Received: 26 April 2019 Revised: 7 June 2019 Accepted: 11 June 2019

DOI: 10.1002/sia.6685

RESEARCH ARTICLE

Application of surface science techniques to study a gilded

Egyptian funerary mask: A multi‐analytical approach

Faramarz Sahra Gard1 | Maria Belén Daizo2,3 | Diego Maximiliano Santos3 |

Emilia Betty Halac1,4 | Eleonora Freire1,4,5 | María Reinoso1,4,5 | Patricia Beatriz Bozzano1,4 |

Silvia Adriana Dominguez1,4 | Ricardo Jesús Montero1,4

1
Centro Atómico Constituyentes, Comisión
Nacional de Energía Atómica, Buenos Aires,
Argentina A wide range of analytical techniques has been used to study an Egyptian funerary
2
Facultad de Filosofía y Letras, Universidad de
mask of the Ptolemaic period (305‐30 BC). Secondary electron (SE) and back‐
Buenos Aires, Buenos Aires, Argentina
3
Departamento de Humanidades, Universidad
scattering (BS) images, recorded by a scanning electron microscope (SEM), provided
Pedagógica Nacional, Buenos Aires, Argentina a detailed representation of the metallurgical techniques used to construct the gilded
4
Escuela de Ciencia y Tecnología, Universidad mask. It is confirmed, that the golden leaf used to cover the mask is the product of an
Nacional de San Martín, Buenos Aires,
Argentina antique refinery practice, so called, cementation process of naturally occurring alloy
5
National Scientific and Technical Research of gold and silver, namely electrum. Complementary results of SEM‐electron disper-
Council (CONICET), Buenos Aires, Argentina
sion spectroscopy (EDS) and electron probe microanalysis (EPMA)–wavelength dis-
Correspondence persion spectroscopy (WDS) provided chemical compositions of the golden leaf as
F. S. Gard, Centro Atómico Constituyentes,
well as in the plaster base of the mask. X‐ray photoemission spectroscopy (XPS)
Comisión Nacional de Energía Atómica.
Buenos Aires, Argentina. revealed the presence of Au, Ag, Si, S, Cl, Ca, and N, in addition to O and C. Relative
Email: fsgard01@gmail.com
concentration of Au/Ag at the surface has been measured by XPS to be 70% to 30%.
XPS depth profiling verified silver‐enrichment at the surface, as ratio of gold to silver
is measured to be 80% to 20% at the depth of 15 nm. XPS chemical mapping images
of gold and silver confirmed a rather inhomogeneous character of Au/Ag relative con-
centration at the surface. The main diffraction peaks in the X‐ray diffraction (XRD)
spectrum coincide with diffraction peaks of pure gold, silver metals, and magnesium
calcite Mg0.03Ca0.97CO3. Whereas, Raman spectroscopy results implied the existence
of Ag2S, a tarnishing compound, on the golden area of the mask.

K E Y W OR D S

cementation process, Egyptian funerary mask, EPMA‐WDS, Raman spectroscopy, SEM‐EDS, XPS,
XRD

1 | I N T RO D U CT I O N
In ancient Egypt, gold, in addition to its materialistic and symbolic
value, had an important role in the religious ceremonies, particularly
in the funerary ritual. The limited number of the golden artifacts dis-
covered form the Egyptian sites cannot give a real picture of the
importance of the usage of gold objects during the funerary practices.
The Egyptian tombs have been excavated and looted since ancient
times, and much precious metal were melted.1 It is suggested that
ancient Egypt was both the largest consumer and producer of gold
in the ancient world.2,3
A few studies4-9 present an overview and a historical perspective
on the use of gold and precious metals in the ancient world in general,
and in ancient Egypt in particular. However, systematic studies

Surf Interface Anal. 2019;1–17. wileyonlinelibrary.com/journal/sia © 2019 John Wiley & Sons, Ltd. 1
2 GARD
overarching the ancient Egyptian golden artifacts are rare, albeit the
great importance of the usage of gold in the ancient Egypt, which is
widely represented as golden artifacts in the archaeological collections
worldwide. Whereas multi‐analytical studies on the golden and gilded
Egyptian artifacts are scant,10 the European golden artifacts have been
studied heavily, using a wide range of analytical techniques, see Sandu
et al.11 and references therein.
In the current study, we present a comprehensive analytical study of
a gilded Egyptian funerary mask from the Ptolemaic period. To the best
of our knowledge, such a detailed study on an Egyptian funerary mask
has not been reported in literature. Nevertheless, similar studies on dif-
ferent types of archaeological artifacts from different cultures and
epochs have been reported. For instance, Ingo et al.12,13 report on the
European golden brooches dating back to the 16th and 17th centuries.
Similar to our study, a wide range of surface science techniques was
used to study gilded archaeological objects. Interestingly, the authors
demonstrated the importance of multi‐analytical approach in order to
study archaeological artifacts. Whereas, Bastidas et al.14 reports on
the analytical study on a pre‐Columbian funeral golden mask.
The primary objective of the current study is to present a panoramic
view on the chemical composition and the metallurgical structure of
the golden leaf used to gilt the mask. We consider that the combined
data acquired by X‐ray photoemission spectroscopy (XPS), X‐ray
ET AL.
diffraction (XRD), Raman spectroscopy, scanning electron microscope
(SEM)–electron dispersion spectroscopy (EDS), and electron probe
microanalysis (EPMA)–wavelength dispersion spectroscopy (WDS)
techniques have given us a significant insight to the antique technique
of gold refinery and gilding process in the ancient Egypt. The second
objective of the current manuscript is to present a comparative case
study on the application of the most common noninvasive analytical
techniques, mentioned above, to investigate a particular archaeological
object. Throughout the length of the paper, mainly in the results
section, we will highlight the limitations and shortcomings or advan-
tages of a particular analytical technique in comparison with the others.
2 | MATERIALS AND SAMPLES
The Museum of La Plata (Museo de La Plata), capital of Buenos Aires
Province, Argentina keeps a little Egyptian collection that includes,
among other objects, a small defective mummy.15 It was considered
to be the mummy of a toddler due to its size, see Figure 1A. However,
in 1980, the computerized tomography (CT) scans reveled that it was
only the head of a not‐mummified adult, whose body was recon-
structed with linen bandages and plaster. The funerary mask was sadly
vandalized, under unknown circumstances, in the 1960s and was
FIGURE 1 A, Photo of the small cartonnage,
preserved at the Museum of La Plata, B,
uncovered part of the mask, C, one of the
fragments, which is used to perform the
analytical studies, and D, cross‐section of a
small fragment, which its optical microscopy
(OM) and scanning electron microscope (SEM)
images are shown in the inset
GARD ET AL.
broken into pieces. New CT studies carried out in 2010 have added
new valuable information to the previous study.16 The characteristics
of the cartonnage17 allow us to locate it, historically, in the Ptolemaic
period (305‐30 BC), probably third century BC. Here, we will not elab-
orate on the archaeological aspects of the cartonnage, as it has already
been presented elsewhere,18,19 and it is beyond the scope of the cur-
rent presentation. Figure 1B shows part of the mask, which has been
assembled from the uncovered broken fragments. It should be empha-
sized that the mask is not reconstructed; neither any adhesive mate-
rials nor any kind of cleaning agents had been used. The base of the
mask is made of linen and covered with plaster, which is then deco-
rated with gold leaves. The face features such as eyes and eyebrows
are painted in black. A green/blue pigment is used to decorate the
upper part of the head and hair. Figure 1C shows a small fragment
of the mask, which among the other smaller fragments, had been used
to perform our analytical studies. It contains a small golden area and
green and black pigments stripes. Panel D shows an optical micros-
copy (OM) dark field image of a small fragment cross‐section, which
of the OM and SEM images are shown inset. The small fragment
was vertically embedded in a resin overnight, then it was polished with
different SiC papers increasing until 1500 grit. The thickness of the
golden leaf is estimated to be in the range 2 to 3 μm.
3 EXPERIMENTAL METHODS AND
| ple area and starting θ angle.
INSTRUMENTATION
3.1 | Scanning electron microscopy
All SEM‐EDS measurements, back‐scattering (BS), and secondary elec-
tron (SE) imaging in the current study were performed using a FEI
Quanta 200 SEM in high vacuum mode. The system is equipped,
among other detectors, with Everhardt‐Thornley (SED) and Solid‐State
(BSD) detectors. Low‐vacuum capability enabled us to perform charge
free imaging and analysis of the mask fragments (nonconductive sam-
ples) without any prior sample preparation. It was very important to
avoid depositing any kind of conducting layer to overcome the charg-
ing effect during the measurement, as we would like to preserve the
native characteristic of sample.
3.2 | Electron probe microanalysis
Electron beam microanalysis was carried out in a CAMECA SXFiveFE.
The system is equipped with a series of large size crystal spectrome-
ters (large lithium fluoride [LLiF], large pentaerythitol [LPET], large
thallium acid pthalate [LTAP], and large pseudo crystals) and with a
high‐quality electron column optimized for microanalysis and high‐
resolution SEM images with the choice of W or LaB6 sources. Four
WDSs (three vertical and one inclined) and one EDS are installed in
the system. A coaxial optical microscope with continuous zoom and
a built‐in Z auto focus device can be used to monitor the region of
interest on the sample before performing the analysis.
3
3.3 | X‐ray photoemission spectroscopy
XPS analysis was carried out in a PHI 5000 VersaProbeII. The base
pressure in the analysis chamber was in the lower range of 10−10 Torr.
A monochromatic aluminum Kα X‐ray source was used to probe the
sample. Unless it is reported otherwise below, for the major part of
the XPS measurement, the X‐ray source condition was set to
100 μm spot size, 25 W, and 15 kV. An argon‐etched, polished, fine‐
grained silver sample was earlier used to measure resolution of the
system. The full width at half maximum (FWHM) of the 3d5/2 peak
of the silver was measured to be 0.49 eV. All the survey scans were
collected under the following conditions: 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 scans, the PE was
set to be 23.7 eV and the step size changed to 0.1 eV. Spectra were
analyzed using CasaXPS software version 2.3.18.
3.4 | X‐ray diffraction
XRD data were collected on a Panalytical Empyrean X‐ray diffractom-
eter equipped with Bragg–Brentano HD optics, a sealed tube copper
X‐ray source (λ = 1.54178 Å), soller slits on both the incident and
receiving optics sides, and a PixCel3D Medipix detector. Antiscatter
slits and divergence slits as well as masks were chosen based on sam-
3.5 | Raman spectroscopy
Raman microscopy analyses were performed on a LabRAM HR Raman
system (Horiba Jobin Yvon), equipped with two monochromator grat-
ings and a charge‐coupled device detector (CCD). An 800 g/mm grat-
ing and 100 μm aperture resulted in a 1.5cm−1 spectral resolution. A
He‐Ne laser line at 514.5 nm was used as excitation source. Laser
power was adjusted in order to avoid overheating on the sample
(around 5 mW). The spectrograph is coupled to an imaging microscope
with 10×, 50×, and 100× magnifications. Typically, the laser spot on
the sample was about 10 and 3 μm diameter for a 10× and 50× mag-
nification, respectively. An advantage of the microscopic facility is the
possibility of analyzing different regions and pigments separately.
4 | EXPERIMENTAL RESULTS
4.1 | SEM with energy dispersive spectroscopy
SEM images were collected by recording both SE and BS electron
(BSE) modes at accelerating voltage of 20 kV. As we wished to pre-
serve the unique character of the samples, we have not deposited
any kind of conducting thin film over the samples. The SEM system
was operated at low vacuum mode, which SEM measurements of
uncoated samples were possible. Figure 2A and 2B shows SEM
images, obtained from the golden part of the mask, with a magnifica-
tion of 1300× and 20 000×, respectively. The images reveal inclusion
4 GARD ET AL.

