the ceramic material (Evershed et al., 2002;
Mottram et al., 1999). Going deeply insights into the characterization of these samples, clear differences can be observed in the
relative amounts of the C16:0/C18:0 fatty acids. The inspection of
objects 1, 3 (pots), 4 (a pan) and 5 (a lid) suggests that they are
general purpose cooking vessels. In their extracts the C16:0/C18:0
ratio is close to 1.
Furthermore, the presence of odd number fatty acids, such as
C15:0 and C17:0 and their branched forms, that might be produced by
ruminant animals due to the activities of gut bacteria, suggests that
these vessels contained ruminant fats (Mottram et al., 1999).
Although GC-C-IRMS was not performed to verify this hypothesis,
these data are in agreement with archaeozoological studies that
have identied rests of ruminants, mainly sheeps and goats in the
vault (Francovich and Valenti, 2002).
Thus we propose that ceramics 1,35 can be considered as
cauldron potsherds (Mottram et al., 1999) and general purpose
cooking vessels, as their content is constituted by lipid residues of
different animal origin.
In contrast, in sample 7 (a pan), the C16:0 component is more
abundant than its higher homologue C18:0, and there are no odd
number fatty acids and their branched forms. All this suggests that
cooking of ruminant animals can be reasonably excluded for
sample 7. These results are similar to those of the so called dripping
dishes used to collect the fat from animal carcasses during spit

C16:0

C18:0

Rel at i ve i nt ensi t y ( ar b. uni t s)

C18:1
C16:0

C18:0
C18:1

C16:0

C18:0
C18:1

C16:0

10

20

30

C18:0
C18:1

40

50

60

min

Fig. 2. Partial GCMS traces of the total lipid extract of samples 1, 3, 4, 5 (top to
bottom) showing the presence of fatty acids.

roasting (Mottram et al., 1999; Evershed et al., 2002), a typical

cooking procedure in Tuscany during the Middle Age. The discovery
of some pig bones in the vault supports the idea that the pan was
used to cook pig meat, or that lard was used in the food processing.
The presence of an animal content in samples 1,35,7 is also
conrmed by the identication of cholesterol in their alkaline
extracts.
In samples 3 and 4, methyl esters of C16:0, C18:0 and of C18:1 were
also found. These molecules are uncommon in archaeological
material. In fact it is known that they may undergo partial
decomposition in open air, likely by autoxidation (Rottlander,
1990). In the present case, the close dried space between the vault
and the upper oor has allowed a good preservation not only of the
ceramic material, as it is suggested by the presence of fatty acid
methyl esters, but also of paper and leather found in the lling
material of the vault.
Not only the pots and pans show the presence of some absorbed
organic residues, but also the lid (sample 5). This is probably due to
an evaporation process and it allows to take into account also these
materials for the study of the ancient dietary habits.
3.2. Group 2. Sample 2
Sample 2 has been obtained from the body of a pot. Its GCMS
trace and the list of compounds identied are reported in Fig. 3, top,
and in Table 2, respectively.
The results are almost different from those of the other samples:
in fact in this case the main component is the C18:1 acid followed by
C16:0, and a minor amount of C18:0 with a ratio of 100:40:17. The
predominance of a monounsaturated derivatives suggests a vegetable origin of the fatty acids, probably olive oil. This is supported by
considering that laboratory degradation experiments performed on
olive oil absorbed in ceramic potsherds showed a lipid prole
similar to that obtained for sample 2 (Dudd et al., 1998). Further, the
alkaline treatment of the insoluble residue of sample 2 shows the
distinctive predominance of the azelaic acid, a bicarboxylic C9:0
acid, and high amounts of 9,10-dihydroxyoctadecanoic acid (Fig. 3,
top, Table 2). These acids are related with the decomposition of the
oleic acid, that is particularly abundant in this sample (see above).
All this strongly suggests that this vessel has contained olive oil
(Regert et al., 1998).
On the other hand, the presence of cholesterol and of linear and
branched C15:0 e C17:0 fatty acids, also found in sample 2, suggests
that this vessel might have been also used to cook animal meet. In
fact sample 2 is a pot and it might have been used in different times
to store the oil and eventually to cook meat broths.
The identication of olive oil markers in sample 2 is very
interesting. And indeed olive oil is supposed to be a very common
food in Tuscany and in the other Southern regions in Italy in the
Middle Age, and also nowadays, while in North Italy, where the
climate was too rigid for olive tree cultivation, lard was the most
common condiment used (Montanari, 2008; Cortonesi et al.,
2002). Nevertheless, some archaeological data contradict such
a concept, showing that the consumption of olive oil was limited
to some parts of the population, while lard and other animal fats
were more common, even in the Southern part of the Italian
Peninsula. Among other data, it is of some interest that the analyses of more than 150 samples from medieval ceramic vessels, all
coming from Tuscany, carried out by us, show the presence of
olive oil only in a few of them. These results, together with
archaeobotanic data coming from different archaeological excavations state that olive oil was less distributed than that we are
used to think.
It is noteworthy the presence of sample 2 in a convent: in fact
institutions, such as hospitals and convents, had better access to

