Microchim.

Acta 142, 115–122 (2003)

DOI 10.1007/s00604-002-0955-z

Original Paper
Physicochemical and Chemometric Characterisation
of Late Roman Amphorae from Straits of Gibraltar

Raquel Vigil de la Villa1 , Rosario Garcı́a Giménez1 , Maria Dolores Petit Domı́nguez2;
,
and Maria Isabel Rucandio3
1
Departamento de Geologı́a, Facultad de Ciencias, Universidad Aut
onoma de Madrid, Madrid, Spain
2
Departamento de Quı́mica Analı́tica y Análisis Instrumental, Facultad de Ciencias, Universidad Aut

onoma
de Madrid, Madrid, Spain
3
Madrid, Spain

Received July 21, 2002; accepted December 2, 2002; published online April 11, 2003
# Springer-Verlag 2003

Abstract. A physicochemical characterisation of a
selected group of late Roman amphorae was carried
out using x-ray diffraction spectrometry, flame atomic
absorption and emission spectroscopy as well as pet-
rographic polarisation microscopy. Most of these am-
phorae were found in underwater environments on both
coasts of the Straits of Gibraltar: Ceuta and Cadiz
(Spain). A multivariate statistical study of the obtained
data for 99 samples and 21 variables (Si, Al, Ca, Mg, K,
Na, Fe, Mn, Ti, Cr, Cu, Ni, Pb, Zn, calcite, quartz,
dolomite, orthoclase, plagioclase, phyllosilicates and
gypsum) was performed. Relations among amphorae
that shared a similar composition were established by
factor analysis. As a result, amphorae coming from
Cadiz showed a different composition than those com-
ing from Ceuta. This is demonstrated by the increase in
concentration of certain chemical elements, such as
Cu, Cr and Ca. This fact supports the archaeological
hypothesis that some amphorae of South-Hispanic
typology found in Ceuta were produced locally, al-
though there is no proof of the existence of kilns in
this area. On the other hand, neither the different typo-
logies nor the food stored or transported in these

Correspondence:DepartamentodeQuı́micaAnalı́ticayAnálisis
Instrumental, Facultad de Ciencias, Universidad Aut
onoma de
Madrid, E-28049 Madrid, Spain. e-mail: mdolores.petit@uam.es
amphorae seem to affect the mineralogical and chem-
ical composition of the ceramic pastes. However, their
porosity contributes to the enrichment in trace elements
and salt contents in those samples that had been in
marine underwater contexts for a large period of time.
Key words: XRD; FAAS; multivariate statistical analysis; Roman
amphorae; archaeometry.
Amphorae were containers widely used in the Roman
age for storing and transporting liquid and semi-liquid
merchandise such as wine, oil, salted fish, honey, etc.
These receptacles have been found in numerous
archaeological sites discovered throughout the Medi-
terranean coast, most of them in marine underwater
environments, since maritime transport was one of the
main ways of establishing commercial ties between
geographically separated regions.
Studying these containers should reveal interesting
data concerning aspects such as raw material origin,
manufacturing process, use, etc. The traditional meth-
od for classifying amphorae was largely archaeologi-
cal and typological. In the last decades, scientists
began to use physicochemical information as a way
of relating the composition of the ceramic materials of
these amphorae to the nature of the raw materials
employed [1–5], to technological aspects of amphora
116
manufacture [6–8] and to foodstuffs stored or trans-
ported in them [9–12]. In this sense, the idea of
separating contaminants and natural components of
ceramic pastes, and what they reveal about the prov-
enance and about the development of industrial com-
plexes at that time is very interesting and important.
Recently, the application of statistical treatment to a
wide range of results has provided an instrument for
scientists to find possible relations among them and to
classify the samples into compositional groups [1–3].
