Microchemical Journal 126 (2016) 446453

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Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Characterization of gold leaves on Greek terracotta gurines:

A PIXE-RBS study
C. Fourdrin a,b,c, S. Pags Camagna a,d, C. Pacheco a,e, M. Radepont a,f, Q. Lemasson a,e, B. Moignard a,e, L. Pichon a,e,
B. Bourgeois a, V. Jeammet g
a

Centre de Recherche et de Restauration des Muses de France, Muse du Louvre, Porte des Lions, 14 quai Franois Mitterrand, 75001 Paris, France
Fondation des Sciences du Patrimoine, Universit de Cergy-Pontoise, 33 bd du Port, 95011 Cergy Pontoise cedex, France
Laboratoire Gomatriaux et Environnement (EA 4508), UPEM, Universit ParisEst, 77454 Marne la Valle cedex, France
d
Institut de Recherche de Chimie Paris, CNRSChimie ParisTech, 11 Rue Pierre et Marie Curie, 75005 Paris, France
e
Fdration de Recherche, 3506 New AGLAECNRS/MCCC2RMF, Palais du Louvre, Paris, France
f
Centre de Recherche sur la Conservation (CRC)USR3224CNRS/MNHN/MCC), 36 rue Geoffroy SaintHilaire, 75005 Paris, France
g
Dpartement des Antiquits Grecques, Etrusques et Romaines, Muse du Louvre, 99 rue de Rivoli, 75001 Paris, France
b
c

a r t i c l e

i n f o

Article history:
Received 15 August 2015
Received in revised form 18 December 2015
Accepted 18 December 2015
Available online 28 December 2015
Keywords:
Gold leaves
RBS
PIXE
Hellenistic
Louvre museum
Tin foils

a b s t r a c t
New insights are presented on the composition, thickness, and application of the decorating gold leaves remaining on Greek terracotta gurines, kept in the Louvre Museum. Excavated from various sites around the Mediterranean basin, the objects are dated to the Hellenistic and Roman period (4th c. BC1st c. AD). The thickness of the
gold leaves was determined using 3 MeV H+ Rutherford backscattering spectroscopy, while the gold concentration was calculated using H+-particle induced X-ray emission. On artifacts exhibiting large gilded areas, mapping
permitted to dene zones of interest in both well-conserved and weathered areas of the leaves for the thickness
calculation. The obtained thicknesses in the different zones are in agreement within the standard deviations, thus
validating the use of point measurements performed for the other objects. For the whole studied corpus, the
thicknesses ranged between 160 and 710 nm for a gold concentration mostly superior to 95%, strongly suggesting
an ancient purication process as well as a developed goldbeating technique during these periods in the ancient
Greek world. Tin leaves were also evidenced on several gurines, but their thicknesses were not estimated due to
a strong oxidation.
2015 Elsevier B.V. All rights reserved.

1. Introduction
In the eld of research on the coroplastic production (i.e., the art of
making terracotta gurines) of ancient Greece, recent scientic studies
have focused on the characterization of clays and on the identication
of the paint materials (pigments and dyes) used by the painter for the
nal polychrome decoration of the objects [13]. Less attention has
been given to the important role played by surface treatments with
metal leaves, such as gilding and, in some rare cases, tin plating [4].
Still it seems obvious that, by determining the elemental composition
and the thickness of the leaves, one might get interesting results on
the characterization of the ancient craftsmanship and eventually on
the provenance discrimination of the artifacts. These analysis could as
well provide some new insights on the relationships existing, in ancient
workshops, between various categories of technites (i.e., craftsmen, in
ancient Greek) such as sculptors, coroplasts, painters, and gilders,
whose activity is attested by Greek texts and inscriptions of the Classical
and Hellenistic periods [57]. Several recent publications have been
Selected papers presented at the TECHNART 2015 Conference, Catania (Italy), April
2730, 2015.

http://dx.doi.org/10.1016/j.microc.2015.12.030
0026-265X/ 2015 Elsevier B.V. All rights reserved.