Please cite this article in press as: Giorgi, G., et al., The meals in a Tuscan building yard during the Middle Age. Characterization of organic
residues in ceramic potsherds, J. Archaeol. Sci. (2010), doi:10.1016/j.jas.2010.01.005

ARTICLE IN PRESS
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G. Giorgi et al. / Journal of Archaeological Science xxx (2010) 15

100
22

16

24
7

26
15
14

50

R el a t i v e

i n t e n s i t y

( %)

1
2

6
34

12
10 11

28
17
18

13

19
20

21
25

23

27

0
22

100

26

17
19
16
4

50

15

2
1

20

12

9
8

10

11

14
13

21
25

24
23

27

20

30

40

50

28

60

70

min

Fig. 3. GCMS traces of the alkaline treatment of the insoluble residue of samples 2 (top) and 4 (bottom). The numbering corresponds to the compounds names as reported in
Table 2.

foodstuffs than others, and they were provided with food in

general, and olive oil in particular, from the lands of which they
were owners (Belli et al., 2004).
Table 2
Compounds found in the GCMS trace of pot 2 after hydrolysis. Their chemical
names, (common names in parentheses) and retention times (min) are also reported. TMS trimethylsilyl residue.
#

Compound

Retention time (min)

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28

2-Hydroxypropanoic acid (Lactic acid) 2TMS

2-Hydroxyacetic acid 2TMS
Oxalic acid 2TMS
b-Hydroxybutyric acid 2TMS
Benzoic acid TMS
Octanoic acid (Caprylic acid) TMS
Glycerol 3TMS
a,u-Butanedioic acid (Succinic acid) 2TMS
Nonanoic acid (Pelargonic acid) TMS
2-Hydroxyheptanoic acid 2TMS
a,u-Pentandioic acid (Glutaric acid) 2TMS
Decanoic acid (Vapric acid) TMS
a,u-Hexanedioic acid (Adipic acid) 2TMS
a,u-Heptanedioic acid (Pimelic acid) 2TMS
a,u-Octanedioic acid (Suberic acid) 2TMS
a,u-Nonanedioic acid (Azelaic acid) 2TMS
Tetradecanoic acid (Myristic acid) 2TMS
a,u-Decanedioic acid (Sebacic acid) 2TMS
Hexadecanoic acid (Palmitic acid) methyl ester
Pentadecanoic acid TMS
a,u-Undecanedioic acid 2TMS
Hexadecanoic acid (Palmitic acid) TMS
Heptadecanoic acid (Margaric acid) TMS
11-trans-Octadecenoic acid TMS
11-cis-Octadecenoic acid TMS
Octadecanoic acid TMS
Eicosanoic acid (Arachic acid) TMS
2-Hydroxy-a,u-decanedioic acid 3TMS

15:77
16:44
19:30
20:41
23:92
24:87
25:92
27:30
29:07
29:63
31:17
33:08
35:30
39:02
42:47
45:92
47:40
49:11
49:82
50:59
52:18
53:76
56:57
58:64
58:84
59:41
64:70
68:04