Today there is documentation of active industrial
complexes having existed on the African coast of
the Straits of Gibraltar (old Mauretania-Tingitana
[13–16]) during the late Roman Empire. They are
known to have existed at least as far back as the I-II
centuries A.D., and are known to have processed and
commercialised local merchandise such as salt-pre-
served fishing products, and to the transport of oil,
wine, etc. from the Spanish coast of the Straits of
Gibraltar, the Baetica. These factories created the need
for amphorae to store or transport these products. The
amphora type used during this period of the late Roman
Empire (from the middle of the III to the V century
A.D.) in the Straits of Gibraltar was mainly the Keay
XIX [17–19], an amphora of South-Hispanic typology.
In the study described in this paper, two archaeo-
logical sites were chosen in order to compare samples
from both sides of the Straits: Ceuta, located on
the African coast of the Straits of Gibraltar (old
Mauretania-Tingitana), and Cadiz, on the Spanish
coast (Baetica). The purpose was to establish differ-
ences and similarities in their physicochemical
composition and therefore to study (i) whether all am-
phorae of South-Hispanic morphology were of the
same provenance or, on the contrary, whether ampho-
rae collected in Ceuta were manufactured locally al-
though there is no proof of the existence of kilns sited
in old Mauretania-Tingitana; and (ii) whether the
presence of certain chemical elements in the ceramic
pastes comes from external sources or from the
manufacturing process.
To reach our objective, we performed a chemical
characterisation of a selected group of 99 amphorae
from underwater contexts (Straits of Gibraltar) on the
basis of the data derived from x-ray diffraction spec-
trometry and flame atomic absorption and emission
spectroscopy analyses. These analytical techniques
let us quantify major and minor constituents of the
raw materials used to fabricate the ceramic paste, as
well as to distinguish ceramic pastes with a different
R. V. de la Villa et al.
composition concerning certain elements. These ele-
ments might have been incorporated by the raw mate-
rials or absorbed and retained by the clay of the
ceramics as contaminants coming from the environ-
ment or from the substances that they formerly con-
tained. Concerning this last point, marine underwater
environment can protect food compounds stored in-
side from degradation effects by oxygen and sunlight.
However, we have to consider that the inner walls of
some of these amphorae were covered with resinous
deposits which isolated the ceramic paste from the
contained foodstuffs [20–23]. This aspect and the pas-
sage of time make it difficult to find residues of these
compounds in the ceramic paste.
Correlation and regression analyses are usually
used to estimate the contribution of the different types
of components to the contaminant accumulation and
to the raw material origin. These approaches are usu-
ally performed after appropriate selection of parame-
ters corresponding to the raw materials, as well as
indicators of the presence of food remains or of the
addition of certain compounds in the manufacturing
process. In the present case, the selected parameters
were: Si, Al, Ca, Mg, K, Na, Fe, Mn, Ti, Cr, Cu, Ni,
Pb, Zn, calcite (Cal), quartz (Q), dolomite (Dol),
orthoclase (Ort), plagioclase (Pla), phyllosilicates
(Phy) and gypsum (Gyp). A statistical treatment by
factor analysis was performed in order to sort out
samples sharing a similar composition and to deter-
mine possible relations among them.
The use of multivariate statistical analysis of chem-
ical and mineralogical data to compare amphorae
from two different sites is a particularly difficult case
because the studied parameter variation may be a con-
sequence of the following factors: (i) raw materials,
(ii) manufacturing process, (iii) application of resin-
ous coatings on the inside of the vessel, (iv) reaction
with ceramic walls and contents (oil, wine, salted
fish), and (v) contamination from the underwater
burial environment.
Experimental
Description of the Samples
The samples consisted of fragments of 99 different amphorae from
archaeological deposits located on both coasts of the Straits of
Gibraltar; 78 of them had been found on the coast of Ceuta and
21 on the coast of Cadiz. Most of them came from marine under-
water environments and are nowadays preserved in the municipal
museums of these Spanish cities.