FIGURE 2 Secondary electron (SE) images of the golden part of the mask: A, magnification 1300× and B, magnification 20 000×, two small voids
and domain boundaries are indicated by arrows

of small particles of different sizes on the golden leaf, which are indi-
cated by arrows in panel A. In a recent study,20 the authors reported
observation of quartz particles on the surface of golden Egyptian arti-
facts. In the current study, the EDS spectrum (not shown here for sim-
plicity) obtained from those particle confirms detection of Si in much
larger amount in comparison with the EDS spectrum off those parti-
cles. The origin of those particles is not clear. However, since the gold
was usually mined in the mineralized quartz veins in the deserts of
Ancient Egypt and Nubian Sudan, we propose that they could be
remains of the quartz contamination. They could also be just sand con-
tamination or residues of purification process of the natural gold ore.
Careful inspection of the images reveals some other interesting
features in the golden leaf. A series of voids (black spots) of different
sizes are also observed. A magnified SEM image (panel B) shows two
of them of dimension smaller than 5 μm, which are also indicated by
arrows. It is also seen that the gold leaf consists of a mosaic of
domains, whose boundaries are also indicated in the image. Similar
features had also been reported in literature.10,21 Their origin has been
related to the parting process of gold from silver in Electrum, namely FIGURE 3 Back‐scattering (BS) image (magnification 1200 M) from
cementation process,10 see below in discussion section. A BSE image the golden part of the mask. Three separate position used to
(magnification 1200×) from the golden part of the mask is shown in perform scanning electron microscope (SEM)–electron dispersion
spectroscopy (EDS) are indicated by A, B, and C
Figure 3. In addition to the micro‐voids in the gold layer, which have
also been observed in the SE images, one can observe that the golden
film of the mask consists of at least two overlapping layers. The top of gold. A small amount of Mg and relatively large quantity of Ca are
layer has been ripped apart and rolled up at different locations. believed to be related directly to the plaster in the form of magnesium
EDS semi‐quantitative analysis has been performed at 20 kV beam calcite. Quartz or sand impurity is manifested by detection of Si in the
voltage, and the spectra have been analyzed by Edax Genesis Apollo X sample. Finally, detection of Na and Cl is particularly significant, as
software. Figure 4 shows a typical EDS spectrum collected from a those elements can be considered as additional indication of the
large area of the golden leaf. The relative concentration of the cementation process of gold ore, where salt is the main ingredient of
detected elements is listed in Table 1. It is worth pointing out that the recipe, see below in the discussion section. However, it should
the weight percent (Wt%) of the elements in Table 1 cannot be consid- be underlined that we cannot discard the possibility of detection of
ered as the absolute concentration values of those elements in the those elements simply due to the existence of natron and chlorine in
sample, as the EDS results have not been verified by any standard the burial soil.
samples. In addition to Au and Ag, we have detected Al and Fe, which In order to obtain a statistical evaluation of the relative concentra-
can be attributed to the impurities in the plaster base of the mask, or tion of gold to silver, we have obtained EDS spectra from three differ-
to material residues, which have been used for the refinement process ent points on the sample, indicated by letters A‐C in Figure 3. For
GARD ET AL. 5

simplicity, those spectra have not been shown here. The relative con-
centrations of gold to silver measured at these three points are listed
in Table 2.
Based on the results in the Table 2, we have estimated the relative
concentration of Au to Ag, in average, to be equal to 95% to 5%. Since
Au and Ag are relatively heavy elements, and considering as well the
morphology of the surface, we estimate an error of 2% in our
measurements.

4.2 | EPMA‐WDS

In order to achieve better energy resolution of the detected elements

and to confirm the relative concentration of gold to silver obtained by
SEM‐EDS technique, we have also performed WDS on the golden
FIGURE 4 Overall scanning electron microscope (SEM)–electron leaf. The most valuable analytical advantages of WDS technique over
dispersion spectroscopy (EDS) spectrum acquired from the golden EDS technique are its high energy resolution and lower detection limit
part of the mask of elements. Typical energy resolutions of WDS and EDS techniques,
depending on the elements, are about approximately 10 eV and
approximately 150 eV, respectively. For example, in the current study,
TABLE 1 Overall chemical composition acquired from the golden sulfur traces were detected in the mask using SEM technique. How-
part of the mask measure by SEM‐EDS ever, due to the relatively poor energy resolution of SEM technique,
Elements Wt % At % the major peak of sulfur is overlapping with that of gold. The major
electron transition line of sulfur, namely Kα, interferes with the transi-
C 16.20 44.08
tion electron line Mα of gold, see Table 3.
O 14.76 29.76
Figure 5A and 5B show WDS spectra collected by a LPET and an
Na 0.30 0.42
LLiF spectrometer, respectively. The spectra were analyzed with Peak
Mg 0.27 0.36 Sight software. The Au Mα and Au Mβ peaks can be identified in panel
Al 0.58 0.70 A and are well‐separated from S Kα peak. Furthermore, the corre-
Si 3.31 3.81 sponding electron transition lines for Ag, Ca, and Si are also indicted
S 0.73 0.73 in the spectrum. In panel B, in addition to the other electron transition
Cl 0.33 0.30 lines of Au and Ag, Fe Kα can be identified. Iron has also been detected

