Applied Physics A (2020) 126:218

https://doi.org/10.1007/s00339-020-3386-y

Pigments analysis of an Egyptian cartonnage by means of XPS

and Raman spectroscopy
F. S. Gard1 · D. M. Santos2 · M. B. Daizo2,3 · E. Freire1,4,5 · M. Reinoso1,4,5 · E. B. Halac1,5

Received: 4 December 2019 / Accepted: 6 February 2020 / Published online: 20 February 2020
© Springer-Verlag GmbH Germany, part of Springer Nature 2020

Abstract
X-ray photoemission spectroscopy and Raman spectroscopy were used to identify pigments on an Egyptian cartonnage
from the Ptolemaic period (305–30 BC). While XPS allowed us to perform a qualitative chemical analysis and establish
the chemical composition of each pigment, Raman spectroscopy was employed to identify the associated minerals. High-
resolution (HR) XPS spectra revealed the existence of Hg and S in the red region of the sample; Raman spectroscopy con-
firmed the presence of cinnabar (α-HgS), as the red pigment. Sulfur and arsenic were detected by HR XPS in the yellow
part of the fragment, which is confirmed to be orpiment mineral ­(As2S3) by Raman spectroscopy. Raman spectra from blue/
green dark-colored regions of the samples corresponds to Egyptian blue pigment ­(CaCuSi4O10). Detection of Cu and Cl by
XPS, from the same region, is a strong indication of a degradation product of the Egyptian blue, namely a polymorph of
trihydroxychloride ­Cu2(OH)3Cl.

Keywords XPS · Raman spectroscopy · Pigments · Egyptian cartonnage

1 Introduction interesting and important area of research, among the others,

Application of nondestructive analytical techniques is now
well established in the field of archaeometry. The number of
analytical studies on archaeological artifacts using the most
sophisticated techniques has been rising during the last dec-
ade, which is directly related to the recent instrumental and
technological improvements of those techniques. One of the
Electronic supplementary material The online version of this
article (https​://doi.org/10.1007/s0033​9-020-3386-y) contains
supplementary material, which is available to authorized users.
* F. S. Gard
fsgard01@gmail.com
1
Centro Atómico Constituyentes, Comisión Nacional de
Energía Atómica, Buenos Aires, Argentina
2
Departamento de Humanidades, Universidad Pedagógica
Nacional, Buenos Aires, Argentina
3
Facultad de Filosofía y Letras, UBA, Buenos Aires,
Argentina
4
Consejo Nacional de Investigaciones Científicas y Técnicas
(CONICET), Buenos Aires, Argentina
5
Escuela de Ciencia y Tecnología, UNSAM, Buenos Aires,
Argentina
in the field of archaeometry is the identification of pigments
and minerals used on polychrome archaeological artifacts.
The most common techniques for pigments analysis are
X-ray fluorescent spectroscopy (XRF) ([1], and references
therein), Raman spectroscopy ([2], and references therein),
and scanning electron microscopy (SEM–EDS) ([3], and
references therein). These techniques detect a wide variety
of elements or compounds, with an excellent sensitivity
and with minimal damage to the samples. However, none of
them can detect all range of elements or compounds since
each technique present its own limitations. For example, in
general, light elements are difficult to be detected by XRF
technique, and in particular by a hand-held XRF, which is
often used by the archaeologists for analysis of the artifacts
on the archeological sites or even in the museums. All the
elements with atomic mass units less than ~ 10 amu are
beyond the detection of XRF ex situ.
A large amount of literature is available on the identifica-
tion of pigments using Raman spectroscopy, and compara-
tive databases have been compiled, see the special issues of
the Journal of Raman Spectroscopy, which are dedicated
only to the cultural heritage studies [4]. However, one
important limitation of the Raman spectroscopy technique
is that it cannot be used for metals and alloys. In addition,