Physicochemical and Chemometric Characterisation of Late Roman Amphorae from Straits of Gibraltar
Fig. 1. Amphora types. (A) Keay V type of North African origin
and (B) Keay XIX-B type of South Hispanic origin
Most of these late Roman amphorae were classified into two
groups according to archaeological and typological criteria [17]:
36 of them were of the Keay V type from North Africa, used mainly
for transporting oil, and 34 were of the Keay XIX type from
Southern Hispania (Baetica and Lusitania), used for storing and
transporting salt-preserved fishing products (see Fig. 1). The remain-
ing amphorae were classified as follows: 12 of Oriental origin, 4 of
Gallic origin and 13 of them of unknown provenance. Of these
amphorae, six were probably used for transporting and storing wine,
and the rest had an unknown use. Since the above classification of
samples was carried out strictly on the basis of archaeological and
typological criteria, the geographical names given do not necessarily
imply the chemical or typological homogeneity of the products.
The analysed samples were taken from the inner part of fragments
found at the bottom of the ceramics with the aid of a scalpel, taking a
minimum part to minimise damage to the archaeological object. Five
samples, taken from several different fragments of each amphora,
were ground with a pestle in an agate mortar before analyses in order
to ensure homogeneity and to reduce the particle size.
Samples for observation of the ceramic pastes by petrographic
polarisation microscopy were taken from the external part. Those
regions are less susceptible to modification caused by contained
foods.
Physicochemical Analyses
Flame atomic absorption spectroscopy (FAAS), using a Perkin
Elmer 503 spectrometer, was employed for determining several
major and minor elements, including Al, Mn, Fe, Ti, Ca, Mg, Cu,
Cr, Ni, Pb and Zn; Na and K were measured using the same instru-
ment in flame emission mode [24]. Silica content was deduced by
difference. The previous dissolution of samples was carried out in
the following way: a minimum amount of sample (between 5 and
20 mg) was accurately weighed and treated with hydrofluoric acid in
an open vessel, and heated to dryness on a hot plate. This treatment
was followed by addition of aqua regia, and again heating to dry-
117
ness. The residue was dissolved in 1 ml of concentrated hydrochloric
acid and diluted with water to volume (10–25 mL) in Teflon volu-
metric flasks. Ultrapure water was used throughout, and all reagents
used were of analytical grade in order to keep contamination by
minor elements to a minimum.
The mineral composition of the samples was determined by x-ray
diffraction spectrometry, by the powder method [25–27], using a
Philips PW-1035 diffractometer and working with Cu K
radiation
and Ni filter. Applied voltage and anodic current were 40 kV and
20 mA, respectively.
Transversal thin sections of the samples (20–25 mm) were cut off
in order to observe several components under a petrographic polar-
isation Orto Plan Pol Leitz microscope. When it was not possible to
obtain adequate thin sections of samples, these were consolidated
with resin and cut off after having been dried as described above.
Statistical Study of Some Chemical
and Mineralogical Parameters
Statistical processing of the data was carried out using the SPSS
program, version 7.5 for Windows+, with 21 variables of chemical
and mineralogical nature corresponding to Si, Al, Ca, Mg, K, Na,
Fe, Mn, Ti, Cr, Cu, Ni, Pb, Zn, calcite (Cal), quartz (Q), dolomite
(Dol), orthoclase (Ort), plagioclase (Pla), phyllosilicates (Phy) and
gypsum (Gyp). Factor analysis was applied in this study with the
aim of establishing possible relations among them. As an archaeo-
metry approach, it is a very important method that enables us to
reduce the space dimension of the variables, as well as the extraction
of new variables called ‘‘factors’’. The system scales factor weights
so that the sum of their squares is equal to the associated eigen-value
and relates to the total variance explained by that factor. In this
paper, an orthogonal rotation and Kaisers normalisation of the data
were performed. Cases with zero weights and data with values under
the detection limit were not considered in the study.
Results and Discussion
Chemical and Physical Characterisation
Chemical analyses of major and minor elements were
carried out for the 99 selected samples as described in
the experimental section. Table 1 shows the average
value with its respective standard deviation, as well as
the smallest and largest concentration obtained for
each major and trace element in all the analysed sam-
ples. For major elements, such as Al, Ca, Mg, K, Na,
Fe, Mn and Ti, concentrations are expressed in weight
percentages of their respective oxides. For trace
elements (Cr, Cu, Ni, Pb and Zn), concentrations
are expressed in ppm. The average accuracy was esti-
mated at about 10%. The results obtained for some
samples with an anomalous behaviour in one or more
parameters are also included in this table. A miner-
al characterisation of samples was carried out in a
similar way. Most of the samples showed a large pro-
portion of quartz and calcite. It is known that calcite is
decomposed at temperatures higher than 900  C.
