JOURNAL OF RAMAN SPECTROSCOPY, VOL.

28, 91È94 (1997)

Non-Destructive In Situ IdentiÐcation of Cinnabar

on Ancient Chinese Manuscripts

Robin J. H. Clark* and Peter J. Gibbs

Christopher Ingold Laboratories, University College London, 20 Gordon Street, London WC1H 0AJ, UK

Kenneth R. Seddon
School of Chemistry, The QueenÏs University of Belfast, Stranmillis Road, Belfast BT9 5AG, UK

Nadezhda M. Brovenko and Yuri A. Petrosyan

Institute of Oriental Studies, Russian Academy of Sciences, St Petersburg, Russia

A standard, non-destructive, in situ analytical procedure has been developed to test the proposal that cinnabar
[ mercury(II) sulphide ] is the principal component of red inks and pigments on pre-tenth century Chinese manu-
scripts. Eight manuscript fragments with traces of red ink or pigmentation, and also one textile fragment, were
examined by Raman microscopy, Fourier transform near-infrared Raman spectroscopy and x-ray Ñuorescence
spectroscopy. Mercury(II) sulphide was unambiguously identiÐed on all four paper samples with red calligraphy
and on the textile fragment with red pigmentation. Mercury(II) sulphide was not detected on three paper fragments
with red legal or punctuation dots or on one paper fragment with a divine image hand-painted in red. The likely
identity of the non-cinnabar pigment is madder. ( 1997 by John Wiley & Sons, Ltd.

Fourier transform near-infrared (FT-NIR) Raman spec-

INTRODUCTION
The International Dunhuang Project (IDP)1 is a
unique collaboration of libraries, archives, museums and
universities dedicated to the conservation and cata-
loguing of the tens of thousands of pre-tenth century
Chinese manuscripts held in many collections through-
out the world. In connection with the IDP, and further
to our earlier reported studies of ancient Chinese dyed
papers,2h7 we have examined several ancient Chinese
manuscript fragments with traces of red ink and pig-
mentation and a textile fragment with red pigmentation.
The research was undertaken in order to develop a
standard, in situ, non-destructive analytical procedure
for libraries and museums, and to test the proposal8
that cinnabar [mercury(II) sulphide] is the principal
component of red ink and inorganic pigments in pre-
tenth century China. The red inorganic pigments that
are known to have been in use in antiquity, although
not necessarily in China, are listed in Table 19 and the
known red organic pigments from the same period are
listed in Table 2.9
The paper fragments were examined by x-ray Ñuores-
cence (XRF) spectroscopy, Raman microscopy and
* Author to whom correspondence should be addressed.
troscopy. XRF spectroscopy has been applied pre-
viously to the analysis of archaeological artefacts.10h13
It has been reported14 that Raman microscopy is the
analytical procedure which is most speciÐc, sensitive,
spatially reÐned and immune to interference for the in
situ analysis of inorganic pigments, and several papers
have been published on its use in this Ðeld.9,14h19 The
relatively new technique of FT-NIR Raman
spectroscopy20 has, as yet, had only limited application
in this area of arch~ometric analysis.9,21
EXPERIMENTAL
Eight paper fragments with traces of red ink or pigmen-
tation and one textile sample with red pigmentation
were generously lent by the Oriental Institute of the
Russian Academy of Sciences in St Petersburg. The
fragments were all uncovered at sites near Dunhuang,
Khara-hoto or Tujuk in north-west China at the turn of
the century. They were identiÐed visually by a codico-
logical expert and are described in Table 3. Two exam-
ples are reproduced in Plate 4.
All of the paper samples were Ðrst analysed by XRF
spectroscopy using a Siemens SRS 303 AS sequential
x-ray spectrophotometer with a 72-position sample

Table 1. Ancient red inorganic pigments9

Pigment Chemical name Formula

Cinnabara Mercury(II) sulphide HgS

Litharge Lead(II) oxide PbO
Realgar Arsenic(II) sulphide As S
4 4
Red lead Dilead(II) lead(IV) oxide Pb O
3 4
Red ochre Iron(III) oxide ½ clay ½ silica Fe O · H O ½ clay ½ silica
2 3 2
a Vermilion.

CCC 0377È0486/97/020091È04 °17.50 Received 22 May 1996

( 1997 by John Wiley & Sons, Ltd. Accepted 25 September 1996
92 R. J. H. CLARK ET AL .

Table 2. Ancient red organic pigments and dyes9

Pigment Formula composition Origin

Carmine Carminic acid C H O Scale insect, cochineal (Aztec)

22 20 2
Kermesic acid C H O Scale insect, kermes (antiquity)
16 10 8
Madder Alizarin C H O , Madder root (3000 BC)
14 8 4
purpurin C H O and
14 8 5
pseudopurpurin C H O
15 8 6