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the unwanted fluorescence signal of impurities and of the
pigment itself may interfere with the Raman spectrum and
can hamper the identification of some compounds.
SEM has been used routinely to examine a wide range
of archaeological materials. In particular, SEM secondary
electron (SE) and back scattering (BS) imaging can pro-
vide wealth information about the surface morphology and
topography of the sample. Besides, chemical composition
can be determined using energy dispersive spectroscopy
(EDS), which provides a relatively quick and nondestruc-
tive means of obtaining qualitative information. However,
it must be emphasized that EDS–SEM technique cannot
distinguish chemical variations of elements based on their
oxidation state.
Clearly XPS technique, due to its unique operational prin-
ciple, can provide valuable information on the surface char-
acteristics of the archaeological artifacts and artistic objects,
often essential for the understanding of their manufacturing
techniques as well as ageing, and the degradation process.
It is interesting to note, that despite many advantages of the
XPS technique over the other nondestructive techniques, its
application in the field of the archaeometry in general and
pigment analysis, in particular, has been rather limited to a
few studies. Our comprehensive literature survey concludes
that, not much longer after the invention of the commercial
XPS systems, Lambert et al. [5, 6] were exploring the appli-
cation of XPS for the analysis of archaeological artifacts.
In addition to those earlier investigations, we can refer to
a handful studies, where XPS as the main technique has
been used to investigate metallic-, ceramic- and glass-made
archaeological objects. For example, Spoto et al. [7] used
XPS among other techniques to study pottery samples. XPS
is used for elemental identification, quantification and espe-
cially for chemical state identification of medieval pottery,
by Bruno et al. [8, 9]. Lambert et al. [10], using XPS and
AES techniques to study glass objects, demonstrated that
the oxidation state of Cu has a crucial role on the color of
the glass. Whereas, Paparazzo et al. [11–13] used XPS tech-
nique to study metallurgical characteristics, corrosion and
formation of patinas on the metallic objects.
The aim of ther current study is to explore the applica-
tion of XPS and Raman spectroscopy as two complementary
techniques to identify the pigments and minerals used to
decorate an Egyptian cartonnage belonging to the Ptolemaic
period. We have focused our study mainly on the primary
colors, namely red, yellow and blue. To our best of knowl-
edge XPS study on the pigments used to decorate an Egyp-
tian cartonnage has not been reported in literature. Even
though XPS technique can provide chemical composition
of the pigments and their degradation products, Raman spec-
troscopy technique is essential to confirm the identification
of the minerals and pigments. We consider that the com-
bined results of XPS and Raman spectroscopy provide an
13
F. S. Gard et al.
important insight over the materials and minerals used as the
pigments, which have been used to decorate the cartonnage.
A comprehensive review of the ancient Egyptian pig-
ments, such as [14, 15], is beyond the scope of the current
study. Nevertheless, in the following, we present a brief
description of the most important pigments used as the
primary colors by the ancient Egyptians.
Among the minerals and materials, which ancient Egyp-
tian artists were using as the red pigment, one can men-
tion red ochers (goethite or hematite), red lead, realgar
and cinnabar [16–19]. Cinnabar is a natural occurring red
mercury (II) sulfide (HgS) mineral, which as synthetic
pigment is known as vermilion. Cinnabar, due to its low
hardness and high density, may have been considered as a
material most suitable for coloring. It was believed to be
used by the Egyptian artists in the late Ptolemaic or even
Roman Period [20], and has been detected in several arti-
facts thereafter [21, 22]. However, a few early examples
have also been reported [23, 24]. Therefore, determining
the exact time when cinnabar was introduced to the Egyp-
tian color palette is difficult, as the number of discovered
artifacts decorated by cinnabar is scant.
On the other hand, among the yellow pigments one can
name yellow ochers [15, 19], and in less degree one can
mention orpiment, jarosite and natrojarocite. It was sug-
gested that yellow ochers were used as a pigment from
the pre-Dynastic Egypt to the Roman period. However,
this point of view has been changed by identification of
orpiment in the 2nd Dynasty artifacts [25]. Jarosite (and
natrojarosite) were first reported as a pigment in a deco-
rated pottery from 11th Dynasty from El Tarif [26].
Orpiment is a yellow sulfide of arsenic ­(As2S3), which
is locally abundant in Egypt in all gold and silver ores [27,
28]. It has been used as a natural and as synthetic mate-
rial in ancient Egypt. Colinart [25] reports, using orpi-
ment as early as the 2nd Dynasty and several later studies
have also reported the usage of orpiment as pigment [27,
29]. There are a few studies that suggest the usage of the
orpiment along with other yellow pigments. El Goresy
et al. [30] stated that orpiment has been used mixed with
yellow ocher in wall paintings from the 18th Dynasty.
McCarthy [31] also reports on detection of orpiment and
yellow ocher in the same samples from the tomb of Suem-
niwet (1430 BC) analyzed by EDX. However, orpiment
was mostly identified as a sole pigment in coffins dated
from the New Kingdom to the end of the third intermedi-
ate period.
Among the primary colors, blue is particularly different