118 R. V. de la Villa et al.

Table 1(A). Statistical parameters obtained for the 99 analysed samples. Major elements are expressed as weight percentages of their
respective oxides. Trace elements are expressed in ppm
Al2O3 CaO MgO K2O Na2O Fe2O3 MnO TiO2 Cr Cu Ni Pb Zn
Mean 16.41 3.55 (1.88) 5.95 10.64 4.82 (0.06) 0.46 (1.0) (9.5) (3.3) (104) 251
Stand. deviation 1.64 3.67 2.34 3.20 10.12 1.42 0.04 0.15 6.1 27.5 22.8 128 173
Smallest value 2.14 0.25 < 0.10 0.24 0.13 1.42 < 0.01 0.12 < 0.5 < 0.5 < 0.5 < 0.5 67
Largest value 18.84 23.00 10.4 25.05 47.23 9.28 0.31 0.86 49 196 202 976 942
Note: The values under detection limit have not been considered in the means in parenthesis.

Table 1(B). Selected samples with anomalous behaviour in their chemical composition. Major elements are expressed as weight percentages
of their respective oxides. Trace elements are expressed in ppm
Sample Al2O3 CaO MgO K2O Na2O Fe2O3 MnO TiO2 Cr Cu Ni Pb Zn
S-27 15.62 1.04 2.69 3.99 8.20 7.57 0.05 0.69 < 0.5 < 0.5 < 0.5 9 478
I-49 16.50 13.55 0.28 11.39 12.74 4.29 0.06 0.63 49 196 < 0.5 245 152
A-207 17.12 3.23 10.40 6.68 22.49 5.45 0.05 0.39 < 0.5 < 0.5 < 0.5 72 107
A-220 17.89 10.20 < 0.10 4.80 30.04 5.26 0.07 0.23 < 0.5 < 0.5 < 0.5 112 238
S-268 17.19 5.30 8.12 9.00 28.31 3.87 0.31 0.56 < 0.5 < 0.5 < 0.5 204 165
G-311 17.27 4.66 6.74 9.90 22.74 8.12 0.11 0.37 < 0.5 < 0.5 < 0.5 150 173
S-314 16.19 2.23 4.50 3.82 6.99 3.71 0.05 0.58 < 0.5 < 0.5 < 0.5 38 342
S-315 17.21 1.03 0.72 6.56 31.80 5.23 0.11 0.60 < 0.5 < 0.5 < 0.5 141 259
O-329 15.90 4.41 6.72 8.90 27.12 3.56 0.07 0.39 < 0.5 < 0.5 < 0.5 196 484
S-329 17.00 11.42 0.39 7.14 6.14 2.15 0.03 0.45 < 0.5 < 0.5 75 < 0.5 95

Therefore, the presence of this mineral as a major
constituent in these amphorae suggests a firing tem-
perature of less than 900  C. Large concentrations of
phyllosilicates, feldspars (orthoclase and plagioclase),
dolomite and gypsum occurred in a few samples only.
Smectite, kaolinite and illite are phyllosilicates of the
raw materials. While illite remains stable at 600  C,
the others disappear. In the amphorae, only illite oc-
curs in large concentrations, and this suggests firing
temperatures of more than 600  C.
The observation of the ceramic pastes by petro-
graphic polarisation microscopy allowed us to distin-
guish two different material types with respect to their
texture and mineralogical composition. Some of the
ceramic pastes revealed large amounts of metamor-
phic rocks, schist, orientated limestone, fossils, poly-
crystalline quartz and chamotte. These substances
lend a porous character to the ceramic paste, decreas-
ing their plasticity and as a consequence making them
more absorbent to external elements in contact with
the pastes (Fig. 2a). The rest of the ceramic materials
is more compact and of a lower degree of porosity
(Fig. 2b). We observed the presence of engobium in
their outer face and flowing lines in the paste. Further-
more, small quartz crystals (bright spots), feldspars
(white spots) and some carbonate accumulations were

Fig. 2. Photographs of transversal thin sections obtained by petrographic polarisation microscopy (X130). (a) Ceramic paste of high
porosity. (b) Ceramic paste of low porosity
Physicochemical and Chemometric Characterisation of Late Roman Amphorae from Straits of Gibraltar
identified. This type of ceramic paste has insulating
properties with respect to the absorption of certain
external elements.