Ag 1.21 0.36
by EDS‐SEM technique. The relative concentration of gold to silver
based on the WDS results yields a value of 96.3% to 3.7%, which is
Ca 13.98 11.25
within the uncertainty range of the EDS measurements
Fe 0.75 0.43
Figure 6A and 6B show an OM image of the sample and a BSE
Au 47.57 7.79
image obtained in situ in the chamber of EPMA system, respectively.
Abbreviations: EDS, electron dispersion spectroscopy; SEM, scanning elec- The BSE image was collected with an accelerating voltage of 20 keV
tron microscope. and electron current of 40 nA. In contrast to the SEM system, where
low vacuum operation mode was possible, the EPMA can only be
operated at high vacuum mode. Therefore, we had complications with
the charging effect that caused alteration of the images obtained by
TABLE 2 Relative concentration of gold and silver measured at dif-
EPMA technique. To overcome this problem, we have analyzed the
ferent points on the sample
sample close to its edge in order to avoid exposure of the entire sam-
Location Elements Wt % At % ple to the electron beam. As a result, a fraction of the electron flux
A Au 98.10 96.58 was dissipated through the conducting tape beneath the sample.
Ag 1.90 3.42 However, we have not been able to acquire high‐resolution images,
B Au 97.25 95.10
Ag 2.75 4.90 TABLE 3 Major electron transition lines of Au and S
C Au 97.41 95.37
Elements Kα1 Kβ1 Lα1 Lβ1 Mα1 Mβ1
Ag 2.59 4.63
Sulfur (S) 2.309 2.465 N/A N/A N/A N/A
Overall Au 96.17 93.23
Ag 3.83 7.77 Gold (Au) 68.806 77.982 9.713 11.443 2.123 2.203
6 GARD
FIGURE 5 Wavelength dispersion spectroscopy (WDS) scans from
the golden part of the mask; A, large pentaerythitol (LPET)
diffractometer; B, large lithium fluoride (LLiF) diffractometer
as the charging effect distorted severely the images. Nevertheless,
major features such as the regions, where the gold leaf has been
peeled off the plaster, can be seen in the image. Larger voids in the
gold leaf related to the gold refinery process are also clearly seen. Fur-
thermore, we have performed chemical mapping of gold and silver
from the same region of the sample. The total distribution of gold
and silver in the golden leaf has been detected and are shown in
Figure 6C and 6D, respectively. It is interesting to notice that there
are some regions in the sample where silver is concentrated in larger
amount with respect to other regions. They are indicated by arrows
in the image. This suggests that the relative concentration of Au to
Ag is not homogenous in the gold leaf
4.3 | XPS survey scan
The elemental composition of the sample was measured by SEM tech-
nique and was confirmed by WDS technique. However, it would be
interesting to identify the oxidation states of those elements. There-
fore, we used XPS technique to probe the sample. Figure 7 shows a
ET AL.
typical XPS survey scan acquired from the golden part of the mask.
The spectrum was obtained after of 2 minute of 2 keV Ar+‐ions
sputtering, in order to remove major part of the native contamination
in the form of oxygen and carbon. The main transition line peaks are
indicated in the spectrum. In addition to the transition lines corre-
sponding to oxygen and carbon, we have detected silver, gold, cal-
cium, nitrogen, sulfur, and chlorine.
4.4 | XPS high‐resolution scan
XPS high‐resolution (HR XPS) scans of the major chemical elements
are acquired from the golden area of the mask. They are presented
and discussed in details in the current section. The X‐ray source was
adjusted to 200 μm spot size, 50 W, and 15 kV in order to increase
the resolution and amplify the details of the spectra. Shirley back-
ground type was applied to remove the contribution of the inelastic
electron scattering for all HR XPS scans.
Figure 8A and 8B shows the HR XPS scans of C 1s and O 1s tran-
sition lines from the golden part of the mask, respectively. The HR XPS
core level transition line of C 1s clearly consists of four components,
which were fitted with Gaussian Lorentzian GL (30) line shapes. The
most dominant one, centered at 284.8 eV, is assigned to an adventi-
tious carbon (AdC) peak of (C─C/C─H). The binding energy values
of the other components in the spectrum are listed in Table 4 and
are compared with the published values in a previous study.22 The C
1s component at 290 eV is assigned to carbonate, as the main compo-
nent in any form of calcite used in the plaster base of the mask
In Figure 8B, four components were identified for HR XPS scan of
O 1s region. GL(30) line shapes were used to fit the peaks. The main
peak, centered at the binding energy of (531.1 ± 0.1) eV, is ascribed
to the contribution of the oxygen atoms in the calcium carbonate,23
whereas the second largest component at (532.5 ± 0.1) eV is attrib-
uted to the organic species (O═C or C─O) on the sample. In addition
to the above‐mentioned components, two rather smaller peaks are
identified at the binding energies of (528.8 ± 0.1) eV and
(530.1 ± 0.1) eV, respectively.24 They are attributed to the oxygen
atoms in the most stable silver oxides, namely AgO and Ag2O, in
agreement with the HR XPS results of the Ag 3d region acquired from
the golden part of the mask, see below.
Figure 9A shows HR XPS spectrum of Ca 2p core level transition
line, obtained from the golden part of the mask, which is rather com-
plex, due to Au 4d3/2 transition line interference. Contribution of cal-
cium is atributed to the calcite in the base of the mask. It is fitted with
a doublet of GL(30) line shape with an energy difference of 3.5 eV and
intensity ratio of 2:1, corresponding to Ca 2p3/2 and Ca 2 p1/2 compo-
nents. They are centered at (347.7 ± 0.1) eV and (351.2 ± 0.1) eV,
respectively. The contribution of the gold atoms in the sample is iden-
tified as an asymmetric single peak for Au 4 d3/2 at (353.0 ± 0.1) eV.
Finally, a relatively strong satellite for Ca at (355.5 ± 0.1) eV can also
be identified in the spectrum
HR XPS spectrum of S 2s transition line from the golden part of the
mask is shown in Figure 9B. A GL(30) line shape component is fitted at
GARD ET AL.
FIGURE 6 A, Optical microscopy photo, and B, back‐scattering image, C, chemical mapping of gold, and D, silver acquired in situ in electron
probe microanalysis (EPMA) chamber. Regions with more concentration of silver are indicated obtained by arrows
binding energy of (226.3 ± 0.1) eV, which is attributed to the silver sul-
fide (Ag2S). HR XPS scan from Cl 2p region is shown in Figure 9C. A
doublet, with an energy difference of 1.6 eV were identified for Cl
2p3/2 at (198.8 ± 0.1) eV and for Cl 2p1/2 at (200.4 ± 0.1), respectively.
They are assigned to the doublet of Cl 2p photoelectron lines for silver
chloride compound, AgCl.25
Figure 10 shows HR XPS spectrum from Ag 3d region. The spec-
trum is fitted with an asymmetric line shape for both for metallic Ag
and Ag oxide components. Identification and quantification of the oxi-
dation states of the transition metal in the XPS spectra comes with a
large uncertainty. Deconvolution of the XPS peaks corresponding to
FIGURE 7 X‐ray photoemission spectroscopy (XPS) survey scan
acquired from the golden part of the mask
7
Ag 4d region, in particular, is not straightforward. A comprehensive
survey of the reported binding energy values in Wagner et al.26
reveals a diverse binding energies for Ag 3d5/2 for metallic silver,
Ag(0), and its stables oxides, AgO, Ag2O, and for silver sulfide Ag2S.
The energy values presented in Wagner et al26 fall between binding
energies of 367.3 eV and 368.5 eV, a narrow range of 1.2 eV. This is
certainly a direct consequence of the charging effect, which is associ-
ated with the insulating samples during the XPS measurements. The
widespread practice to overcome this problem is using electron flood
gun to compensate the charging problem. However, traditional elec-
tron flood gun charge neutralization is not effective in neutralizing
the localized positive charge created by the X‐ray beam, because the
samples static charge interferes with the low energy electron beam.
In the current study, we have used PHI's patented dual beam charge
neutralization method, which uses a low energy 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, a reference point was necessary to calibrate the XPS spec-
tra. The dominant peak of AdC, namely (C─C/C─H), is the most pre-
ferred reference point to calibrate the binding energy scale.27 We
have calibrated all the XPS spectra using the position of C 1s transition
line at 284.8 eV.
In the current study, we interpreted and fitted the Ag 4d spectrum
based on the study reported by Ferraria et al.28 and Kaushik.25 The
authors presented a comprehensive discussion over the binding ener-
gies of a pure metallic silver standard sample and its various com-
pound including AgO and Ag2O in Ref. 28 and HCl and H2S in Ref.
8 GARD ET AL.