from the others. The material basis in the form of herbal
and animal constituents and minerals for blue color were
not sufficiently available in the ancient time. Blue is not an
earth color. Colors provided by the surface soil are referred
as so-called earth colors. One can only imagine, how lack
Pigments analysis of an Egyptian cartonnage by means of XPS and Raman spectroscopy Page 3 of 12 218
of easy-accessible of blue pigments would have generated
frustrations and challenges to the ancient artisans [32].
The principal naturally-occurring minerals used as blue
pigment in the ancient epoch were lapis lazuli (lazurite) and
azurite, which were needed to be mined. Precious gemstone
lapis lazuli (Na, Ca)8(AlSiO12)(S, ­SO4, Cl) was only available
from the area of present day Afghanistan. Whereas, azurite,
a blue hydrated copper carbonate mineral 2­ CuCO3Cu(OH)2,
could be found locally in Sinai desert [32].
There are not any convincing studies to suggest that
ancient Egyptian artisans were using lazurite as blue pig-
ment. However, it has been suggested that azurite has been
used. The oldest detection of azurite in ancient Egypt from
the 4th Dynasty has been reported by Lucas et al. [18]. It
has also been reported to be used to paint a mummy of the
5th Dynasty [18]. Reports on detection of azurite on Egyp-
tian artifacts from 5th Dynasty on-wards are rare, mainly
because of the invention of the oldest synthetic pigment,
namely Egyptian blue (­ CaCuSi4O10). The earliest known use
of Egyptian blue is reported on a sarcophagus from the 4th
Dynasty, and it is believed that it was used up to the Roman
period [25, 33].
2 Materials and methods
The Museum of La Plata (Museo de La Plata), capital of
Buenos Aires province, Argentina keeps a little Egyptian
collection, including a small defective mummy [34], which
was considered to be the mummy of a toddler, due to its
size (Fig. 1a). However, in 1980, computerized tomography
(CT) scans reveled that it was the head of an adult, whose
body was reconstructed with linen bandages and plaster.
Further studies carried out in 2010 and the reappearance
of fragments of its gilded mask and cartonnage have added
new valuable information to the previous study [35]. The
characteristics of the cartonnage [36] allow us to locate it,
historically, in the Ptolemaic period (305–30 BC), probably
third century BC, similar method has been used by Cokitte
et al. [37].
Figure 1b–e show three fragments of the cartonnage,
mounted on a 60 mm XPS sample stage. Theses, among
other smaller pieces, were used to analyze the pigments.
The cartonnage was made of woven layers of linen, which
was later covered by plaster. A multicolored pattern was
then painted on the surface. A visual inspection of the frag-
ments reveals red, yellow, orange and rather blue/green dark
regions. The cartonnage was accompanied with a funerary
mask (not shown here), which had been shattered to pieces
under some unknown circumstances almost 50 years ago.
The mask was originally decorated with golden leaves. A
rather comprehensive study over the gilded mask has already
been published [38], where we have presented and discussed
extensively the ancient Egyptian gold parting and metallur-
gical technique of gilding process.
3 Experimental methods
and instrumentation
3.1 Raman spectroscopy
Raman microscopy analyses were performed on numerous
fragments using a LabRAM HR Raman system (Horiba
Jobin Yvon), equipped with two monochromator gratings
and a charge coupled device detector (CCD). An 1800 g/
mm grating and 100 μm aperture resulted in a 1.5 cm−1 spec-
tral resolution. An Ar laser line at 514.5 nm and a He–Ne
laser line at 632.8 nm were used as excitation sources. Laser
power was adjusted to avoid overheating on the sample. The
spectrograph is coupled to an imaging microscope with 10X,
50X and 100X magnifications. Typically, the laser spot
on the sample was about 10 and 3 μm diameter for a 10X
and 50X magnification, respectively. An advantage of the
microscopic facility is the possibility of analyzing different
regions and pigments separately.
3.2 X‑Ray photoemission spectroscopy
XPS measurements were also carried out on several frag-
ments in a PHI 5000 VersaProbeII system. It is equipped
with a monochromatic aluminum K ­ α X-ray source
(1486.6 eV), and a spherical capacitor analyzer (SCA). The
multichannel detection system consists of a pair of micro-
channel plates and a 16-channel anode. The detector’s sen-
sitivity is optimized using the entire focal plane of the SCA.
The base pressure during the measurements in the analy-
sis chamber was in the lower range of 1­ 0–10 Torr. The experi-
mental condition of the X-ray source was set to 100 μm spot
size, X-ray power of 25 W, and bias voltage of 15 kV.
An Ar-etched, polished fine-grained silver foil was earlier
used to measure the resolution of the system. The Full Width
at Half Maximum (FWHM) of Ag ­3d5/2 peak was measured
to be 0.49 eV. All the XPS survey scans were collected under
the following conditions. The energy range: 0–1400 eV, the
Pass Energy (PE): 187.85 eV, the step size: 0.8 eV, and the
time per step was set to 50 ms. For the high resolution (HR)
XPS scans the PE was set to be 23.75 eV and the step size
changed to 0.1 eV. Spectra were analyzed using CasaXPS
software version 2.3.18.
The cartonnage fragments are made of insulating mate-
rial; therefore, the charging effect during the XPS measure-
ments is inevitable. The widespread practice to overcome
the complication associated with the charging effect is using
an electron flood gun. However, traditional electron flood
gun charge neutralization is not effective in neutralizing the
13
218 Page 4 of 12 F. S. Gard et al.