devoted to the characterization of gold alloys polychromy, i.e., the

ratio of gold/copper/silver, as well as the presence of platinum group element (PGE) inclusions, which are a marker of the use of alluvial gold,
with regard to ancient jewelry from Egypt and Prehispanic cultures in
particular [815]. However, the question of the thickness of metal leaves
still preserved on historical artifacts remains less documented, and their
analysis is usually complicated due to the condition of the leaves and
therefore their heterogeneity [16,17]. The thickness of the thin metal
covering can be estimated by various spectroscopic analysis such as
X-ray uorescence spectroscopy (XRF), Rutherford backscattering spectroscopy (RBS) measurements [18], or X-ray reectometry. While the
detection limit of XRF is reached when the thickness is lower than
1 m [7], X-ray reectometry enables a detection down to the nanometer but usually requires a large sample area [19]. Therefore, in order to
distinguish a possible production difference in a complex corpus in
which the leaves are expected to exhibit a thickness below the micrometer, micro-beam RBS appears as a powerful technique.
Owing to the precious character of the artifacts, micro-samples
were not extracted. The metal leaves present on Greek terracotta were
non-invasively investigated by particle-induced X-ray emission (PIXE)
coupled to RBS measurements with 3 MeV protons. The combination

C. Fourdrin et al. / Microchemical Journal 126 (2016) 446453

of those techniques enables the determination of (1) the metal leaf

composition, (2) the qualitative composition of the different layers of
the stratigraphy, and (3) the metal leaf thickness. Furthermore, the imaging possibilities developed recently at the AGLAE facility [20,21] provided the opportunity to investigate the heterogeneity of the leaf. The
determination of the thicknesses in areas more or less concentrated in
gold is important to validate the use of point measurements for artifacts
exhibiting a poorly kept leaf.

447

subsequent burnishing treatment; it might also have been used as a way

of modifying the gold polychromy [7]. The bolus is not present on all
studied artifacts: on some of them, the metal leaf was applied directly
onto the preparation layer. Finally, on some particularly rened objects,
a burnishing tool was used to gently polish the gold leaf.
3. Methods
3.1. Experimental

2. Studied corpus
The corpus is composed of gurines and of small decorative objects
held in the Department of Greek, Etrucan and Roman Antiquites in the
Louvre museum. The 24 terracotta artifacts (and one wooden object)
are dated to the Hellenistic and Roman period and originated from different sites of the ancient Greek world (Fig. 1): Athens and Tanagra
(Mainland Greece), Myrina and Smyrna (actual Turkey), Cyrenaica
(actual Lybia), South Italy, and Apollonia Pontica (actual Bulgaria).
Some of the objects, such as buttons or owers are modest items, nevertheless completely gilded as a substitute of real jewelry pieces for funerary purposes. The rest of the corpus has a greater artistic value: some
gurines made at Smyrna were totally gilded in order to imitate bronze
statuettes. For the other ones, gilded highlights were used to embellish
decorative accessories such as earrings, bracelets, necklaces, and diadems, worn by female gures. An exceptional gurine stands alone in
the corpus: the so-called Lady in Blue (MNB 907). Found in Tanagra
(Boeotia) and made in a local workshop around 330300 BC [22], this
statuette of a standing draped woman is ornamented with a magnicent and rare golden stripe, kept in a perfect condition along the
lower edge of the blue mantel (Fig. 2a). The remaining leaves on other
artifacts are generally weathered (Fig. 2c). Besides gilding, it has been
recently noticed that some objects exhibiting dark grey areas might
have been decorated with another type of metal plating (Fig. 2d),
which needed to be analyzed.
The gilding technique at work on these objects is usually the following (Fig. 3): the rst white layer applied on the terracotta body is called
the preparation layer [1,2]; on the preparation layer, a yellow or red
layer called bolus is observed and is composed mainly of iron oxides
(goethite and hematite) [7,23]. This bolus is used to enhance the adhesion between the gold leaf and the preparation layer, and to allow for a

