Spectrochimica Acta Part B 61 (2006) 1224 – 1228

www.elsevier.com/locate/sab

Characterization of pigments and colors used

in ancient Egyptian boat models ☆
Katja Hühnerfuβ a , Alex von Bohlen b,⁎, Dieter Kurth a
a
Archäologisches Institut, Universität Hamburg, Johnsallee 35, 20148 Hamburg, Germany
b
ISAS — Institute for Analytical Sciences, Bunsen-Kirchhoff-Str. 11, 44139 Dortmund, Germany
Received 23 December 2005; accepted 15 September 2006
Available online 7 November 2006

Abstract

The analyses of pigments originating from well dated ancient boat models found in Egyptian graves were used for characterization and for
dating tasks of unknown objects. A nearly destruction free sampling technique using cotton buds was applied for sampling these valuable artifacts
for a subsequent Total Reflection X-Ray Fluorescence Spectrometry (TXRF) analysis. Two relevant collections of Egyptian object of art were at
our disposal, one of the Ägyptisches Museum Berlin and the second of the British Museum London. Three groups of colors were studied, they
originate from white, red and blue/green paints, respectively. The results of the analyses performed on micro-amounts of paints (b 1 μg) show that
some artifacts were misclassified and belong to other epochs. Some others were retouched with modern colors. In general, it can be stated that
results obtained by Total Reflection X-Ray Fluorescence Spectrometry may dissipate some uncertainties when applying classical archaeological
dating methods.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Egyptology; TXRF; Total Reflection X-ray Fluorescence; Historical pigments; Burial boats models

1. Introduction
In ancient Egypt religion played an important role in daily
life. For this reason the graves have been laid out very carefully.
The most important items for the afterlife can be found in nearly
every grave: a sarcophagus, washabties, scarabs, jewelry, as
well as models and representation of the quotidian life like
bakeries or ships. Boats, added as models, were necessary for
the deceased to cross the big water “Nun” to meet the gods in
the afterlife. Most graves contained two of these small boats,
one has been fitted out for rowing, the other for sailing. As the
Nile was the most important landmark in ancient Egypt, it
played a central role in life. To navigate upstream a sailing boat
was needed and a rowing boat was used for floating down-
☆
This paper was presented at the 11th International Conference on Total
Reflection X-ray Fluorescence Spectrometry and Related Methods (TXRF-2005),
held in Budapest, Hungary, 18–22 September 2005, and is published in the special
issue of Spectrochimica Acta Part B, dedicated to that conference.
⁎ Corresponding author.
E-mail address: vonbohlen@isas.de (A. von Bohlen).
0584-8547/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.sab.2006.09.010
stream. On the Nile goods were transported, import and export
was traded, troupes took their routes, etc. Generally spoken, the
stream spent life and death.
The fact that so many graves contain boat models increased
the interest in an evaluation of the possible use of these objects
for dating tasks of unidentified finds. A catalogue of precisely
dated artifacts has been used to concept a list of classical dating
criteria [1] and for the classification of unassigned objects.
These criteria are based on the handicraft, the finishing, the used
colors and materials, etc. Sometimes the deduced conclusion
applying the set of criteria does not imply a verifiable result.
Independent methods have to be gone in view of new pos-
sibilities for archaeologists. A junction between Archaeology
and Natural Sciences led to impressive results in the past. An
interdisciplinary collaboration between Egyptology and Chem-
istry has been established and the classical methods of
archaeology were combined with modern analytical methods.
Among others, Total Reflection X-Ray Fluorescence Spectrom-
etry (TXRF) has been chosen for multielemental analysis.
Nowadays, one of the crucial tasks in archaeology concerns
the dating of objects. Many difficulties have to be taken into
 K. Hühnerfuβ et al. / Spectrochimica Acta Part B 61 (2006) 1224–1228 1225