Fig. 1  a Photo of the small

defective mummy, preserved at
the Museum of La Plata, b–e
some of the fragments mounted
on the XPS sample stage of
diameter 60 mm. The red dots
on the samples show the loca-
tions, where XPS micro analysis
has been performed

localized positive charge created by the X-ray beam, because 4 Results

the samples static charge interferes with the low energy elec-
tron beam. In the current study, we have used PHI’s patented
dual beam charge neutralization method, which uses a low
energy ­Ar+ ion beam (~ 5 eV), along with an electron beam
(~ 1 eV), to eliminate the samples static charge, allowing the
low energy electron beam to reach the sample and neutralize
the localized positive charge created by the x-ray beam. In
addition to that, the dominant component of adventitious
carbon (AdC) namely (C–C/C–H) in the C 1 s energy region
at 284.8 eV (not shown here) was used as a reference point
to calibrate the XPS spectra.
4.1 Raman spectroscopy
Raman spectroscopy technique provides mineral identifica-
tion, using an extensive available database [39, 40]. Figure 2
presents typical Raman spectra collected from the red, yel-
low and blue/green dark regions. Raman spectra of relevant
standard minerals have also been included as references.
Four different fragments containing red pigment areas
were studied using an He–Ne laser (631.8 nm) as excit-
ing source. Altogether, five Raman spectra were obtained

13
Pigments analysis of an Egyptian cartonnage by means of XPS and Raman spectroscopy Page 5 of 12 218

and analyzed, where two spectra have been acquired from

a single sample but at different locations. We have identi-
fied bands at 252, 284, and 342 cm−1 with a shoulder at
349 cm−1 which has been associated with cinnabar: mercury
sulphide in the α-phase (trigonal). Raman spectrum reported
for α-HgS presents a band c.a. 254 cm−1, assigned to sym-
metric ­A1 mode, and others at 284 and 345–353 cm−1, cor-
responding to degenerated E mode [40, 41]. In some Raman
spectra from red regions, Raman peaks associated with
calcite ­(CaCO3) were also identified (not shown here for
simplicity). A typical Raman spectrum from the red region
containing calcite is presented in the electronic supplemen-
tary materials, see figure S1, where the characteristic Raman
shifts associated with cinnabar and calcite are identified. The
origin of the calcite is confirmed to be associated to the plas-
ter base of the cartonnage, see the electronic supplementary
materials, figure S2, which shows Raman spectra acquired
from two different locations on the bare plaster region with-
out any pigments.
Figure 2b shows one of the typical Raman spectra
obtained with an Ar laser (514.5 nm) from yellow areas of
three fragments, samples A and C, see Fig. 1, and an addi-
tional fragment, not shown here. The identified bands cor-
respond to those reported for orpiment ­(As2S3). Orpiment
has a tetramolecular monoclinic unit cell of C ­ 2h symmetry,
where ­As2S3 layers are parallel to the (010) plane and are
held by Van der Waals forces. In this structure, AsS-spiral
chains are running parallel to the c-axis [41]. The spectrum
shown here from the yellow part of the sample is in good
agreement with the results reported by Scheurmann et al.
[41] and Frost et al. [42]; the bands at 382 and 355 cm−1
were assigned to As-S antisymmetric and symmetric vibra-
tions, respectively.
Raman spectroscopy measurements from the blue/green
dark regions on two fragments, samples A and B, were
performed with an Ar laser (514.5 nm). The spectra pre-
sent some low-intensity Raman lines, superimposed on a
strong fluorescence background, not shown here for sim-
plicity. Background subtraction revealed the Raman peaks
in more details. Figure 2c shows a characteristic processed
Raman spectrum from a blue/green region. The subtraction
process did not affect the peak frequencies of the strongest
Raman shifts at 120, 430, 1087 cm−1. Comparison between
our results with the literature data, also shown in Fig. 2c,
which confirms that the blue/green dark region contains
Egyptian blue, calcium copper tetrasilicate. Egyptian blue,
as we stated above, is the oldest synthetic pigment. Its char-
acteristic bright blue color is originated from blue crystals of
calcium copper (II) silicate, ­CaCuSi4O10 [32]. Even though
Fig. 2  Raman spectra from a red, b yellow, and c blue/green dark
Raman spectroscopy results provide a strong indication of
regions
the presence of Egyptian blue in the blue/green dark region
of the fragments, this technique could not explain the dis-
coloring observed in these regions. One can only speculate