FIGURE 8 X‐ray photoemission spectroscopy high‐resolution (HR

XPS) spectrum from C 1s and O 1s regions collected from the
golden area of the mask

TABLE 4 Adventitious carbon (AdC) line components obtained from

the golden area of the mask in comparison with the published values
in a previous study22

Component Current study (eV_ Previous study22 (eV)

(C─C/C─H) 284.8 284.8

C─O─C) 286.2 ~286.0
O─C═O 288.5 ~288.5
Carbonate 290 288–290

25. In contrast to the other studies such as in Ref. 29, where AgO is
considered to be Silver peroxide, the authors, in Ref. 28 have argued
the presence of Ag(I) and Ag(III) in AgO with 1:1 (v/v) stoichiometry,
as it is predicted by magnetic properties of AgO and other studies.30,31 FIGURE 9 X‐ray photoemission spectroscopy high‐resolution (HR
Assuming the existence of the most stable and common silver oxides, XPS) spectrum from Ca 2p, S 2s, and Cl 2p regions collected from
the golden area of the mask
namely AgO, and Ag2O, together with metallic silver, and Ag2S and
AgCl (in accordance with HR XPS results from the S 2 s and Cl 2p
regions), we have performed an empirical fitting process using
GARD ET AL. 9

in Ag2S and AgCl compounds. Considering only the Ag 3d HR XPS

FIGURE 10 X‐ray photoemission spectroscopy high‐resolution
(HR XPS) scan from Ag 3d region collected from the golden part of
the mask
proposed components for Ag(0), AgO, and Ag2O in Ref. 28 and for
(0)
Ag2S and AgCl as in Ref. 25 The main transition lines of Ag
(0)
and Ag 3d3/2 are fitted with a doublet with an energy separation
of 6.0 eV and a fixed intensity ratio of 3:2, due to spin‐orbit splitting,
at binding energies of (368.2 ± 0.1) eV and (374.2 ± 0.1) eV,
respectively.
Subsequently, the absolute values of the binding energies of AgO
and Ag2O components were constrained within a range of ±0.3 eV
of the suggested values in Ref. 28 This method has culminated in a
well‐fitted envelope to the raw data. The binding energy values for
Ag 3d5/2 components are compared with the reported values of silver
oxides in Ref. 28 in Table 5. The binding energies of Ag 3d5/2 transition
line for Ag(0) for pure silver and Ag(I) component in AgO,28 in Ag2S, and
25
in AgCl are reported to be 368.2 eV and 368.2 eV, and 368.3 eV
respectively. Therefore, we have assigned the major component of
Ag 3d5/2 centered at (368.2 ± 0.1) eV to Ag(0) and Ag(I) in AgO and
spectrum in order to distinguish silver corrosion product, would not
be very informative because AgO, Ag2S, AgCl, and metallic Ag compo-
nents do not exhibit appreciable binding energy shifts. It is crucial to
analyze the HR XPS of Ag 3d regions along with those of O 1s, Cl
2p, and S 2 s regions. In Ref. 28 the authors assigned two peaks
located at 369.4 eV and 371.4 eV as the satellites of Ag(III) in AgO.
We have detected an additional component centered at 370.6 eV. It
is assigned as one of the Ag(III) satellites, namely Ag(III) sat2, as its
energy difference between the previous satellite and the following is
the same, which was measured to be (1.4 ± 0.1) eV. The extra satellite
peak detected in the current study could be due to the high resolution
of the energy spectrometer or it could be related to Ag2S or/and AgCl
compounds. The origin of these compounds can be related to the cor-
rosion of silver in contact with air or with the burial soil. Silver‐
contained archaeological objects can undergo two types of corrosion
process,32 so‐called tarnishing or mineralization. Tarnishing is mainly
referred to the corrosion due to exposure to air pollutants in the atmo-
sphere. For the major cases, the main component of the tarnish prod-
3d5/2 uct was identified as Ag2S.33 H2S and organic sulfur compounds, such
as carbonyl sulfide (OCS), so‐called reduced sulfur gases, are the main
components in the air, which generate this process.34-36 In some cases
chlorargyrite (AgCl) has also been identified as a major tarnishing com-
ponent,37,38 which can be related to the exposure of chloride‐
containing airborne particles for example from scattering of marine
salts.39
Mineralization is a corrosion process which affect objects buried
under chloride‐rich soil or to those which remain under water (mainly
saltwater). The important characteristic of this type of corrosion is the
long time of contact to adverse environment. Regardless of the harm-
ful species in the soil, it is important to underline its severe corrosivity
effects in the present of oxygen and water. The object, in the absent
of air and in the contact with pH neutral soil, will undergo so‐called
biodegradation.40 Formation of silver sulfide has also been reported

TABLE 5 Major components of transition line of Ag 3 d5/2 collected from the golden part of the mask in comparison with the values in Ferraria
et al.28

BE [eV] Ag Ag2O AgO AgO + Ag2O Assignments

a
Ag 3d5/2 368.3 Ag(0)
368.6 368.7 Ag(I) in Ag2O
367.8 367.6 Ag(III) in AgO
368.4 368.2 Ag(I) in AgO
369.4 369.2 Ag(III) sat
371.5 371.4 Ag(III) sat
b
Ag 3d5/2 368.2 Ag(0) /Ag(I) in AgO and Ag2S
368.7 Ag(I) in Ag2O
367.6 Ag(III)
369.3 Ag(III) sat1
370.6 Ag(III) sat2
371.8 Ag(III) sat3
a
From Ferraria et al.28
b
From the current study.
10
due to sulfide‐reducing bacteria.41 However, this kind of corrosion is
not usual, as it happens only at considerable high relative humidity
and at the presence of abundant sulfur. It is very unlikely that our
object has been in such environment considering arid and dry condi-
tion in the Egyptian desert.
HR XPS spectrum of Au 4f region obtained from the golden part of
the mask is shown in Figure 11. The curve fitting for the main compo-
nents is done using an asymmetric doublet, with an energy difference
of 3.7 eV, centered at (84.1 ± 0.1) eV and (87.8 ± 0.1) eV, with a fixed
intensity ratio of 4:3 corresponding to Au(0) 4f7/2 and Au(0) 4f5/2,
respectively.
Subsequently, the relative concentration of gold to silver at the
surface was estimated using the ratio of the peak area of Au 4f7/2 to
the Ag 3d5/2. The contribution of the Ag(III) satellites were excluded
in this calculation. We have evaluated that the relative composition
of the gold to silver is in the order of 70% to 30%. This surprising high
value of silver concentration at the surface, measured by XPS, will be
discussed and compared with the results obtained by SEM below in
the discussion section.
4.5 | XPS depth profiling
The evolution of the relative concentration of gold to silver in the
most top layer of the golden part of the mask was analyzed by a shal-
low XPS depth profiling. The sample was first exposed to Ar+ ions of
2 keV for 2 minute in order to sputter the contamination layer, native
oxygen, and carbon in the form of organic or inorganic. A moderate
exposure time of 1 minute has been chosen to minimize the erosion
of the actual gold layer due to Ar+ ions bombardment. The energy of
the Ar+‐ions was then reduced to 1 keV, with a raster size of
2 × 2 mm, a depth profile was acquired with the steps of 1‐minute
intervals. A relative lower energy of the Ar+ was chosen in order to
achieve a moderate erosion rate. The erosion rate of the Ar+‐ions
was pre‐calibrated using a Si standard sample with a 100‐nm thick
FIGURE 11 High resolution X‐ray photoemission spectroscopy
(XPS) scan from au 4f region collected from the golden part of the
mask
GARD ET AL.
FIGURE 12 X‐ray photoemission spectroscopy (XPS) depth profiling
(15 nm) of the golden part of the mask
SiO2 overgrown layer. The erosion rate of Ar+ ions with an energy
of 1 keV and raster size of 2 × 2 mm was estimate to be (1.5 ± 0.2)
nm/min. The ratio of the atomic concentration of Au to Ag was esti-
mated by analyzing the main transition lines of Au 4f7/2 and Ag 4f5/2
from each spectrum and is plotted as a function of depth in
Figure 12. The relative concentration of Au to Ag at the surface, after
removing the top layer of the contamination, was estimated to be 68%
to 32%. The atomic concentration of gold is increased, whereas the
atomic concentration of silver is decreased as a function of depth.
The relative concentration fraction of Au/Ag is hovering around 80%
to 20% in the range of 10 to 15 nm depth.
4.6 | XPS chemical mapping
In order to investigate lateral distribution of gold and silver on the sur-
face, XPS elemental maps for Au and Ag were generated over an area
of 1 × 1 mm from two arbitrary different locations (points 1 and 2) on
the mask. The X‐ray beam diameter was set to 100 μm and dual beam
charge neutralization was activated. The spectra were collected at
high speed using a multichannel detector to capture a single element
spectrum in one event.
Figure 13A and 13B show the lateral variation of gold and silver at
a certain location on the sample (point 1), whereas panels C and D
show the lateral variation of Au and Ag at different location (point
2), respectively. Comparison between the chemical mapping of gold
and silver at point 1 and 2 demonstrates a rather inhomogeneous ratio
of Au/Ag concentration at the surface, which is more severe at point
2. Visual assessment of panels C and D shows that lateral concentra-
tion of gold at the center part of panel C is the highest, whereas in
panel D, the surface concentration for silver is highest at the right
hand side of the image. However, at point 1, the pattern formed by
the silver concentration at the surface (panel B) is roughly similar to
the pattern shaped by the gold concentration (panel A). This indicates
a rather patchy character, in terms of relative concentration of Au to
Ag, at the surface. This is a convolution of two major factors: first,
GARD ET AL.
FIGURE 13 X‐ray photoemission spectroscopy (XPS) chemical mapping of Au and Ag from two different locations on the golden part of the
mask
irregular surface morphology of the sample, and second, different level
of surface segregation of the Au‐Ag alloy. Surface segregation process
will be discussed in more details below in the discussion section.
4.7 | Raman spectroscopy results
It is well known that one of the most important limitations of Raman
spectroscopy technique is that it cannot be used for pure metals and
alloys. Nevertheless, Raman spectroscopy results, acquired from the
golden leaf in the current study, revealed an interesting feature in
the spectrum. Figure 14A presents a typical Raman spectrum collected
from the golden part of the mask. The spectrum was analyzed using
CrystalSleuth software. The background and the cosmic ray events
(CREs) have been removed. It is possible to distinguish three Raman
−1
shifts at 124, 206, and 245 cm . However, the range of 300 to
650 cm−1 is characterized by a broad band. It should be emphasized
that because of the low level of counts and peak to noise ratio, these
values come with a significant uncertainty. Nevertheless, they are cer-
tainly reproducible, since our results from different parts of the mask
exhibit similar features with some negligible variation of the above‐
11
mentioned values. In the light of the HR XPS results and our extensive
search in the literature on the Raman spectra reported in previous
studies42-44 including the RRUFF database,45 the most likely candidate
among the silver products, which has similar Raman spectrum to the
one shown in Figure 14A is silver sulfide (Ag2S). It is worth mentioning
that due to photosensitivity of the Ag2S, like most of the silver com-
pounds, the number of the available literature containing credible
Raman spectra is limited. It is well known that the photosensitive
materials can decompose to the secondary chemical compounds due
to the photo‐decomposition effect of laser.46 Therefore, it is essential
to reduce the laser power using high‐density filters, which on the
other hand may reduce the signal‐to‐noise ratio. This means, achieving
a high‐resolution spectrum may not be possible. To collect a Raman
spectrum with a high intensity and a less noisy baseline, one has to
balance between the laser power and a short exposure time46 for
the photosensitive compounds.
For the purpose of comparison with our results, Raman spectrum of
acanthite mineral (Ag2S), RRUFF ID: (R070578), which was collected by
a Thermo Almega XR 532 nm @ 10% of 150 mW is shown in Figure 14
B. The Raman spectrum of the acanthite standard sample is character-
ized by three intense Raman shifts in the range of 100 to 300 cm−1. In
12 GARD ET AL.