The micro-PIXE/RBS experiments were conducted at the AGLAE facility (Paris, France) using the external micro-beam line of the 2 MV tandem accelerator. Two high-energy SDD X-ray detectors with 50-mthick Al absorbers measured heavy elements (from Fe to U) and one
low energy SDD X-ray detector enabled the detection of light elements
(from Na to Ni) thanks to a 2-L/min He ow [11]. For the RBS analysis,
the detector was set at a distance of approximately 3 mm and at a
backscattered angle of 130. The 3 MeV H+ beam of a few nA exhibited
a diameter of 50 m during the experiments. Two types of measurements were performed. When the artifact exhibited a poorly conserved leaf, point measurements with the size of the beam were
acquired. In order to have better insights for the RBS data analysis,
at least four measurements were done for each artifact (one point per
stratigraphic layer). When possible, maps were acquired with a pixel
size of 10 10 m2.
3.2. PIXE data analysis
The point measurements were analyzed by GUPIXWIN [24] and
TRAUPIXE [20] in order to obtain a quantitative analysis on matrix and
trace elements using the pivot method assuming the targets as thick
and homogeneous. The acquired maps were extracted to the EDF le
format, which can then be treated either by AGLAEMAP (to visualize
maps and to extract spectra from specic areas) or by TRAUPIXE_EDF
(to produce elemental quantitative maps by processing each pixel),
both programs developed at the AGLAE facility [20,25]. For each pixel,
three PIXE spectra corresponding to each detector and an RBS spectrum
can be extracted. It provides the possibility to rebind pixel or to select
only part of the initial map and thus to obtain an average elemental
concentration or thickness of the selected area. The maps exported by

Fig. 1. Origin of the studied artifacts exhibiting gold leaves. The number of artifacts studied per regions is indicated in parentheses. Kerch and Apollonia Pontica are not reported on the map.

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C. Fourdrin et al. / Microchemical Journal 126 (2016) 446453

Fig. 2. Examples of studied artifacts: (a) Lady in Blue (MNB907) in front of the beam exit; (b) ower exhibiting a large area of a well conserved gold leaf; (c) Corymbe showing a poorly
conserved leaf and illustrating the difculties encountered linked to the artifacts geometries; (d) dark grey metal foil observed on several artifacts.

AGLAEMAP are presented in arbitrary units after dening regions of

interest (ROI) in the spectra.
For some artifacts presenting a large area of a well-conserved leaf,
for example, on the Lady in Blue (MNB907, Fig. 2a), it was possible to acquire maps of a relative large size (2.56 2.80 mm2 on Fig. 4). From this
map, it was evidenced that copper is present in the gold leaf and also in
the substrate (Fig. 4). The quantitative method used in GUPIXWIN is
based on a thick and homogeneous layer, which is not representative
of the system. Therefore, we choose to assume a constant copper concentration in the gold leaf substrate to calculate the gold concentration.

The concentration of Au/Ag/Cu in the gold alloy is calculated without

taking into account the PGE concentration, which are in our case close
to the detection limit and assuming that iron is not present in the gold
alloy [26].
3.3. RBS data analysis
The RBS spectra were simulated using SIMNRA v6.5 software [27].
The tting option of SIMNRA was not used due to the numerous parameters involved (e.g., the number of layers and their elemental composition, the roughness parameters) [28]. The spectra were simulated layer
after layer starting by the terracotta using the approximated composition obtained by GUPIXWIN for the terracotta, knowing that from the
second layer the obtained elemental composition corresponds to the
mean elemental composition of the underlying layers.
In this work, the penetration depth in the studied materials of the
3 MeV protons is approximately 100 m (calculated with SRIM/TRIM
in the gold plus substrate [29]), meaning that the complete stratigraphy
can participate to the RBS spectra. Accordingly, a target of a least 4 layers
was dened to take into account the different contributions. The thickness of the gold alloy leaf was evaluated using the following formula
using the concentrations of gold, silver and copper obtained in the corresponding layer:
ETFU cAu Au cAg Ag cCu Cu

Fig. 3. Example of stratigraphy observed on several artifacts: (1) terracotta layer; (2) white
preparation layer; (3) red bolus; (4) metal leaf.

where E is the thickness obtained in SIMNRA in TFU (1.1015 atoms cm2);

[Au], [Ag], and [Cu] are the atomic concentrations in Au, Ag, and Cu in
the layer, respectively; and cAu, cAg, and cCu are a conversion factor
(from TFU to nm) related to the atomic densities of the pure Au, Ag,
and Cu compounds, respectively. The standard deviations were derived