account for solving the problem in a satisfactory way. The

difficulties arise on the one hand by i) the unknown provenance
of objects, ii) some objects consist only of some essential
fragments of the original piece and iii) on the other hand
unknown or not documented restorations might have been done.
These alterations and/or scarce information might give an
erroneous, even a false impression of an object and the classical
archaeological dating criteria fail. In some of these cases
chemical analyses will supply important additional and totally
independent information.
Especially, when combining a fast and reliable micro ana-
lytical method of Instrumental Analytical Chemistry, here
TXRF, with a gentle sampling procedure to collect only the
necessary μg amounts for the analysis, the analysis of unique Fig. 2. Object 1289, Ägyptisches Museum, Berlin. The detail shows some
artifacts become possible. In this way, valuable data of pig- incomplete colored figures of oarsmen. At the marked position a red sample was
taken for analysis. (For interpretation of the references to colour in this figure
ment's composition used in ancient Egypt can be expected. The legend, the reader is referred to the web version of this article.)
proposed combined procedure has been successfully applied for
the characterization of diverse historical pigments, inks, var-
nishes and glasses [2–4]. can be recognized without effort, a notably different grade of
In our particular case the Egyptian pigments should reveal conservation is given. These two objects characterize in a good
specific information about their elemental composition, even if way the diversity of the group of objects available for the
the colors have been vanished and discolored during the cen- classification via modern instrumental analyses. The positions
turies. Based on the analysis of 45 samples of different colors of sampled areas are marked on the pictures.
collected of 21 ancient burial boats stored in the Ägyptisches After sampling the loaded Q-tips were sent to the laboratory.
Museum Berlin (5 pieces) and in the British Museum London There the pigments were analyzed by means of TXRF. A simple
(16 pieces) the potential of the a.m. combined procedure of sample preparation is used for the deposition of the pigment
gentle sampling and microanalysis will be tested. The objects grains adhered to the cotton wool of the Q-tip. They have only
were classified by conventional methods of archaeology and to be knocked out or struck off the Q-tip onto a clean TXRF
were attributed to belong to the Old Kingdom (2686–2134 BC) sample carrier. The method has been described in detail else-
until the Middle Kingdom (2134–1782 BC). where (e.g. http://www.e-preservationscience.org and [5,6]),
therefore only the relevant parameter for these analyses will be
2. Experimental presented here. A Seifert and Co. (Ahensburg, Germany) Extra
II TXRF total reflection X-ray fluorescence device connected
Pigments were collected from boat models by gently wiping to an Oxford QX 2000 Analyser System (High Wycombe,
the surfaces by the aid of cotton buds (Q-tip). Only μg quantities
of material were removed and each Q-tip was deposited
immediately after sampling in a clean container. Two examples
of Egyptian boat models, a total view of object EA9524, British
Museum, London, and a detail of object 1289, Ägyptisches
Museum, Berlin, are shown in Figs. 1 and 2, respectively. As it