3.3. Group 3. Samples 6, 8, 9

The content of the extracts obtained by samples 6, 8, 9 is quite
poor and, differently from the other objects, the presence of fatty
acids was undetectable. This is an interesting result for two
different reasons: a) the very scarce presence of organic molecules
in these samples, that were collected in the same area of the others,
suggests that all the ceramic objects have not received environmental contamination; b) from an archaeological point of view, it
shows that vessels 6, 8 and 9 were not used to contain vegetable or
animal oils, broth or any other food rich in fats. It is likely that
sample 6 (base of a pot) was probably used to contain or to boil
water, and possibly vegetables and cereals, while sample 9 (base of
a lid) might have been used to strain water, although the burnt
traces on the external part suggest that it was exposed to the re. Its
shape and the burnt traces in the outside and inside of the vessel
point to the possibility that it was used for roasting chestnuts,
a very common food during the Middle Age. In fact the form of the
pan is very similar to that of modern metal casseroles still used in
Tuscany for the same aim. To support this hypothesis, we performed an experiment burning one hundred chestnuts in a ceramic
pan with holes, similar to that reported in Fig. 1, bottom. The
analyses of the samples recovered from the pan before and after the
experiment show that no organic residues are produced by this
activity, and that burnt traces are present in the inside of the vessel
due to the burning of the peel and in the outside due to the re of
the stove. These results are compatible with those obtained for
sample 9. Furthermore, we know that chestnuts were consumed in
the Carmine Convent, because chestnut peels were found in the
lling material of the vault, together with animal bones, fruit seeds
and other food waste.
It is noteworthy that, with the exception of sample 2, in all the
samples traces of dehydroabietic acid have been found. This is

Please cite this article in press as: Giorgi, G., et al., The meals in a Tuscan building yard during the Middle Age. Characterization of organic
residues in ceramic potsherds, J. Archaeol. Sci. (2010), doi:10.1016/j.jas.2010.01.005

ARTICLE IN PRESS
G. Giorgi et al. / Journal of Archaeological Science xxx (2010) 15

a marker of resinous material from Pinaceae trees, probably used as

covering material of ceramic manufacts. This shows that the habit
of a coarse coating in vessels was more common than that is usually
thought (Salvini et al., 2008).
4. Conclusions
This study was aimed at the characterization of the organic
residues in ceramic vessels found in a vault of the convent of
Carmine (Siena, Italy). These rests are probably waste of the meals
of the laborers of the yard or the monks that lived in the convent.
A GCMS approach, both on chloroform/methanol extracts
and owing to alkaline hydrolysis, has shown the presence of
different fatty acids, with well dened ratios, in the samples
analyzed. The differentiation of the extracts depends upon the
nature of the ceramic samples and suggests a different use of
these objects.
On the basis of the total lipid proles, the nine objects can be
grouped into three main groups. The results obtained by samples 1,
3, 4, 5, and 7, that constitute the rst group, suggest that these
vessels might have been used to cook different kinds of foodstuffs,
including animals. This is in agreement with the identication of
bones of domestic animals, mainly ruminant, such as goats and
sheep, in the convent. These animals were consumed mostly when
they were adults, after they had nished their working life. It was
common to boil their meat and the broth might be eaten with other
food, such as cereals, legumes, vegetables.
The olive oil traces in sample 2 seem to point out that this vessel
was surely used in the convent, while the animal origin of the
residues is in agreement with the so called practice of the
monopoly of the broths, a common practice in the Middle Age
(Giovannini, 1994).
Due to the absence of high amounts of animal fatty acids in pot
2, it is supposable that it was not used for extensive cooking of
animal meat, but mainly as olive oil container. In this sample
neither traces of dehydroabietic acid nor related acids were identied, excluding the presence of a waterproong of the vessel.
The absence of fatty acids in samples 6 and 9 suggests that they
were used for containing or boiling water or other substances not
rich in fats. In particular, sample 8 might have been used as a colander
or to roast chestnuts, a common food during the Middle Age.
These results, together with others obtained by archaeozoological and archaeobotanical analyses, have yielded important
information on the use of the ceramic potsherds found in the
Carmine Convent in Siena and, as more generally, on the dietary
habits in a Tuscan building yard during the Middle Age.

Acknowledgements
The Archaeological project was carried out under the direction
of late Prof. Riccardo Francovich and Prof. Marco Valenti of the
University of Siena. The archaeobotanical data were analyzed under
the direction of Prof. Gaetano di Pasquale (University of Naples) and
the archaeozoological analyses have been carried out by Dr Franco
Salvadori (University of Siena).

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Please cite this article in press as: Giorgi, G., et al., The meals in a Tuscan building yard during the Middle Age. Characterization of organic
residues in ceramic potsherds, J. Archaeol. Sci. (2010), doi:10.1016/j.jas.2010.01.005