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449

Fig. 4. Quantitative elemental distribution of (a) Au, (b) Cu, (c) Si (in weight ppm) determined on the (a) Au L, (b) Cu K, (c) Si K emission lines. Size of the map: 250 286 pixels, each
pixel measuring 10 10 m2.

according to the procedure described by Mayer [28,30] and are related

to the thickness distribution of the gold leaves. The used atomic concentrations of Au, Ag, and Cu respect the ratios Au/Ag and Au/Cu obtained
by GUPIXWIN; however, they are not directly imported from the PIXE
atomic concentration since this layer is also composed of a silicon
oxide in order to obtain a correct simulation.
4. Results and discussion
4.1. Metal leaves composition
Two types of metal plating observed were characterized by PIXE/
RBS. The obtained compositions for the gray and yellow leaves are detailed below.
4.1.1. Tin foils
For all the 5 studied artifacts exhibiting a grey metal foil (Table 1), tin
was evidenced (Fig. 5). To one exception, all the tin foils were deposited
directly on the preparation layer, suggesting a different adhesion protocol. Aside from studies reported on Hellenistic vases, this is one of the
rst evidence of the use of tin foils on Hellenistic terracotta artifacts
[4], which are often confused with dust due to the alteration of the tin
foil. Tin plating was also evidenced on other Greek artifacts analyzed
by XRF recently at the C2MRF. Due to the alteration state of the foils, it
was not possible to have further insights either on the metal tin foil
composition or on their thicknesses.
4.1.2. Gold leaves
The obtained Au/Ag/Cu atomic percent values for the artifacts are
given in Table 2. They are showing a high gold concentration around
the Mediterranean basin, most of them exhibit a purity higher than
90 at.% (except MN695 and Cp9429, containing around 10 at.% of copper). In Myrina and Smyrna (Fig. 1), the gold concentration reaches
9799 at.% for the 7 artifacts, and the silver concentration does not

Table 1
Tin leaves, origin of the artifacts, and presence (or not) of a bolus below the metal leaf.
stands for the bolus absence. One artifact exhibits both tin and gold leaves.
Inventory no.

Provenance

Gilding

Bolus

CA 514
Cp 4765

Italy

Tin
Tin

Myrina 276
Myrina 695
MNE 1334

Myrina

Tin
Tin and gold
Tin

Present for gold

Present for tin

exceed 1 at.%. Concerning objects coming from continental Greece

(Attic, Tanagra), the gold purity ranges between 94 at.% and
99 at.%, while the silver concentration reaches 2 at.%. This high gold
concentration is also conrmed on other supports such as wood on
one artifact excavated in Kerch but created in Attic (S2713, Table 2).
In Cyrenaica and Italy, the gold purity exhibits more scattered values between 84 at.% and 99 at.% for the 10 artifacts. Although the number of
studied objects is not sufcient to conclude, the gold leaves high concentration suggests either an alluvial origin or an ancient purication
process [26].
The dispersion observed on the Lady in Blue (MNB 907), for which
the Au concentration ranges from 94.8 at.% to 98.5 at.%, should also be
discussed. This high variation can be related to the amount of copper
present under the form of Egyptian blue grains in a gray layer reported
on this artifact [7]. Egyptian blue is a copper pigment, CaCuSi4O10, synthesized since III millenary BC and used around the Mediterranean
basin during Antiquity [3133].
Regarding the color of the leaf, e.g., the gold polychromy, it appears that the studied artifacts are mainly gold (except two of
them, MN695 and Cp9429, which are reddish) since the silver concentration does not exceed 3 at.%, and the copper concentration is
below 10 at.% [12].
4.2. Gold leaves thicknesses
Fig. 6 presents the typical RBS spectra obtained when the simulation
was considered as satisfactory for a well-conserved leaf (not folded, or
faded). For this artifact, one can observe the gold peak, from approximately 27002900 keV, corresponding to the layer used for the thickness calculation. Below 2700 keV, the contribution of atoms (other
than Au, Ag, and Cu) present in the different layers of the stratigraphy
appears. The shape of the gold peak can be strongly modied by the
leaf thickness or its porosity and the distribution thickness due to
roughness [28,30,34].
The obtained thicknesses with their standard deviation are reported
in Table 2. The thicknesses for the corpus range from 160 to 710 nm, and
the highest standard deviation reaches 270 nm. As for the PIXE results
concerning the gold concentration on the Lady in Blue (MNB 907,
Table 2), the dispersion on the thicknesses values is quite important
for the same object (ranging from 230 to 470 nm). The highest value
(470 nm) was acquired on a different zone of the gurine (fan), for
which the placing was more difcult. Besides, this could also result
from a superposition of two leaves.
Despite the important standard deviations, several conclusions can
be pulled out from Fig. 7. First, all the analyzed leaves exhibit a thickness
below one micrometer, thus conrming the previous results obtained