13
218 Page 6 of 12
that the strong fluorescence background and unidentified
peaks in the spectra are due to the degradation products and
impurities in these regions. This is a classical example that
shows XPS technique can provide further information about
the chemical composition of the fragments, which can sub-
sequently explain the origin of the darkening the Egyptian
blue pigmen.
4.2 X‑ray photoemission spectroscopy (XPS)
Figure 3 shows typical XPS survey scans obtained from red
(panel a), yellow (panel b), and blue/green dark (panel c)
regions, respectively. A characteristic optical microscopy
(dark field) image of each single pigment is also shown along
with the corresponding XPS survey spectrum. The spectra
were acquired after 5 min of 2 keV ­Ar+-ions sputtering, to
remove the most top layer of the native contamination in the
form of oxygen and carbon. Elemental chemical composition
in each color region of the samples, as identified by survey
scans, are indicated in the spectra, and listed in Table 1. The
common elements detected by XPS regardless of the color
were O, C, Ca, N, Si. In addition to the above-mentioned
elements, Hg and S; As and S; Cu and Cl were detected for
red, yellow and blue/green dark region, respectively.
HR XPS spectrum of Hg 4f transition line obtained
from the red area of the sample is shown in Fig. 4a. Shirley
background was applied, to remove the contribution of the
inelastic electron scattering. The main components of Hg 4f
transition line were fitted by a doublet, with an energy dif-
ference of 4.0 eV and intensity ratio of 4:3, due to spin–orbit
coupling. They are assigned to be Hg 4­ f7/2 and Hg 4­ f5/2 tran-
sition lines, centered at (100.9 ± 0.1) eV and (104.9 ± 0.1)
eV, respectively, corresponding to the mercury atoms in cin-
nabar mineral. This result agrees very well with the Raman
spectroscopy results. To achieve the best possible fitting to
the raw data, an extra doublet was also required, which can
be attributed to Si 2p transition line. The doublet consists
of two GL (30) line shape peaks of Si 2­ p3/2 and Si 2­ p1/2,
with an energy difference of 0.6 eV, centered at (103.2 ± 0.1)
eV and (103.8 ± 0.1) eV, respectively [43]. We suggest that
they are related to S­ iO2 in the form of sand or quartz con-
tamination. There have also been reports on mixing quartz
with the material used to make the plaster base, in ancient
Egypt, to strengthen its structure. Figure 4b shows HR XPS
spectrum of S 2p region. Two pairs of doublets are used to
fit the spectrum. The first doublet was identified as the S
­2p3/2 and S ­2p1/2 components of sulfur atoms from cinnabar,
centered at (162.2 ± 0.1) eV and (163.4 ± 0.1) eV, respec-
tively [44]. The other doublet at higher binding energy, cen-
tered at (169.0 ± 0.1) eV and (170.2 ± 0.1) eV, respectively,
can be related to sulfate ­(SO4)−2. This is consistent with
the well-known mechanism of the atmospheric corrosion
of the archeological artifacts, so called weathering process.
13
F. S. Gard et al.
The first step of the weathering process is the formation of
metal oxides, in the current case is mercury oxide. Subse-
quently, the oxides continue to transform to the correspond-
ing basic carbonate by reaction with the ­CO2, in the vicinity
of water. Finally, when the S ­ O2 concentration in the air is
high enough, carbonate anions can be displaced by ­SO2,
forming sulfates. Nevertheless, it should be noted that we
cannot discard the possibility of traces of gesso contamina-
tion ­CaSO2 2(H2O), in the plaster base of the cartonnage
[45], which can also explain the second doublet of sulfur at
higher energy.
It is noteworthy to mention that some fragments were also
studied by a conventional X-ray diffraction (XRD). To our
opinion, the best analytical technique, based on the X-ray
diffraction, would be μ-XRD, where the X-ray beam can
be focused on a certain pigment area. The X-ray beam in a
conventional XRD system is rather broad and can generate
signals from all other pigments on the sample, as the frag-
ments containing, only one pigment, were not available. The
XRD spectrum from the only available fragment containing
red color is presented in the electronic supplementary mate-
rials, see figure S3, where the diffraction lines for cinnabar
can be identified. The other main diffraction lines in the
spectrum are attributed to ­CaCO3 the main compound in the
plaster base in accordance with Raman spectroscopy results.
In addition to the above-mentioned doublet, a rather weak
feature at ~ 167 eV can be seen as a shoulder to the doublet
at higher binding energy. We propose that it is originated
from Si 2s satellite. We did not fit an extra component in this
spectrum, as its location would be accompanied with a large
uncertainty, because the spectrum is rather noisy. However,
we have identified a similar feature, but much stronger, in the
HR XPS spectrum of S 2p region collected from the yellow
pigment areas. In this case, since the spectrum is consider-
ably much less noisy, we were able to fit an extra peak. The
exact location of the extra component was then identified
with much higher certainty, see Fig. 5a.
HR XPS spectrum of O 1s region is shown in Fig. 4c.
Two types of oxygen contributions can be observed. The
main one, at (531.9 ± 0.1) eV, can be attributed to oxygen in
the sulfates and/or hydroxides. The second, at (533.0 ± 0.1)
eV, may be assigned to the adsorbed water and/or ­SiO2.
Figure 5a shows a HR XPS spectrum of S 2p transition
line obtained from the yellow region of the sample. The
background removed using a Shirley function. The spec-
trum is qualitatively similar to that of S 2p transition line
from the red region of the sample. Two pairs of doublet
were used to fit the raw spectrum. The first one, centered
at (162.5 ± 0.1) eV and (163.7 ± 0.1) eV, is assigned to S
­2p3/2 and S 2­ p1/2 related to orpiment (­ As2S3) [46], in agree-
ment with Raman spectroscopy results. Whereas the other
doublet, centered at (169.3 ± 0.1) eV and (170.5 ± 0.1) eV,
is assigned to S ­2p3/2 and S ­2p1/2 related to sulfates and/
Pigments analysis of an Egyptian cartonnage by means of XPS and Raman spectroscopy Page 7 of 12 218