Statistical Processing of Data
The data corresponding to the mineralogical and
chemical characterisation (21 parameters) of the 99
analysed samples was subjected to a correlation study
that provided a statistical interpretation of the results.
The first step was to obtain the correlation matrix for
different variables (input data matrix 2199). The
most outstanding results obtained for a high signifi-
cant level (P ¼ 0.1%) showed a significant negative
correlation between silicon and other elements, such
as sodium (r ¼  0.912), potassium (r ¼  0.541),
manganese (r ¼  0.448), and, in a decreasing order,
calcium and iron. Similarly, aluminium and lead
showed a significant correlation coefficient
(r ¼  0.635), as did copper and chromium
(r ¼ 0.649) and calcium and copper (r ¼ 0.529),
among others.
After an orthogonal rotation of the correlation ma-
trix, the new factors of the components were deduced.
The 21 initial parameters were reduced to eight fac-
tors that explained 70.37% of the total variance. The
factor loadings (higher than 0.5) of the components
are indicated in Table 2.
Factor 1 (F1) explains the maximum percentage of
variance (15.53% of the total variance). It is made up
by several parameters: in the negative part of the
factor, silicon represents the raw material; and the
positive part it groups certain variables (sodium, man-
ganese, potassium and, with a lower influence, iron)
related to the raw materials and to accumulated ele-
ments. The enrichment of certain elements in the
ceramic paste, such as sodium and potassium, could
be due to long periods spent under water and perhaps
to the nature of the salted food stored or transported in
these amphorae.
Table 2. Mineralogical and chemical parameters of every factor with a charge higher than 0.500
F1 F2 F3 F4
Si  0.940 Cu 0.898 Pb 0.853 Cal 0.840
Na 0.913 Cr 0.823 Al  0.841 Q  0.684
Mn 0.603 Ca 0.609
K 0.581
Variance Variance Variance Variance
15.53% 11.37% 9.85% 7.92%
119
The parameters gathered in F2 (Cu, Cr and Ca) are
elements from the raw material which were deliber-
ately added to the original ceramic paste in order to
improve the physical properties during the amphora
manufacturing process: firing temperature controllers
(fluxes), colloidal solutions as external coatings to en-
hance the appearance (engobium), and glazes.
F3 is made up, in the negative part, of Al, an ele-
ment coming from the raw material and, in the posi-
tive part, of lead, an element that can be considered as
indicative of the addition of engobium to the ceramic
paste. In this case, environmental pollution as another
source of lead enrichment is not considered, since
these amphorae stayed in marine underwater, in un-
derground archaeological sites or in the basement of
the museum. This factor does not allow an amphora
classification as a function of criteria used in this
study, such as provenance, typology and stored or
transported food.
The major crystalline mineral constituents of the
ceramic pastes are gathered in the factors F4, F5, F6
and F7. It is remarkable that an excess of quartz, dis-
tributed in the negative part of F4, could come from
substances added in order to decrease the plasticity of
the ceramic paste during baking. F6 represented the
presence of feldspars, being those of K (orthoclase) in
the positive axis and those of Ca and Na (plagioclases)
in the negative one. The extremes of this axis are in-
dicative of the addition of fluxes and the other
above-mentioned substances. Finally, F8 represents
the variations in Mg and Ti concentrations.