Fig. 1. Object EA9524 British Museum London. Some μg samples were taken at
the marked positions and analyzed by TXRF for characterization of the element
composition of pigments.
Fig. 3. TXRF spectrum of green color (sample L12, 3 Fig. 1) of object EA9524,
British Museum, London is shown. The insert gives the absolute amounts (ng)
of detected elements. The total mass of all detected elements is about 100 ng.
10 μl of a solution of Germanium containing 0.1 ng mL− 1 was added and the
solvent was evaporated before analysis. Ge was used as internal standard. (For
interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)
1226 K. Hühnerfuβ et al. / Spectrochimica Acta Part B 61 (2006) 1224–1228
England) was used. In order to detect as many elements as
possible, starting with Si (Z = 14), the samples were irradiated in
a first run with Mo–K radiation and in a second with W-
continuum radiation (max. ∼33 keV). The X-ray fluorescence
signals were integrated over a period of 200 s and stored for
later evaluation. A typical spectrum of a green pigment is
presented in Fig. 3.
3. Results and discussion
3.1. White pigments
The number of white colors used in ancient Egypt was
limited for long time to only two types of pigments, calcium
carbonate (CaCO3) obtained from the mineral Calcite, and
calcium sulphate (as CaSO4 or its hydrate CaSO4·2 H2O),
gypsum [7]. In 1974 Riederer discovered a further white
pigment, Huntite (CaCO3·3 MgCO3), used for ceramics in the
second Intermediate Period (1782–1570 BC) and in the New
Kingdom (1570–1080 BC) [8]. This pigment was found later
also on other objects, especially on wall paintings in Thebes,
New Kingdom. Systematic analyses of ceramic, wooden or
stone objects made by the Departments of Egyptian Art of the
Metropolitan Museum of Art, New York, showed that Huntite
was used only for wall paintings and ceramics, and very seldom
for wooden models except for painted sarcophagi [7]. The
Huntite could be associated with Magnesite or Dolomite depo-
sits near Abu Rawash in the north-western desert. Meanwhile,
Huntite could be proved on wall paintings from the Predynastic
Period (3150–2686 BC) up to the Late Period (525–380 BC)
with an improved purity of the pigment in the time of the New
Kingdom (1570–1080 BC) [8].
The elemental composition of white colors used for painting
boat models are shown in Fig. 4. The main constituents Ca, Ti,
Fe, Zn, and Pb and the sum of minor constituents K, Mn, Ni,
Cu, Zr, and Sn summarized as ‘rest’ are shown. No big dif-
ferences were detected in samples of the Ägypisches Museum,
Fig. 4. Element composition determined by TXRF of white colors used for
painting Egyptian boat models. The samples of the Ägyptisches Museum Berlin
are marked with B, those of the British Museum London with L.
Berlin and of those of the British Museum, London. One sample
from Berlin (B4.1) shows lower Ca content and higher amounts
of Fe and Zn in comparison to the other samples and one of
London (L14.3) has to be regarded as a modern restoration due
to its high Ti and Pb content. The pigment titanium white was
produced in a good quality and used for artists' colors first in
1938. In addition to the detection of modern restorations, no
valuable information in view of a possible use for rough dating
objects containing white paints can be obtained from the
determined element composition. Unfortunately, the most
important element for the differentiation of white pigments
used in ancient Egypt, namely Mg, is not detectable by TXRF.
That means that the use of Huntite cannot be distinguished from
chalk or gypsum.
3.2. Red pigments
The majority of red pigments used in ancient Egypt were
earthen based colors containing iron oxide. Especially, the
mineral Haematite (αFe2O3) was very common. It could be
applied on wood, on stone or as usual in some other cultures
even for skin-paintings [9,10]. These Fe-based colors are longer
lasting and light faster than others, and are sometimes of
astonishing brilliance.
In contrast to the Fe-based red pigments red colors based on
arsenic sulphide (αAs4S4, Realgar, of natural resource) vanish
more easily and even the color cannot be seen any more. A
careful interpretation of the analysis of arsenic compounds is
required due to the deterioration of Realgar, which changes with
light as well as in darkness into Pararealgar (γAs4S4). The
results are discoloration into a yellow/orange color. Another
possible reaction with oxygen leads to the white As2O3. These
changes are accompanied with an expansion of crystallites
lattice and the colored layers might flake off. Additionally, the
identification of Realgar and Pararealgar may be hindered if the