FIGURE 14 Raman spectrum acquired from the golden part of the
mask, (A). Raman spectrum of Ag2S, downloaded from RRUFF
database, (ID: R070578), (B).
modes (no bending modes) of the molecule. The sharp peak at 152 cm
−1
is assigned to Ag lattice vibrational modes, whereas the other peaks
at 198 cm−1 and 240 cm−1 are attributed to the Ag‐S‐Ag symmetric
stretching modes.
The resemblance between three initial Raman shifts in our mea-
surements from the mask and those of acanthite is striking. Acanthite
mineral is one of the main silver ores used to extract silver. However,
it is also observed as the most common corrosion product of silver due
to the weathering of the silvery objects.
Red discoloration of Egyptian gold objects has been reported
before, which has been examined by Xray diffraction,EDS, and other
methods.47 The authors have concluded that these colorations are
most often associated with tarnish films, in which the predominant
species are a silver‐gold‐sulfide, in the form of AgAuS or Ag3AuS2,
rather than Ag2S, depending on the silver contents of the objects.
Another famous example is the gilded red mask on the mummy of
Ukhhotep. A. Lucas in Carter' study48 also describes that the surface
of many golden objects found in the tomb of Tut‐Ankh‐Amen were
characterized with patches or sometimes the whole surface with a
red color. Bastidas et al14 have also reported on formation of a reddish
tarnish film on a pre‐Columbian funeral golden mask, after 3 years,
even in a climate‐controlled environment. The authors identified the
film as the tarnish products of Ag2S and Ag2SO4. In the current study,
we have not observed any confirmation of the existence of silver‐gold
sulfide or silver sulfate tarnish over the mask. It can be related to low
level of silver concentration in the mask.
The OM photos of the sample provide confirmation of red tarnish
on the surface. Figure 15A and 15B show photos acquired from the
sample by an optical microscope from two different locations. The
photos present noticeable different colors of the gold film. Some ran-
dom patches of brownish red color are seen on the surface. Taking to
account the XPS and Raman spectroscopy results, we suggest that the
discoloring of the gold leaf of the mask is the product of environmen-
tal exposure to the sulfur ions.
4.8 | XRD results

addition to the initial three Raman shifts, a relatively wide band in the
range of approximately 300 to 650 cm−1 can be identified. The possible
Raman shifts in the spectrum of acanthite and the ones obtained from
golden part of the mask are identified and are listed in Table 6.
Ag2S is a triatomic and nonlinear molecule; therefore, the Raman
shifts in the spectrum can only be related to the symmetric stretching
In addition to the most common surface science techniques men-
tioned above, XRD technique was also used to study the fragments.
XRD data were collected in the range of 10° ≤ 2θ ≤ 70°, in the step
mode (0.0260° per step), using the Panalytical Data Collector soft-
ware.49 The total acquisition time was 15 minutes. Figure 16 shows
a typical XRD spectrum obtained from the golden part of the sample.

TABLE 6 Proposed assignment for the main Raman shifts acquired from the golden leaf in comparison with acanthite

Molecular and Acanthite Molecular and

Mask Vibrational Mode Mineral Vibrational Mode

Band Shifts/cm−1 Band Shift (cm−1)

100‐300 124 Ag lattice vibrational mode 100–300 152 Ag lattice vibrational mode
206 Ag‐S stretching modes 198 Ag‐S stretching modes
245 240
GARD ET AL. 13

FIGURE 15 Optical microscopy images acquired from two different positions on the sample

by XPS technique due to the detection limit of the measurements,

whereas it was certainly detected by EDS‐SEM.
The other drawback of XRD technique is manifested by the lack of
detection of any kind of corrosion products, which was detected by
XPS. For instance, the most common silver corrosion products such
as Ag2O, AgO, have not been detected by XRD. It is certainly due to
small the amount of those products in the sample, which is below
the detection limit of the XRD technique. It is also worth mentioning
that the major diffraction peaks of those products also overlap with
those of silver and gold. As a result, it would be difficult to detect
those corrosion products solely by XRD technique, whereas existence
of a small amount of those species was indisputably detected by XPS
measurements.

TABLE 7 Major X‐ray diffraction peaks of pure gold and silver and
magnesium calcite
FIGURE 16 X‐ray diffraction pattern acquired from the golden area
of the mask Element/Compound Crystallographic Direction 2 θ°

H k l
Gold 1 1 1 38.185
Search/Match phase identification was performed using the 2 0 0 44.393
HighScore50 software of Panalytical against the ICCD PDF2+ and 2 2 0 64.578
ICDD PDF4/Organics database.51 Major peaks of the relevant ele- Silver 1 1 1 38.262
ments are indicated according to powder diffraction database. The 2 0 0 44.473
2 2 0 64.713
most intense peaks in the spectrum coincide with those of pure gold
and silver metals. The other features in the pattern are identified as Mg0.03Ca0.97CO3 1 0 4 29.50
1 1 0 36.056
the corresponding XRD peaks of Mg0.03Ca0.97CO3, which is certainly
1 1 3 39.517
the main ingredient of the plaster base of the mask. A comprehensive 2 0 2 43.269
list of the diffraction peaks of pure gold and silver metals and magne- 0 2 4 47.250
sium calcite is compiled in Table 7. Comparison between the main dif- 0 1 8 47.703
1 1 6 48.669
fraction peaks of gold and silver reveals that it would be very difficult
2 1 1 56.707
to identify and distinguish the peaks of silver from gold in general. 1 2 2 57.549
Therefore, without any pre‐knowledge of the elemental composition 1 0 10 58.336
of the mask, obtained by other techniques such as XPS or SEM, detec- 2 1 4 60.841
2 0 8 61.222
tion of small quantity of silver in the golden mask is almost impossible,
1 1 9 61.617
solely based on the results of XRD. However, detection of 1 2 5 63.242
Mg0.03Ca0.97CO3 by XRD confirms that Ca and CO3 species 3 0 0 64.829
detected by XPS technique are attributed to magnesium calcite in 0 0 12 65.930
2 1 7 69.418
theplaster base. It should be underlined that Mg was not detected
14 GARD ET AL.