The amphora representation as a function of the
factors F1 and F2 explains the maximum percentage
of the total variance and it allows their classification
according to the provenance, Ceuta or Cadiz, inde-
pendently of their typology and use (Fig. 3). Corre-
spondingly, amphorae coming from Cadiz are located
on the positive side of F2 and have relatively high
concentrations of Cu, Cr and Ca. They belong to dif-
ferent typologies and, consequently, were used to
F5 F6 F7 F8
Phy 0.942 Ort 0.811 Gyp 0.789 Mg 0.808
Pla  0.774 Ti 0.554
Variance Variance Variance Variance
7.58% 6.79% 6.74% 6.59%
120
transport materials of varied nature, such as oils, salt-
ed food, wine or other unknown products. It is con-
ceivable that Cu, Cr and Ca enrichment found in the
Cadiz amphorae is due not only to differences in the
raw materials, but also to the fabrication process, i.e.
the addition of certain components to the ceramic
paste in order to improve their physical properties
(engobium, glazes and fluxes). On the other hand,
amphorae from Ceuta are distributed in the negative
axis of F2 and also in the positive one, but close to the
origin. The different behaviour with respect to F2 al-
lows us to distinguish two groups of amphorae: those
from Ceuta and those from Cadiz, and others that re-
main unclassified (Fig. 3). This classification is possi-
bly due to the enrichment in Ca concentration and
mainly to the relatively high content of Cu in Cadiz
amphorae. While those from Ceuta have a content of
Cu lower than the detection limit, those from Cadiz
show a Cu concentration range of between 28 and
196 ppm. In the same figure, two amphora samples
are located in the positive extreme of the F2 axis:
number 44 (Gallic typology and used for transporting
wine), and number 49 (indeterminate typology). This
extreme situation is attributed to the relatively high
R. V. de la Villa et al.
Fig. 3. Projection of the archaeological sam-
ples into the plot defined by F1 and F2 factors
concentration of Cr occurring in both the mentioned
Cadiz samples (36 and 49 ppm, respectively), in com-
parison with the low Cr content found in the remain-
ing amphorae (  1 ppm).
The data analysis confirms that not all amphorae of
South-Hispanic typology were of the same prove-
nance: the Cadiz manufacture was more sophisticated,
and amphorae from Ceuta were manufactured locally.
Also, this hypothesis is supported by investigations
conducted to find analogies between the nature of
the clay from the Ceuta surroundings and the ceramic
paste composition [3], despite the fact that there is no
proof of the existence of kilns in this area.
According to F1, Fig. 3 shows an amphora group in
the centre of the figure whose provenance and typo-
logy is impossible to distinguish. Some amphorae
from Ceuta are on the positive side of this factor,
showing a high content of Na and K. This group con-
sists of amphorae of diverse typology, and they were
used to store or transport different substances: salted
fish (amphorae number 207 and 209 of North-African
typology, as well as amphorae 268 and 315 of South-
Hispanic typology), oil, wine (amphora 311 of Gallic
typology) or even an unknown food (amphora 322 of
Physicochemical and Chemometric Characterisation of Late Roman Amphorae from Straits of Gibraltar
indeterminate typology and amphora 329 of Orient
typology). It can be concluded that the high salt con-
tent (Na and K) of some amphorae from Ceuta shows
no relation to the nature of the transported substances.
On the other hand, there are some amphorae that were
used for transporting salted food (314 South-Hispanic
and 218, 209 North-African typologies) located at the
opposite end of the F1 axis. Consequently, the high
salt content is not only traceable to the transport or
storage of salted fish, but also derives from the marine
underwater environment where these amphorae were
collected. In this sense, the porosity of the ceramic
paste is an outstanding aspect that undoubtedly affects
the enrichment of some constituents, and it could help
explain some extreme situations as explained at the
end of. Those samples showing the highest porosity
are now located at the positive extreme of the F1 axis.
Contrarily, the presence of resinous deposits covering
the inner walls of Roman age amphorae contributes to
the isolation of the ceramic paste from the food,
avoiding enrichment in these elements.