Fig. 3  Survey scans of each region along with the corresponding optical microscopy images from a Red, b yellow and c blue/green dark regions

13
218 Page 8 of 12 F. S. Gard et al.

Table 1  Chemical compositions of pigments detected by XPS tech-

nique
Color region Chemical composition

Red O, C, Ca, N, ­Sia, S, Hg

Yellow O, C, Ca, N, Si, S, As
Blue/green Dark O, C, Ca, N, Si, Cl, Cu
a
Si 2p interferes with Hg 4f

or gesso in the plaster, in accordance with the XPS results

from the red part of the sample. The extra peak observed at
(154.1 ± 0.1) eV, is related to ­SiO2, whereas the Si 2 s satel-
lite, as explained above, can be recognized as a shoulder
centered at (167.3 ± 0.1) eV.
HR XPS spectrum of As 3d region is shown in Fig. 5b. A
Shirley background was also applied to the spectrum. The
raw data was fitted with a pair of components at (43.1 ± 0.1)
eV and (43.9 ± 0.1) eV, corresponding to the contribution
of As 3­ d5/2 and As 3­ d3/2 originated from the arsenic atoms
in orpiment mineral, and a single peak at (43.6 ± 0.1) eV
related to the Ca 3 s transition line. Calcium is the main ele-
ment in the material used to make the plaster base namely
calcite, which its presence is confirmed by Raman spectros-
copy results.
HR XPS spectrum of Cu 2p transition line from a frag-
ment containing dark blue/green region is shown in Fig. 6a.
Two main peaks, corresponding to the Cu ­2p1/2 and Cu ­2p3/2
doublet with a spin–orbit splitting of around 20.0 eV, are
identified at 933.1 and 953.1 eV, respectively. Two shoulders
on each side of the mean peaks are identified and their loca-
tions are indicated in the spectrum. A weak satellite system
is observed in the range of 943–947 eV, which is an strong
indication of a small amount of ­Cu+2 species.
As it is stated above, Raman spectroscopy results indi-
cated the existence of Egyptian blue pigment (­ CaCuSi4O10)
in this region, but could not explain the observed dark
color. However, discoloration of Egyptian blue, from blue
to dark green and even brownish color, has been reported
and explained due to degradation of the pigment. Therefore,
in the following, we will analyze HR XPS spectra of Cu
­2p3/2 and Cl 2p, based on the previous studies that suggest
Egyptian blue in the vicinity of ­Cl− ions may convert to
atacamite, ­Cu2(OH)3Cl or one of its polymorphs, parata-
Fig. 4  HR XPS spectra of: a Hg 4f, b S 2p, and c O 1s regions,
camite or clinoatacamite. They are degradation products of
obtained from a red color region
Egyptian blue in contact with saline environment via the
following chemical reaction [47, 48]:
account the presence of atacamite, three different chemical
2CaCuSi4 O10 + 5H+ + Cl− components can be identified at (931.0 ± 0.1), (933.2 ± 0.1)
⇔ Cu2 (OH)3 Cl + Ca2+ + 8SiO2 + H2 O. and (935.3 ± 0.1) eV binding energies, which correspond
to Cu(OH)2, CuCl, and C ­ uCl2 species, respectively. These
HR XPS spectrum of Cu 2­ p3/2 is fitted in more details, to values are in a good agreement with those reported by
reveal the chemical states of Cu atoms, see Fig. 6b. Taking to Boita et al. [49] and Han et al. [50]. It is clear that the main