5 | DISCUSSION conditions.60 The other important factor, which can accelerate surface
segregation in a bimetallic alloy, is the presence of water molecules, as

5.1 | Gold‐silver alloy surface segregation moisture in the air.61

In all binary alloys, one element tends to be present at the surface in a
greater concentration than in the bulk due to surface segregation pro-
cess. For the surface of any bulk bimetallic alloy, the large volume
inside can act as a semi‐infinite source for one atom and a sink for
the other. 52
The concept of surface segregation of the binary metal
alloys in general 53,54
and Au‐Ag alloy in particular 55,56
is well‐known
and has been studied. This phenomena, for instance, has also been
reported for Cu‐Ni alloy of the Argentine coins, where Ni surface
enrichment has been observed. 57
Surface segregation in the bimetallic alloys depends on a few fac-
tors, which the most important ones are the thermodynamics aspects
of the process, such as surface‐free energy, and the oxide formation
enthalpy of the metals. The process of surface segregation was theo-
retically studied by Gibbs,58 and one of the significant results of this
study is Gibbs adsorption isotherm equation (GAIE), as given below.
 
∂σ
ΓA ¼ − ;
∂μA T;P
where ΓA is basically the “surface excess” of component A (in an A‐B
binary system), σ is the surface free energy (surface tension for liq-
uids), and μA is the chemical potential of A. GAIE implies that a constit-
uent element of an alloy, which can lower the surface free energy, will
be segregated to the surface and, consequently, the concentration of
that atom increases at the surface region.
Enthalpy and Gibbs free energy of gold and silver, AgCl, Ag2S,
Ag2O, and AgO are listed in Table 8.59 Enthalpy and Gibbs free energy
values for pure silver and gold are null. Therefore, according to the
GAIE equation, one should not expect that surface segregation of gold
and silver atoms of Au‐Ag alloy could be occurred, as surface enrich-
ment of any of those metals would not be energetically favorable over
the other corrosion products. This fact would be true if the alloy was
in the vacuum and in the absence of surface adsorbates. The condition
is more complex in the case of Au‐Ag alloy of the mask in the ambient
environment due to chemisorptions‐induced surface segregation. The
presence of oxygen‐containing adsorbates such as CO2, CO, and pre-
dominantly oxygen itself in the air will radically change the
The role of the oxygen chemisorptions‐induced segregation is
probably more important than that of the other gases in the air. The
oxygen in the air preferentially pulls one component to the surface
and thus enriches the surface in that component. Negative enthalpy
values for the formation of Ag2O (−31.0452 kJ/mol) and AgO
(−24.2672 kJ/mol) indicate that Ag oxides are preferentially formed
at the surface. Basically, oxygen literally “drags” the Ag atoms to the
surface and enriches the surface with silver. The enthalpy values for
the formation of AgCl and Ag2S are −127.06808 kJ/mol and
−29.41352 kJ/mol, respectively. That means the chemical reaction
between silver and sulfur and chlorine ions in the atmosphere, can also
contribute to the surface segregation process.
The Gibbs free energies for AgCl, Ag2S, Ag2O, and AgO are
−109.804896 kJ/mol, −29.41352 kJ/mol, −11.21312 kJ/mol, and
27.6144 kJ/mol, respectively. Negative values for the Gibbs free
energy of those components (except for AgO) is yet another indica-
tion of Ag preferentially segregation to the surface of the mask.
Therefore, in light of the thermodynamic argument above, we
propose that the overall surface segregation of the bimetallic alloy
Au‐Ag of the mask, happened along the time, and the surface is con-
sequently enriched with silver. Taking into account the surface seg-
regation, it would be clear the origin of the inconsistency of the
Au/Ag relative concentration measurements by SEM and by XPS.
Due to the extreme surface sensitivity of XPS measurements, the
ratio of Au/Ag of 70% to 30% is originated on the top most layer
(10 nm) of the mask. It is an indication of silver‐enrichment of the
surface. However, under usual working conditions, SEM‐EDS permits
the investigation of materials to a depth of order of 1 mg/cm2, ie, in
order of 1 μm depth for a material of average density. Therefore,
the relative concentration of Au to Ag of 95% to 5% is rather the

TABLE 8 Enthalpy and Gibbs free energy values for the metallic
species detected by HR‐XPS scan of the gold‐alloy of the mask

Formula Enthalpy [kJ/Mol] Gibbs Free Energy [kJ/Mol]