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C. Fourdrin et al. / Microchemical Journal 126 (2016) 446453

Fig. 5. Tin leaf example. (a) Analyzed zone; (b) tin selection (ROI around 25.27 keV); (c) iron selection (ROI around 6.40 keV). Panels b and c are presented in color scale in arbitrary units.

by XRF on a limited corpus [7]. As for the gold alloy composition, no

major difference is observed among the studied excavation sites. Finally,
the gold concentration and the thickness obtained by the beating technique are not correlated. Such correlation could have been expected for
leaves with lower gold content [16].

4.3. Gold leaf heterogeneity

Using point measurement with a beam size of 50 m2 on rough surfaces questions the validity of the performed analyses. Actually, for most
of the corpus, due to the weathered aspect of the leaves and the placing
difculties, it was not evident to acquire replicates. In this view, for suited artifacts (i.e., with large gilded areas), one can take advantage of the
mapping possibilities to study the dispersion of the thicknesses values
calculated in several areas of the map. The benet of the simultaneous
acquisition of the PIXE-RBS spectra can be illustrated with the map performed on the Lady in Blue (Fig. 4) for which we exported the summations of RBS spectra corresponding to chosen areas in the PIXE map. For
this purpose, a region of interest was dened around the Au L peak
(from 9.42 to 10.04 keV on high-energy X-ray detectors). From the Au

L map, several areas related to the relative Au intensity were specied

using the following ratio: intensity at pixel/maximal intensity.
The exported RBS spectra were simulated with SIMNRA. Calculated
thicknesses for the corresponding areas are reported in Fig. 8. A mean
result for the relative Au intensity 20%100% is also reported on this gure. To the exception of the rst point (2040% Au relative intensity),
the thicknesses calculated by SIMNRA in TFU are approximately
constant with increasing relative Au intensity, but the gold atomic
concentration increase, leading to an expected general increase of the
thickness.
Besides, one can observe on Fig. 8 that the thicknesses calculated
for the different relative intensities are in agreement with the mean
thickness for the map (within the standard deviations). It should be
noted here that the area selected for the rst point (20%40% Au relative intensity) corresponds to the gold leaf border where the beam
is across gold and substrate and would not have been selected to perform a point measurement. Nevertheless, this result suggests that
the use of point measurements acquired on other artifacts is relevant. During the experiment, the location of the point measurement
is selected by both visual observation of the gold leaf and general
shape of the RBS spectrum.

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451

Table 2
Gold leaves, composition of the gold alloy determined by PIXE, and thickness of the metal leaf calculated by SIMNRA using RBS data. stands for non determined.
Inventory no.

Point analyzed

Origin

Au (at.%)

Ag (at.%)

Thickness (nm)

Standard deviation (nm)