13
Pigments analysis of an Egyptian cartonnage by means of XPS and Raman spectroscopy Page 9 of 12 218
Fig. 5  HR XPS spectra of: a S 2p, and b As 3d regions, obtained
from yellow color region
component in the Cu 2­ p3/2 region is CuCl, whereas C ­ u+2
species in the form of Cu(OH)2 and C ­ uCl2 were detected in
much smaller quantities. This is consistent with the weak
satellites observed in the spectrum of Cu 2p. It has been sug-
gested that relative ratios of these three components depend
directly on the types of polymorphs of ­Cu2(OH)3Cl [49].
HR XPS scan from Cl 2p region is shown in Fig. 6c. A
doublet, with an energy difference of 1.6 eV, was identi-
fied for Cl ­2p3/2 at (198.7 ± 0.1) eV and for Cl ­2p1/2 at
(200.3 ± 0.1), respectively. They are assigned to the doublet
of Cl 2p photoelectron lines for cupper (I) chloride com-
pound, CuCl, which are consistent with reported values in
ref. [51]. It should be noted that the presence of chlorine is
also confirmed by other analytical techniques such as scan-
ning electron microscopy (SEM) and electron probe microa-
nalysis (EPMA) [52]. Therefore, we suggest that degradation
of Egyptian blue caused the formation of ­Cu2(OH)3Cl at
the surface, as it has been detected by XPS but its amount
is below detection limit of Raman spectroscopy technique,
due to the significant fluorescence background.
5 Discussion
In the following, we present a brief review of cinnabar, orpi-
ment and Egyptian blue degradation process and possible
products. A comprehensive review of this topic is beyond
the scope of the current study. However, we believe that it is
important for the potential readers to be able to reflect on our
findings on a background of a few previous studies.
5.1 Cinnabar (α‑HgS)
Alteration and darkening of vermilion pigment have been
reported and discussed in detail in literature [53, 54]. Among
the major natural factors, which can aggravate aging phe-
nomenon and consequently degradation of cinnabar pig-
ment, we can mention light/UV radiation, humidity, and
chemical reaction to halogen ions. It has been reported that
cinnabar will degrade underexposure of the sun light, with
a final by-product of metacinnabarite, a black modification
of HgS [55]. It has also been reported that even moonlight
might be harmful to the pigment [56]. Light-induced discol-
oration of cinnabar has also been reported elsewhere [57,
58]. Blacking occurrence of cinnabar has been explained by
light-induced oxidation of sulfur, or other Hg- and S-chem-
ical products [54].
The most common halogen ion in the environment is
−
­Cl ions, which can be originated from the traces of chlo-
rine in the air that can cause discoloration of any pigments.
Surface darkening of cinnabar has also been reported at the
vicinity of Cl-ions, under an ideal condition of humidity
[59]. It is explained that cinnabar goes through a structural
alteration and then free H­ g0 and S
­ 0 are created at the surface
[60]. Free mercury subsequently reacts further with chlo-
rine, to generate mercury chloride products, whereas sulfur
is oxidized to sulfur dioxide, which can be released to the
environment.
Our analytical XPS and Raman spectroscopy stud-
ies failed to detect any degradation by-products of cinna-
bar. XPS technique cannot distinguish between Cinnabar
(α-HgS), and metacinnabarite (HgS), as their electronic
structure are similar. Cl has not been detected, within the
detection limit of XPS technique, in the red area of the frag-
ments. Whereas it has been detected in the blue regions of
the fragments. Therefore, we can discard any possibility of
­Cl−-ions induced process of cinnabar degradation.
13
218 Page 10 of 12
Fig. 6  HR XPS spectra of: a
Cu 2p, b Cu 2­ p3/2, and c Cl 2p
regions, obtained from blue/
green dark color region
5.2 Orpiment ­(As2S3)
There are contrary reports on the degradation and discol-
oration of the orpiment. The fading of orpiment has been
reported in [61]. Green [29] confirmed that the fading of
orpiment is due to the oxidation of arsenic sulfide to white
arsenolite ­As2O3, which consequently leads to loss of sulfur
from orpiment, which can subsequently react with the other