Au(0) 0 0
Ag(0) 0 0
AgCl −127.06808 −109.804896
Ag2S −29.41352 −39.45512
Ag2O −31.04528 −11.21312
FIGURE 17 Ternary diagram Au/Ag/Cu of some ancient Egyptian
AgO −24.2672 27.6144
golden objects
GARD ET AL.
bulk concentration of those elements in the mask. The relative
concentration of gold to silver in the mask is compared with the
available data of some Egyptian golden objects in Figure 17. It is
noteworthy to mention that a small amount of copper (less than
1%), along with silver and gold, has been detected in a various
20
Egyptian golden objects. The authors used a range of certified
gold‐silvercopper standard samples, in order to perform elemental
10
quantification. Klemm et al presented relative concentration of
Au/Ag/Cu of some well‐known Egyptian golden objects in a ternary
plot. In Figure 17, we have reproduced the diagram along with data
of the mask in the current investigation. It should be emphasized
that, in the current study, copper was not detected either by XPS
or by SEM.
5.2 | Gold parting (refinement)
There is no doubt about the skills of the ancient Egyptians for mining
and processing of the precious metals.1 Gold refinery in general is con-
sidered to be practiced by the ancient Egyptian gold‐smelters and
goldsmiths in about 500 BC. Nevertheless, chemical analysis results
from various golden objects as far as 2000 BC indicate that the degree
of purity of the gold in those objects is superior to that of natural
occurring gold. This could be an indication that the gold refinery
62
started much earlier than 500 BC. The date of commencing gold
refinery in the ancient Egypt is still up to discussion, due to insufficient
scientific facts and historical sources.
The first documented evidence of gold refinery in the ancient
Egypt is given by Diodorus Siculus in his Bibliotheca Historica III
14.63 He recounts the description of Agatharchides of Cidus, a Greek
geographer, who had visited Egypt in the second century BC and
witnessed the entire process of gold mining and purification. Notton64
reproduced part of that travel journal, as it is translated by
Oldfather,65 which contains an instruction of gold refinery technique,
so called cementation process.
The basic idea of the cementation process was to place the
impure gold along with salt and bricks or ceramic dust inside a sealed
clay pot and to heat the pot below the melting temperature of the
gold. Metallic impurities in the gold, particularly silver, which had
not been separated in the preceding process of cupellation, would
volatilized as AgCl (g) and absorbed to the brick dust or to the interior
wall of the clay pot.
Notton64 repeated this process under a modern condition. The
author placed gold alloy sheet containing both copper and silver with
salt and brick dust inside a crucible and heated at 800°C for 5 days. He
could raise the initial gold content of 37.5% to a final value of 93%.
The procedure removed all the copper impurity and a large amount
of the silver.
The natural occurring gold ore is called electrum (an alloy of gold
and silver), which was mined in the quartz mine. The ratio of the
gold to silver was varying and was dependent on the mines. In
Klemm et al,10 figure 4.1 presents an interesting graph of the ratio
of the concentration of Au/Ag from different Electrum mining sites.
15
It shows a tendency of decreasing silver contents of 30% in north
(Egyptian deposits) to 8% in south (Sudanese deposits). The ratio
of gold to silver of some golden Egyptian artifacts is above 90% to
10%. It shows that the ancient Egyptian craftsmen were able to sep-
arate silver from gold through the cementation process. Schorsch1
has also pointed out to the linguistic evidence that suggest gold,
silver, and electrum were only gradually distinguished as separate
words.
The other direct evidence of the cementation process, based upon
analytical studies on an antique Egyptian artifact, is presented by
Klemm et al.10 Their extensive SEM studies on gold fragments of
Akhenaten sarcophagus (~1350 BC) showed that the fragments were
forged of several porous gold layers. The authors have also observed
holes between 1 and 3 μm in diameter and grain boundary in the gold
foil. These features in the gold foil are explained as the physical conse-
quences of out‐diffusion of the AgCl gas during the cementation pro-
cess. Similar features have also been observed in the Sardian (Lydia)
66
gold foil from about 550 BC.
SE and BS images acquired by SEM and EPMA techniques repre-
sented in the current work show clearly similar physical evidences of
the cementation process such as micro‐holes and grain boundaries in
the gold layer of the mask. In addition to the SE and BS images, we
can corroborate this hypothesis by taking to account the results of
SEM‐EDS and XPS. A small amount of chlorine and sodium was
detected by SEM‐EDS, which could be the residue of the salt, the
main ingredient of the cementation process. The XPS survey scan
shows also a clear Cl‐peak related to AgCl. It should be emphasized
that detection of silver chloride due to exposure to Cl‐‐ions in the air
or in the soil cannot be discarded as we have discussed above.
6 | CO NC LUSIO N
The combined use of wide range of nondestructive analytical tech-
niques such as XRD, XPS, SEM–EDX, EPMA‐WDS, and Raman spec-
troscopy provided an excellent insight into the surface chemical
composition and microstructure of the golden part the funerary Egyp-
tian mask. The results can in general be used to explain the ancient
manufacturing of gilded Egyptian funerary masks.
SEM imaging (BS‐images, SE‐images) provided a direct evidence of
the ancient gold refinery method, namely cementation process, as
small voids and domain boundaries were observed in the gold film.
These are the consequence of parting silver from gold in electrum,
where the silver is out diffused of Electrum as AgCl gas through the
voids and the domain boundaries. SEM‐EDS and EPMA‐WDS con-
firmed that the relative atomic concentration of Au/Ag in the bulk is
95%/5%, with an error of 2%. Chemical composition of the mask mon-
itored by SEM‐EDS, in addition to the elements identified by XPS,
detected small traces of Mg, Al, Na, and, Fe.
XPS survey scan provided detailed results on the elemental com-
position of the mask. In addition to the principle elements such as O,
C, Au, and Ag, other chemical elements which were detected are S,
Ca, N, and Cl. HR XPS scan of the Au 4f region did not show any
16
evidence of existence any other gold compounds rather than the
metallic gold, whereas HR‐XPS scan from the Ag 3d region indicates
the presence of not only metallic silver, but also its stable oxides in
form of AgO, Ag2O, AgCl, and Ag2S. HR‐XPS O 1s, S 2s, and Cl 2p
regions results collaborate very well with that of the Ag 3d region.
The ratio of Au/Ag concentration at the top most layer of the surface
is measured to be 70%/30%. The difference between the Au/Ag con-
centration obtained by SEM and XPS is due to silver enrichment of the
surface. XPS depth profiling confirmed silver enrichment at the sur-
face, due to surface segregation of Au‐Ag alloy. It demonstrated that
the relative concentration of Au/Ag is changed to 80%/20% at a
depth of 15 nm. The major peaks in the XRD pattern coincide very
well with the diffraction pattern of pure gold and silver; furthermore,
it confirmed that the main mineral used in the plaster base of the mask
is Mg0.3Ca0.97CO3.
Silver sulfide (Ag2S) was detected by Raman spectroscopy on the
golden area of the mask, whereas the spectrum collected from the
plaster section of the mask confirmed that calcite is the major com-
pound used to construct the base of the mask, in accordance with
the XRD results. Overall results of the analytical techniques used to
study the golden part of the mask have shed light on the ancient
manufacturing method of Egyptian funerary masks from Ptolemaic
period. Details of the ancient gilding process were presented. High‐
resolution SEM images show that at least part of the golden layer of
the mask consists of two gold leaves.
Finally, we would like to emphasize that it is essential to study the
archaeological objects using a broad range of complementary analyti-
cal techniques in order to achieve complete information.
ACKNOWLEDGMENTS
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 provid-
ing access to the valuable Egyptian collection of the museum. Mr
Cristian Oubiña, Mr Lucas S. Pascual, and Mr Jesus Pachado are
acknowledged for technical assistance for XRD and WDS measure-
ments. Dr A.G. Grunfeld and Dr G. Duffo are acknowledged for proof-
reading the manuscript. Finally, Dr. D. Vega is acknowledged for
discussion and interpretation of XRD results.
ORCID
Faramarz Sahra Gard https://orcid.org/0000-0001-5332-2570
RE FE R ENC E S
1. Schorsch D. Precious‐metal polychromy in Egypt in the time of
Tutankhamun. J Egypt Archaeol. 2001;87(1):55‐71.
2. Lucas A, Harris JR. Ancient Egyptian Materials and Industries. New York:
Dover Publications; 1999 [1962]:224‐235.
3. Nicholson P, Shaw I. Ancient Egyptian Materials and Technology.
Cambridge university Press; 2000:161‐166.
4. Uda M, Yoshimura S, Ishizaki A, Yamashita D, Sakuraba Y.
Tutankhamun's golden mask investigated with XRDF. Int J PIXE.
2007;17:65‐76.
GARD ET AL.
5. Craddock PT. Historical survey of gold refining. Surface treatments and
refining worldwide, and in Europe prior to AD 1500. In: Ramage A,