changer. The radiation source was a rhodium lamp with
wide-band excitation. Each sample was analysed for
traces of the metallic elements associated with known
ancient red pigments, i.e. mercury, lead, iron and arsenic
(see Table 1).
The samples analysed by XRF spectroscopy revealed
to have possible traces of an inorganic pigment were
then analysed by Raman microscopy. Single grains of
the red pigments were analysed in situ using an
Olympus BH-2 microscope with a 100] objective
coupled to a DILOR XÈY triple-grating spectrometer
with a photodiode-array detector. The light source was
a Coherent I301 krypton ion laser, operating at an exci-
tation wavelength of 647.1 nm and a power of 5 mW.
Finally, the samples analysed by Raman microscopy
were also studied by FT-NIR Raman spectroscopy
using a Nicolet 910 spectrometer. The light source was
an Nd : YAG laser operating at 1064 nm and a power
of 60 mW.
RESULTS AND DISCUSSION
High levels of mercury were detected on four paper
samples (BÈE) and on the textile sample (A) by XRF
spectroscopy. The spectra obtained, and the spectrum of
an HgS standard, are shown in Fig. 1. Samples FÈI
showed no evidence of the presence of the metals associ-
ated with known ancient red inorganic pigments (see
Table 1).
Samples AÈE were then studied by Raman micros-
copy, and the red ink or pigment was determined in
each case to be cinnabar. The spectra obtained are
shown in Fig. 2, together with the spectrum of a cinna-
bar standard.
Finally, samples AÈE were further studied by
FT-NIR Raman spectroscopy and the identity of the
red pigment was unambiguously conÐrmed to be cinna-
bar (see Fig. 3).
XRF spectroscopy is not an ideal tool for pigment
analysis as it is non-speciÐc and has poor spatial
resolution.14 In this instance, however, it does serve as
an e†ective Ðlter to determine whether a sample has any
trace of inorganic pigment before a Raman spectro-
scopic technique is applied. This is important for valu-
able artefacts, as the laser power required for detectable
Raman scattering from an in situ inorganic pigment
may damage a paper sample with only an organic
pigment.
Raman microscopy has already been established as
the most suitable technique for inorganic pigment
analysis,9,14 but FT-NIR Raman spectroscopy has also

Table 3. Ancient manuscript and textile data

Sample Description

A A finely woven silk, possibly a fragment of a scroll case, with red and maybe
green or black dye (catalogue number TM006)
B A paper fragment with Chinese script in black ink with red ink corrections.
The feathering of calligraphy is probably due to bad paper and not printing.
The paper is crude (catalogue number TM016)
C A paper fragment with one side of calligraphy solely in red ink. The paper is
crude and possibly dyed yellow (catalogue number TM036)
D Chinese scripted paper fragment with both red and black characters. The
paper is undyed and the calligraphy is freehand and particularly fine. It is
possibly a fragment of a secular document (catalogue number DU023)
E A paper fragment with heavy red and black calligraphy (possibly non-
Chinese). The paper has heavy laid (horizontal) lines and a heavy sand or dirt
deposit that has been affected by water and turned into a mud (catalogue
number TM018)
F Three paper fragments which are definitely related. There is single-sided
Chinese calligraphy (black ink) which shows through to the other side of the
thin paper. There is a hand-painted red divine image on the reverse (catalogue
number TM001)
G Chinese paper fragment with black script on both sides, one in a freer, less
formal hand. There is a faint red dot on one side (catalogue number
DU019)
H Chinese undyed paper fragment with black script. There are red dots on both
sides which may be legal or punctuation marks (catalogue number DU020)
I A rough Chinese paper fragment with crude black script on both sides. The
paper is coarse and degraded and there are red legal or punctuation dots on
both sides (catalogue number DU021)

( 1997 by John Wiley & Sons, Ltd. Journal of Raman Spectroscopy, Vol. 28, 91È94 (1997)
 IDENTIFICATION OF CINNABAR ON ANCIENT MANUSCRIPTS
Figure 1. XRF spectra (wide-band excitation, rhodium lamp) of
samples A–E and of an HgS standard.
Figure 2. Raman spectra (by Raman microscopy, excitation at
647.1 nm, power 5 mW) of the red ink or pigment on samples A–E
and of an HgS standard.
( 1997 by John Wiley & Sons, Ltd.
93
Figure 3. Raman spectra (by FT-NIR Raman spectroscopy, exci-
tation at 1064 nm, power 60 mW) of the red ink or pigment on
samples A–E and of an HgS standard.
been shown here to be very e†ective for the identiÐca-
tion of cinnabar on ancient papers. The FT-NIR
Raman spectrometer is the cheaper instrument, and it is
simpler to use for routine analysis. The higher power
used greatly reduces the collection time required to
obtain an adequate spectrum, and the interference from
Ñuorescence of the binder and support is much less of a
problem at the irradiating wavelength. However, the
e†ectiveness of FT-NIR Raman spectroscopy is limited
by the size of the sample compartment (which limits the
size of document that can be analysed), the spatial
resolution and, most important, the very real risk of
macroscopic damage to the document if the instrument
is not used carefully and correctly.
This study has illustrated a rapid, non-destructive
method for the in situ identiÐcation of cinnabar on
ancient Chinese manuscripts and textiles. In each
instance where red calligraphy was present on the
ancient paper analysed, it was unambiguously identiÐed
as cinnabar ; this supports the belief 8 that cinnabar was
the most important component of red inks in pre-tenth
century China.
Analysis of paper samples with red legal or punctu-
ation marks, and of a paper sample with a divine image
hand-painted in red, revealed no trace of any inorganic
pigment. The pigment is, therefore, probably organic,
the most likely red organic pigment in use in pre-tenth
century China being madder (see Table 2).22
Journal of Raman Spectroscopy, Vol. 28, 91È94 (1997)
94 R. J. H. CLARK ET AL .
These results further increase the understanding of
ancient Chinese manuscripts and, under the direction of
the IDP, will help to ensure their conservation. The
proven e†ectiveness of the devised non-destructive, in
situ analysis will allow valuable artefacts to be exam-
ined safely and conÐdently in the future.
CONCLUSIONS
A rapid, non-destructive method for the in situ identiÐ-
cation of cinnabar on ancient Chinese manuscripts and
textiles has been devised. Cinnabar has been demon-
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Journal of Raman Spectroscopy, Vol. 28, 91È94 (1997)