yellow Orpiment (As2S3) was also used. In their investigation
Middleton and Humphrey showed that Realgar was not used
before the New Kingdom (1570–1080 BC) [11]. This fact might
be a helpful hint when discussing the pigment characterization
of Egyptian ancient objects based on TXRF analysis.
Two further red pigments have been imported to Egypt by
the Romans: Red lead or Minium (Pb3O4) and Vermillion
(HgS). If these pigments are found on ancient objects, it can be
assumed to be produced not earlier than the first century B.C.
Red colors were sampled from 6 objects at Ägyptisches
Museum and from 10 objects stored at the British Museum. The
element pattern, shown in Fig. 5, was calculated from TXRF
analysis and is normalized for each individual sample to the sum
of all detected elements. In general the most predominant
elements are Ca, Fe, Zn, and Pb. Only one sample of the Berlin
collection and one of the London collection show significant
deviations and the differences are obvious (cf. Fig. 5).
Sample B5,1 (Berlin) shows the highest lead amount with
71.3% (Pb3O4) and sample L14,2 (London) contains only small
amounts of Ca (6.7%) and much more Fe (65.1%) and Zn
(26.3%) in comparison to the other samples. For painting the
‘normal’ samples fine grinded Haematite seems to be used, as
 K. Hühnerfuβ et al. / Spectrochimica Acta Part B 61 (2006) 1224–1228
was confirmed by micro Raman spectroscopy for sample B 4,2,
L 10,1 and L 13,1. In the case of sample B 5,1 either the
sampled object does not belong to the group of ancient objects
from the earlier kingdoms or it was restored without notification
of it. In the first case it has to be dated to be much younger than
the other pieces due to the use of a lead containing pigment. The
second possibility can be explained by the use of a non-
adequate lead containing pigment in an unknown restoration.
For the other sample deviating from the ‘normal’ group an Fe
rich pigment was used for painting the red line L14, 2 of the
border of the boat shown in Fig. 1. The same questions as before
concerning the genuineness, the dating of the object as well as
of an unknown restoration of the object are to be asked for. The
high Zn amount in the red color may originate from a Zn
containing white mixed to a dark Fe red to obtain the right hue
of the finally used red color.
3.3. Ochre, blue, green and black
The first approach presented in this work contains data of
only a small number of samples painted with other colors. These
data could not be used for serious characterization. In a current
investigation more objects will be sampled for a better
comparison and for the characterization of pigments in different
colors.
Nevertheless, some similarities could be observed for pig-
ments in blue and green colors. These pigments seem to be
obtained from minerals, e.g. Azurite, Malachite, etc. This
assumption originates from the element pattern of both blue and
green sampled colors. The main constituents detected in both
were Ca, Cu, and Fe. The total amount of these three elements
ranges between 82% and 96%. In Fig. 6 Ca, Fe and Cu as well
as the minor constituents summarized again under ‘rest’ (mix-
tures with varying amounts of K, Ti, Mn, Ni, As, Sr, Ba, Hg, and
Pb) are represented. The total amount of minor constituents
Fig. 5. Element pattern of red colors found after TXRF analyses. The main
elements were plotted while minor constituents, among others K, Ti, Mn, Ni, Sr,
Ba, and Pb, were summarized under ‘rest’. (For interpretation of the references
to colour in this figure legend, the reader is referred to the web version of this
article.)
1227
Fig. 6. Element pattern found after TXRF in blue and green colors. The small
number of analyzed samples shows similar elemental composition. The use of
powdered minerals like Malachite, Chrysochola and/or Azurite seem to be
possible, however, the use of Egyptian blue could not be confirmed (cf. text).
Samples marked g are painted with green and those marked with b are painted
with blue. (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)
does not exceed 18% relative to the sum of all detected
elements. The presence and existence of Egyptian Blue
(CaCuSi4O10) [12,13] on these objects is of high interest.
Even if the Si-signal is missing, the Cu: Ca ratio for the three
blue samples is 1:1.08, 1:2.14 and 1:15.4, respectively. The first
is close to the expected theoretical value for Egyptian Blue, the
other two may be regarded as mixtures of it with a Ca-con-
taining white pigment. However, an additional characterization
is indispensable. The use of Egyptian blue in the Middle