Craddock PT, eds. King Croesus' Gold. London: British Museum Press;
2000:27‐53.
6. Troalen LG, Tate J, Guerra MF. Goldwork in ancient Egypt: workshop
practices at Qurneh in the 2nd Intermediate Period. J Archaeol Sci.
2014;50:219‐226.
7. Oddy WA. Gilding: an outline of the technological history of the plating
of gold on to silver or copper in the Old World. Endeavour.
1990;15:29‐33.
8. Oddy WA. Gilding through the ages. Gold Bull. 1981;14:75‐79.
9. Hatchfield P. Ancient Egyptian gilding methods. In: Gilded Wood:
Conservation and History. Madison (Connecticut): Sound View Press.
10. Klemm R., Klemm D., Gold and gold mining in ancient Egypt and Nubia,
Natural Science in Archaeology, 21, https://doi.org/10.1007/978‐3‐
642‐22508‐6_2, Berlin: © Springer‐Verlag Berlin Heidelberg 2013.
11. Sandu ICA, de Sá MH, Pereira MC. Ancient ‘gilded’ art objects from
European cultural heritage: a review on different scales of characteri-
zation. Surf Interface Anal. 2011;43:1134‐1151.
12. Ingo GM, Guida G, Angelini E, Di Carlo G, Mezzi A, Padeletti G. Ancient
mercury‐based plating methods: combined use of surface analytical
techniques for the study of manufacturing process and degradation
phenomena. Acc Chem Res. 2013;46(11):2365‐2375.
13. Ingo GM, Riccucci C, Pascucci M, et al. Combined use of FE‐SEM+EDS,
ToF‐SIMS, XPS, XRD and OM for the study of ancient gilded artifacts.
Appl Surf Sci. 2018;446:168‐176.
14. Bastidas DM, Cano E, González AG, et al. An XPS study of tarnishing of
a gold mask from a pre‐Columbian culture. Corros Sci.
2008;50(6):1785‐1788.
15. Daneri A. Las piezas egipcias del Museo de La Plata (Primera Parte).
Revista del Instituto de Historia Antigua Oriental. 1978;4:129‐134.
16. Santos DM, Daizo MB, Pucciarelli H, et al. Prácticas funerarias del
Antiguo Egipto. Museo. 2011;21:46‐55.
17. Schweitzer A. L'évolution stylistique et iconographique des parures de
cartonnage d'Akhmîm du début de l'époque ptolémaïque à l'époque
romaine. Bulletin de l'Institut français d'Archéologie Orientale.
1998;98:322‐352.
18. Santos DM, Pucciarelli HM, Daizo MB, Abramzon F, Lesyk S. Las
momias egipcias del Museo de La Plata. Estudios Recientes. Aegyptus
Antiqua. 2012;13:52‐55.
19. Daizo M. B., Pucciarelli H. M., Santos D. M., Abramzon F., Lesyk S., A
defective mummy at the museo de La Plata in Buenos, 7th World Con-
gress on Mummy Studies, University of San Diego, San Diego, (2011)
20. Tissot T, Troalen LG, Manso M, et al. A muti‐analytical approach to
gold in ancient Egypt: studies on provenance and corrosion.
Spectrochimica Acta B. 2015;108:75‐82.
21. Murr A Geologische Kartierung der Goldlagerstättenbezirke Fatira und
Dungash in der Ostwüste Ägyptens, Masterthesis, (1994), LMU Uni-
versity, Munich
22. http://xpssimplified.com/elements/carbon.php
23. Demri B, Muster D. XPS study of some calcium compounds. J Mater
Process Technol. 1995;55(3‐4):311‐314.
24. https://xpssimplified.com/elements/oxygen.php
25. Kaushik VK. XPS core level spectra and Auger parameters for some sil-
ver compounds. J Electron Spectrosc Relat Phenom.
1991;56(3):273‐277.
26. Wagner C. D., Naumkin A.V., Kraut‐vass A., Allison J.W., Powell C.J.,
Rumble Jr. J.R., NIST Standard Reference Database 20, Version 3.4
(web version), http://srdata.nist.gov/xps/.
GARD ET AL.
27. Swift P. Adventitious carbon—the panacea for energy referencing. Surf
Interface Anal. 1982;4(2):47‐51.
28. Ferraria AM, Carapeto AP, Botelho de Rego AM. X‐ray photoelectron
spectroscopy: silver salts revisited. Vacuum. 2012;86:1988‐1991.
29. Schultz EJ. Fully exploiting the potential of the periodic table through
pattern recognition. Chem Educ. 2005;82:1649‐1657.
30. Yvon K, Bezinge A, Tissot P, Fischer P. Structure and magnetic proper-
ties of tetragonal silver(I,III) oxide, AgO. J Solid State Chem.
1986;65:225‐230.
31. Jansen M, Fischer PJ. Eine neue Darstellungsmethode für monoklines
Silber (I,III)‐oxid (AgO). Einkristallzüchtung und Röntgenstrukturanalyse.
J Less‐Common Met. 1988;137:123‐131.
32. Costa V. The deterioration of silver alloys and some aspects of their
conservation. Stud Conserv. 2001;46(sup1 1.18):18‐34.
33. Sharma RC, Chang YA. The Ag‐S system. Bull Alloy Phase Diagr.
1986;7(3):263‐269.
34. Graedel TE, Franey JP, Gualtieri GJ, Kammlott GW, Malm DL. On the
mechanism of silver and copper sulfidation by atmospheric H2S and
COS. Corros Sci. 1985;25:1163‐1180.
35. Franey JP, Kammlott GW, Graedel TE. The corrosion of silver by atmo-
spheric sulfurous gases. Corros Sci. 1985;25(2):133‐143.
36. Graedel TE. Corrosion mechanism for silver exposed to the atmo-
sphere. J Electrochem Soc. 1992;139(7):1963‐1970.
37. Fukuda Y, Fukushima T, Sulaiman A, et al. Indoor corrosion of copper
and silver exposed in Japan and ASEAN countries. J Electrochem Soc.
1991;138:1238‐1243.
38. Bouquet S, Bodin C, Fiaud C. Influence relative des composes soufres
et chlores sur le ternissement de l'argent en milieu atmospherique.
Comptes Rendus de I'Academie des Sciences Pans. 1993;316:459‐464.
39. Rice DW, Peterson P, Rigby EB, Phipps PBP, Cappell RJ, Tremoureux
R. Atmospheric corrosion of copper and silver. J Electrochem Soc.
1981;128:275‐284.
40. Stambolov T. The Corrosion and Conservation of Metallic Antiquities and
Works of Art. Amsterdam: Central research laboratory for objects of art
and science; 1985:153‐167.
41. McNeil MB. Microbiologically influenced corrosion of silver in the
marine environment. In: Dowling NJ, Mittelman MW, Danko JC, eds.
Microbially Influenced Corrosion and Biodeterioration. Knoxville,
Tennessee: University of Tenneesee; 1990:8.17‐8.21.
42. Socrates G. Infrared and Raman Characteristic Group Frequencies: Tables
and Charts/George Socrates. 3rd ed. Hoboken (New Jersey): Wiley;
2001.
43. Nakamoto K. Infrared and Raman Spectra of Inorganic and Coordination
Compounds. Part A: Theory and Applications in Inorganic Chemistry. 6th
ed. Hoboken (New Jersey): Wiley; 2009.
44. Wang CB, Deo G, Wachs IE. Interaction of polycrystalline silver with
oxygen, water, carbon dioxide, ethylene, and methanol: in situ Raman
and catalytic studies. J Phys Chem B. 1999;103(27):5645‐5656.
45. Lafuente B, Downs RT, Yang H, Stone N. The power of databases: the
RRUFF project. In: Armbruster T, Danisi RM, eds. Highlights in Mineral-
ogical Crystallography. Berlin, Germany: W. De Gruyter; 2015:1‐30.
46. Martina I, Wiesinger R, Jembrih‐Simbürger D, Schreiner M. Micro‐
Raman characterization of silver corrosion products: instrumental set
up and reference database. e‐PS. 2012;9:1‐8. ISSN: 1581–9280 web
edition
17
47. Frantz JH, Schorsch D. Egyptian red gold. Archeomaterals.
1990;4:133‐152.
48. Carter H. The Tomb of Tut‐Ankh‐Amen. 3rd New York: Copper Square
Publishers, Inc.; 1923‐33.
49. Data Collector, XRD Data Collection software, Version 5.3 (5.3.0.62),
PANalytical B.V., Almelo, The Netherlands, 2015.
50. HighScore, Version 4.5, PANalytical B.V., Almelo, The Netherlands,
2015.
51. ICDD (2018). PDF‐2+ 2012 and PDF4/Organics (Database), edited by
Dr. Soorya Kabekodu, International Centre for Diffraction Data,
Newtown Square, PA, USA.
52. Peng L, Ringe E, Van Duyne RP, Marks LD. Segregation in bimetallic
nanoparticles. Phys Chem Chem Phys. 2015) Online journal. https://
doi.org/10.1039/c5cp01492a
53. Barnett RN, Landman U, Cleveland CL. Surface segregation in simple
metal alloys: an electric theory. Phys Rev B. 1983;28(12):6647‐6658.
54. Burton JJ, Hyman E, Fedak DG. Surface segregation in alloys. J Catal.
1975;37:106‐113.
55. Manzhos RA, Krivenko AG, Doronin SV, Chba MA, Safonov VA. Sur-
face segregation of silver on Au‐Ag alloys to data of laser‐heating
induced temperature potential shifts, XPS and conventional electro-
chemical methods. J Electroanal Chem. 2013;704:175‐182.
56. Kim K, Kim KL, Lee SJ. Surface enrichment of Ag atoms in Au/Ag alloy
nanoparticles revealed by surface enhanced RAMAN scattering spec-
troscopy. Chem Phys Lett. 2005;403(1‐3):77‐82.
57. Gard FS, Duffo G, Bergamasco P, Forlerer E. X‐ray photoelectron spec-
troscopy on 1‐peso and 2‐pesos of the Argentine Republic. Appl Surf
Sci. 2018;436:720‐731.
58. J. W. Gibbs Collected Works. I New Haven, Connecticut: Yale University
Press; 1948:219‐233.
59. http://www.drjez.com/uco/ChemTools/
StandardThermodynamicValues.pdf
60. Tomanek D, Mukhjerjee S, Kumar V, Bennemann KH. Calculation of
chemisorption and absorption induced surface segregation. Surf Sci.
1982;114:11‐22.
61. Zhu B., Gao Y, Water‐induced bimetallic alloy surface segregation: A
first principle study, arXiv:1601.02346v1 (cond‐mat.mtrl‐sci)
62. James TGH. Gold technology in ancient Egypt: mastery of metal work-
ing methods. Gold Bull. 1972;5(2):38‐42.
63. Diodorus Bibliotheca Historica edidit Fr. Vogel, ed. tertia, vol. I,
Stutgardiae, in aedibus G B. Teubner, 1985 [1888], 283–284.
64. Notton JHF. Ancient Egyptian gold refining: a reproduction of early
techniques. Gold Bull. 1974;7:50‐56.
65. Siculus Diodorus, Book III, 12–14; C. H. Oldfather translation, Loeb
Classical Library, (1935), 115–123.
66. Geçkinli AE, Özbal H, Craddock PT, Meeks ND. Examination of the
Sardis gold and the replication experiments. In: Remage A, Craddock
P, eds. King Croesus' Gold, Excavations at Sardis and the History of Gold
Refining. London: British Mus. Press; 2000:184‐199.
How to cite this article: Gard FS, Daizo MB, Santos DM, et al.
Application of surface science techniques to study a gilded
Egyptian funerary mask: A multi‐analytical approach. Surf Inter-
face Anal. 2019;1–17. https://doi.org/10.1002/sia.6685