MNB907

Braid 1
Braid 1
Braid 1
Braid 2
Braid 3
Braid 3
Draped
Fan
Head

Tanagra

97.0
96.9
97.7
98.3
97.3
97.4
95.8
96.4
94.8

0.7
0.8
0.8
0.5
1.2
1.3
1.7
1.5
1.8

2.3
2.3
1.5
1.2
1.4
1.2
2.5
2.0
3.5

230
330
290
310

270
470
280

40
60
70
60

50
160
100

Breast
Arm
Head

Tanagra

97.2
98.5
97.7

2.3
1.1
2.0

0.5
0.3
0.3

Head 1
Head 2

Attic

99.2
99.5
98.6

0.0
0.0
0.0

0.8
0.5
1.4

CA2552

CA1457
S2713

Kerch

CA 1776

Apollonia Pontica

MYR 33
MYR 162
MYR418 bis
Myrina 695
MYR72

S6113

92.5

0.4

7.1

710

270

99.6
99.5
98.7
99.1
97.4

0.2
0.2
0.3
0.3
0.6

0.2
0.2
1.0
0.6
2.0

520
320
250
370
230

110

50
70
60

Smyrna

98.6
98.6

0.8
0.9

0.6
0.5

160
330

130
70

Italy

98.3
98.0

0.4
0.1

1.3
1.8

Italy (Tarentum)

86.8
98.3
99.8
98.4

2.8
1.7
0.0
0.4

10.3

0.2
1.2

430
240

510

100
50

130

Cyrenaica (Cyrene)

90.3
99.1
83.9
99.6
99.6

0.9
0.5
2.4
0.2
0.1

8.8
0.5
13.7
0.2
0.3

440
340
410
420
690

70
110
120
80
260

Myrina

CA723
CA706
Nose
Cheek

CP 9429
CP 9557
CP5230
CP5230
MN 694
MN 700
MN 695
MN681
MN 684-21

Cu (at.%)

4.4. Concluding remarks

leaves, the used techniques permitted to analyze a complex corpus in

which the leaves were expected to measure less than 1 m [7]. The

The simultaneous acquisition of PIXE/RBS spectra allowed to noninvasively evidence two types of metal decorations which are constituted of tin for the grey foils and of gold for the yellow ones (with a gold
concentration around 95 at.%). As the tin foils were highly weathered,
it was not possible to precise their thicknesses. Concerning the gold

Fig. 6. Example of simulation obtained with SIMNRA. For the sake of clarity, only the major
contributions and the total simulated spectrum are shown.

Fig. 7. Gold leaf thicknesses as a function of the gold alloy purities obtained by the PIXE/
RBS point analysis. Semi-led squares: point analysis on the Lady in Blue (MNB 907);
circles: other artifacts.

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C. Fourdrin et al. / Microchemical Journal 126 (2016) 446453

Fig. 8. Determined gold leaf thickness as a function of the relative Au intensity selected on
the PIXE map (lowhigh borders) and standard deviation associated. The blue zone
corresponds to the mean value obtained for the 20%100% selection (the central line
corresponds to the thickness derived, 270 nm; and the dotted lines correspond to the
standard deviation, 70 nm).

obtained values, although exhibiting large discrepancies, are all below

the micrometer and most of them are below 500 nm (19 of the 23 measurements). Furthermore, when possible, the combination of PIXE-RBS
analyses provided insights on the leaves heterogeneity. This heterogeneity was investigated by selecting several areas in the PIXE map and
by determining the gold leaves thicknesses. It was observed that the obtained thicknesses are in agreement within the standard deviation.
In the light of these new results, it will be interesting to re-read ancient writers such as Pliny the Elder who commented on the issue of the
various thicknesses of gold leaves and foils used in Roman time [35,36].
The extreme thinness of the leaves used on earlier, Greek productions,
combined to the high purity of the gold metal suggests ancient purication techniques, such as cupellation and cementation, and elaborated
goldbeating skills [37]. Although it is difcult to conclude on the gold origins in the present study, since the PGE elements were in the limit of
detection; the gold leaves production appears almost homogeneous
around the Mediterranean Sea in the Hellenistic period. Further studies
should be pursued on ancient gilded objects produced in Ptolemaic and
Roman Egypt in order to compare the traditional Greek production with
the Graeco-Egyptian one. Finally, this study helps for a better understanding of the high degree of know-how involved in the polychrome
ornamentation of the Greek gurines. The results point out to the
specic expertise of gilders, capable of perfectly handling and mastering
extremely thin leaves. The work of these anonymous, so far unrecognized craftsmen of the ancient Greek world can thus be better appreciated and understood.
Acknowledgements
The authors are grateful to the Fondation des Sciences du Patrimoine
and the PATRIMA labEx for the nancial support of the PILINA program
and to an anonymous referee for his/her comments.
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