Kingdom is not mentioned in the literature and unfortunately, it
cannot be detected unambiguously by TXRF. The difficulty
concerns the poor sensitivity of TXRF for the detection of light
elements like silicon.
For a reliable characterization of the other colors of the
palette of Egyptian boat painters, a more sensitive method to the
analyses of element species – e.g. micro Raman spectroscopy or
micro X-ray diffraction – is required. These methods are
supposed to present adequate information to recognize
pigments like ochre, diverse blacks, or those containing Cu or
As, and thus to characterize blue and green colors.
4. Conclusions
From the point of view of archaeology, the most important
question is the efficient characterization of objects by means of
the data supplied by TXRF. In this context the versatility of the
method has already been proved for examinations of paintings
[2], medieval manuscripts [14] and for historical varnishes [15].
The micro analytical features of TXRF combined with a gentle
sampling procedure could be applied successfully to the
characterization of colors used for painting ancient Egyptian
boat models. Promising pigments contained in colors for such a
characterization are white, red, blue and possibly green. They
1228 K. Hühnerfuβ et al. / Spectrochimica Acta Part B 61 (2006) 1224–1228
can also be used for the detection of modern restorations, for the
characterization of the homogeneity of colored surfaces and for
detection of similarities of non-identified fragments. Based on
these experiences several other objects made of wood, e.g.
several sarcophagi, were allowed to be sampled in Berlin,
Ägyptisches Museum, and London, British Museum. The
element characterization of paints and pigments used for these
unique objects might give an additional hint to historians and
restorers.
Acknowledgement
The authors are much obliged to Dr. Peter Vandenabeele,
University of Ghent, Belgium, for performing micro Raman
analyses of some samples.
References
[1] K. Huehnerfuss, Datierungskriterien für altägyptische Bootsmodelle vom
Alten bis Mittleren Reich, MA thesis, 2003, Universität Hamburg.
[2] R. Klockenkämper, A. von Bohlen, L. Moens, Analysis of pigments and
inks on oil paintings and historical manuscripts using Total-Reflection X-
Ray Fluorescence Spectrometry, X-Ray Spectrom. 29 (2000) 119–129.
[3] R. Klockenkämper, A. von Bohlen, Survey of solid sampling suitable for
microanalysis by total reflection X-ray fluorescence spectrometry, J. Anal.
At. Spectrom. 14 (1999) 571–576.
[4] A. von Bohlen, Total reflection X-ray fluorescence spectrometry — A
versatile tool for ultra-micro analysis of objects of cultural heritage, e-PS-
http://www.e-preservationscience.org 1 (2000) 23–34.
[5] R. Klockenkämper, A. von Bohlen, L. Moens, W. Devos, Analytical
characterization of artists' pigments used in old and modern paintings by
total reflection X-ray fluorescence, Spectrochim. Acta Part B 48 (1993)
239–246.
[6] W. Devos, L. Moens, A. von Bohlen, R. Klockenkämper, Ultra micro
analysis of inorganic pigments and painted objects by total reflection X-ray
fluorescence analysis, Stud. Conserv. 40 (1995) 153–162.
[7] A. Heywood, The use of huntite as a white pigment in ancient Egypt, in:
W.V. Davies (Ed.), Colour and Painting in Ancient Egypt, Oxbow Books,
London, 2001, pp. 5–9.
[8] J. Riederer, Archäologie und Chemie-Einblicke in die Vergangenheit,
SMPK/Rathgen-Forschungslabor, Berlin, 1987.
[9] L. Green, Colour transformations of ancient Egyptian pigments, in: W.V.
Davies (Ed.), Colour and Painting in Ancient Egypt, Oxbow Books,
London, 2001, pp. 43–48.
[10] M. Uda, S. Sassa, S. Yoshimura, J. Kondo, M. Nakamura, Y. Ban, H.
Adachi, Yellow, red and blue pigments from ancient Egyptian palace
painted walls, NIM B 161–163 (2000) 758–761.
[11] A. Middleton, S. Humphrey, Pigments on some middle Kingdom coffins,
in: W.V. Davies (Ed.), Colour and Painting in Ancient Egypt, Oxbow
Books, London, 2001, pp. 10–16.
[12] H. Berke, Chemie im Altertum: Die Erfindung von blauen und purpurnen
Farbpigmenten, Angew. Chem. 14 (2002) 2595–2600.
[13] S. Bouherour, H. Berke, H.-G. Wiedemann, Ancient man-made copper
silicate pigments studied by Raman Microscopy. Art and Chemical
Sciences, CHIMIA 55 (11) (2001) 942–951.
[14] A. von Bohlen, P. Vandenabeele, M. De Reu, L. Moens, R. Klock-
enkämper, B. Dekeyzer, B. Cardon, Pigmente und Tinten in mittelalter-
lichen Handschriften-Eine andere Art zu lesen: extreme Mikroanalysen,
Restauro 2 (2003) 118–122.
[15] A. von Bohlen, F. Meyer, Arsen und Blei im Geigenlack-Zur Elementar-
analyse in kleinsten Lackproben, Restauro 7 (1996) 472–478.