minerals and causing discoloration. The formation of white
arsenic trioxide when orpiment was exposed to light, or to
ozone in the absence of light is also reported [62].
On the other hand, the fading phenomenon has not been
reported by Colinart [25], in all the artifacts that he has stud-
ied. It has been suggested that a varnish layer can protect the
13
F. S. Gard et al.
orpiment from degradation process. Our methodical results
of XPS and Raman spectroscopy, to detect any byproduct
of the degradation process of orpiment were inconclusive.
5.3 Egyptian blue ­(CaCuSi4O10)
Egyptian blue consist of small crystals of cuprorivaite and
a glassy phase of copper-containing wollastonite [47]. In
general, Egyptian blue was considered a very stable pig-
ment, in comparison to the other pigments [63]. However,
basic copper chloride compounds were first detected in
ancient Egyptian paintings from the Middle Kingdom. Sub-
sequently, atacamite was reported from tombs of the 11th
Dynasty in Deir el Bahari [47]. This was believed to be a
Pigments analysis of an Egyptian cartonnage by means of XPS and Raman spectroscopy Page 11 of 12 218
degradation product of a blue pigment instead of an actual
pigment [64]. Another important alteration product of Egyp-
tian blue, ­CuCaSi4O10 is copper chlorides as isomers of tri-
hydroxychloride ­Cu2(OH)3Cl [65]. The visual effect of this
transformation is reported to be changing of the original blue
color to a dark green bluish color. It has also been reported
that decomposition of Egyptian blue to a combination of
cuprite mixed with one of the copper trihydroxychloride
would also give a visual appearance of dark brown color.
It is noteworthy to mention that visual inspection the frag-
ments used in the current study, reveals also discoloration
of Egyptian blue to a dark green color, and some to a rather
black brownish color. On the other hand, Daniels et al.[66]
advocate that surface dirt and aging process of gum Arabic
may also cause discoloring the Egyptian blue to a rather
dark brownish color. Our XPS analytical study confirmed
the process of Egyptian blue degradation by so called cop-
per chloride cancer. It is important to emphasize that, in the
current study we cannot discard other processes of darken-
ing of the Egyptian blue pigment, such as dirt or weathering
process of gum Arabic.
6 Conclusion
X-ray photoemission spectroscopy provided chemical com-
position of the minerals of three primary color pigments,
namely, red, yellow and blue, used in a polychrome Egyptian
cartonnage from the Ptolemaic period (305–30 BC). The
common elements detected by XPS regardless of the color
were O, C, Ca, N, Si.
In addition to the above-mentioned elements, Hg and S;
As and S; Cu and Cl were detected for red, yellow and blue/
green dark region, respectively. Raman spectroscopy tech-
nique allowed us to identify the associated minerals of the
pigments for each color. It is confirmed that red, yellow, and
blue/green dark color are made of cinnabar, α-HgS; orpi-
ment, ­As2S3; and Egyptian blue, C ­ aCuSi4O10 pigments,
respectively.
HR XPS spectra obtained from different color regions,
to identify the degradation products, were inconclusive for
red and yellow pigments. Degradation by-products were not
detected in the red and yellow regions. However, HR XPS
spectra of Cu 2p and Cl 2p transition lines obtained from the
dark green region confirmed the alteration of Egyptian blue,
to a polymorph of trihydroxychloride ­Cu2(OH)3Cl.
Acknowledgements The authors gratefully acknowledge the Museum
of La Plata (Museo de La Plata), and its former Director, Dr. Silvia
Ametrano. We are also grateful to Dr. Susana A. Salceda, and Dr.
Mariano del Papa for providing access to the valuable Egyptian col-
lection of the museum. We also thank Cristian Oubiña for the XRD
measurements. The corresponding author, F.S. Gard, would like to
express his appreciation to CNEA, for providing only a working place.
He is not affiliated to CNEA, and do not receive any form of stipendium
or financial help from CNEA.
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