Figure 4 represents the amphorae distribution as a
function of the factors F4 and F5, which represent the
raw material. The F4 components are also indicative
of the manufacturing process, since quartz and calcite
are components of the substances added to decrease
121
Fig. 4. Projection of the archaeological sam-
ples into the plot defined by F4 and F5 factors
the plasticity of the ceramic paste and to control the
firing temperature, respectively. It is remarkable that
samples with enrichment in the elements correspond-
ing to F1 and F2 are distributed at random in the ex-
tremes of the axes F4 and F5. This data suggests a high
content of phyllosilicates (322 from Ceuta), phyllosil-
icates and carbonates (268 from Ceuta), carbonates
(44 from Cadiz and 329 from Ceuta) and quartz (49
from Cadiz and 207, 315 and 220 from Ceuta). The
data represented in Fig. 4 suggests that it is not pos-
sible to establish differences between amphorae of
either locations based on the raw materials of the
ceramic pastes and the manufacturing processes.
Conclusions
The advantages of multivariate statistical analysis of
physical, chemical and mineralogical data are demon-
strated as applied to a large data set, composed of 21
parameters in 99 amphora samples.
The results obtained from this statistical treat-
ent lead us to important conclusions: (i) Relations
among amphorae according to their composition are
established by studying the mineralogical and
chemical characterisation of late Roman amphorae
collected in underwater environments of both coasts
122 Physicochemical and Chemometric Characterisation of Late Roman Amphorae from Straits of Gibraltar
of the Straits of Gibraltar, Ceuta and Cadiz (Spain).
(ii) Amphorae coming from Cadiz and Ceuta show
differences. This is demonstrated by the increase in
concentration of certain chemical elements, mainly
Cu and Ca, in the ceramic paste from Cadiz and by
the enrichment in Cr in two Cadiz amphorae. More-
over, these results allow us to classify amphorae of
South-Hispanic typology according to their prove-
nance: Cadiz or Ceuta, confirming the local manufac-
ture of the latter. (iii) Neither the different typologies
nor food stored or transported in these amphorae seem
to affect the mineralogical and chemical composition.
(iv) The increase in ceramic paste porosity is an out-
standing aspect that contributes to a rise in the absorp-
tion of certain external elements.
References
[1] P. Mirti, A. Casoli, Analysis and Classification of Ceramic
Material Excavated on a South Italian Archaeological Site,
Annali di Chimica 1995, 85, 519.
[2] M. S. Larrechi, F. X. Rius, Chemometric Characterization of
5th Century A.D. Amphora-Producing Centres in the Medi-
terranean, Talanta 1993, 40, 1749.
[3] R. Vigil de la Villa, R. Garcı́a Gimenez, J. Cuevas Rodriguez,
D. Bernal Casasola, An Assay on Simulation of the Late
Roman Amphoric Ceramic Raw Materials, Thermochim. Acta
1988, 322, 9.
[4] J. A. Remola, J. Lozano, I. Ruisanchez, M. S. Larrechi, F. X.
Rius, J. Zupan, New Chemometric tools to Study the Origin of
Amphorae Produced in the Roman Empire. Trend Anal. Chem.
1996, 15, 137.
[5] Andr
es Gomez, G. Garcı́a Ramos, M. Raig
on Pichardo, P.
Sánchez Soto, Propiedades Cerámicas de Arcillas Procedentes
de Guadix (Granada), Boletı́n de la Sociedad Espa~ nola de
Cerámica y Vidrio 1990, 29, 37.
[6] M. C. Gonzalez-Vilchez, F. Gonzalez-Garcia, G. Garcı́a-
Ramos, Materias Primas y Datos Tecnol
ogicos de Piezas
Cerámicas Antiguas del Yacimiento Arqueol
ogico de Cerro
Macareno (Sevilla) (I), Boletı́n de la Sociedad Espa~ nola de
Cerámica y Vidrio 1985, 24, 173.
[7] M. C. Gonzalez-Vilchez, G. Garcı́a-Ramos, F. Gonzalez-
Garcia, Materias Primas y Datos Tecnol
ogicos de Piezas
Cerámicas Antiguas del Yacimiento Arqueol
ogico de Cerro
Macareno (Sevilla) (II), Boletı́n de la Sociedad Espa~ nola de
Cerámica y Vidrio 1985, 24, 219.
[8] M. Doval-Montoya, J. M. Martin-Pozas, Sobre el Mecanismo
de Descomposici
on T
ermica de la Dolomita, Estudios
Geol
ogicos 1974, 30, 435.
[9] R. H. Michel, P. E. Mcgovern, V. R. Badler, The First Wine &
Beer. Chemical Detection of Ancient Fermented Beverages.
Anal. Chem. 1993, 65, 408A.
[10] S. Passi, M. C. Rothschild-Boros, P. Fasella, M. Nazzaro-
Porro, D. J. Whitehouse, An Application of High Performance
Liquid Chromatography to Analysis of Lipids in Archaeologi-
cal Samples, J Lipid Res. 1981, 22, 778.
[11] J. Condamin, F. Formenti, M. O. Metais, M. Michel, P.
Blond, The Application of Gas Chromatography to the Trac-
ing of Oil in Ancient Amphorae, Archaeometry 1976, 18, 195.
[12] M. D. Petit-Dominguez, J. Martı́nez-Maganto, Transporte de
Alimentos y Anforas Romanas. La Pez y sus Componentes a
Trav
es de Análisis Orgánicos, Caesaraugusta 1997, 73, 309.
[13] F. Villada, J. M. Hita, El asentamiento romano de Ceuta.
L’Africa romana, Sassari 1993, p. 1.
[14] J. Bravo Perez, J. Bravo Soto, Inmersi
on y Ciencia 1972, 4, 49.
[15] J. Bravo Perez, R. Mu~ noz, Arqueologia Submarina en Ceuta.
Madrid, 1965.
[16] C. Posac Mon, Estudio Arqueol
ogico de Ceuta. Ayuntamiento
de Ceuta, 1981.
[17] S. J. Keay, Late Roman Amphorae in the Western Mediterra-
nean. A Tipology and Economic Study: the Catalan Evidence.
BAR International Series, Oxford, 1984, pp. 196 (i, ii).
[18] A. Alarc° ao, F. Mayet, As Anforas Lusitanas. Tipologia,
Produc° ao. Com
ercio, Conimbriga, 1990.
[19] J. A. Remola Vallverdu, A. Abello Riley, Les amphores en
VV.AA. Un abocador del segle V d.C. en el forum provincial
de Tarraco, Tarragona 1989, 249.
[20] N. Robinson, R. P. Evershed, W. J. Higgs, K. Jerman, G.
Eglinton, Proof of a Pine Wood Origin for Pitch from Tudor
(Mary Rose) and Etruscan Shipwrecks: Application of Ana-
lytical Organic Chemistry in Archaeology, Analyst 1987, 112,
637.
[21] D. Bernal-Casasola, M. D. Petit-Dominguez, Caracterizaci
on
de Resinas en Anforas Romanas por Cromatografı́a de
Gases. Resultados y Aplicaciones en Espa~ na, Alebus 1995,
4–5, 84.
[22] J. Martinez-Maganto, M. D. Petit-Dominguez, La Pez y la
Permeabilizaci
on de Envases Anf
oricos Romanos. Estudio
Analı́tico de una Muestra e Interpretaciones Historico-
Econ
omicas, Archivo Espa~ nol de Arqueologı́a 1998, 71,
265.
[23] M. D. Petit-Dominguez, J. Martinez-Maganto, MCF Fast
Derivatization Procedure for the Identification of Resinous
Deposit Components from the Inner Walls of Roman Age
Amphorae by CG/MS, Talanta 2000, 51, 727.
[24] I. A. Vo€novich, Analyse del Sols, Roches et Ciments. Mason,
Paris, 1988.
[25] Powder Diffraction File, Inorganic Phases, International Cen-
tre for Diffraction Date Swarthmore. PA, USA, 1989.
[26] D. M. Moore, R. C. Reynolds, X-Ray Diffraction and the
identification and analysis of clay minerals. Oxford University
Press, New York, 1989, p. 332.
[27] L. G. Schultz, Quantitative Interpretation of Mineralogical
Composition from X-Ray and Chemical Data for Pierre Shale.
U.S. Geol. Surv. Prof. Pap. 1964, pp. 391-C.