Spectrochimica Acta Part A 92 (2012) 2128

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Raman spectroscopy analysis of pigments on 1617th c. Persian manuscripts

Vnia S.F. Muralha a, , Lucia Burgio a,b , Robin J.H. Clark a
a
Christopher Ingold Laboratories, University College London, 20 Gordon Street, London WC1H 0AJ, UK
b
Victoria and Albert Museum, Science Section, Conservation Department, London SW7 2RL, UK

a r t i c l e i n f o a b s t r a c t

Article history: The palette of four Persian manuscripts of the 16th and 17th centuries were established by Raman
Received 1 November 2011 microscopy to include lazurite, red lead, vermilion, orpiment, a carbon-based black, lead white, mala-
Received in revised form 31 January 2012 chite, haematite, indigo, carmine and pararealgar. The rst ve pigments were identied on all four
Accepted 6 February 2012
manuscripts, as previously found for other Islamic manuscripts of this period. The ndings were com-
pared with information available in treatises on Persian painting techniques. Red lead, although identied
Keywords:
on all of the manuscripts analysed in this study as the main red pigment, is seldom mentioned in the litera-
Raman microscopy
ture. Two unusual pigments were also identied: the intermediate phase between realgar and pararealgar
Pigments
Persian manuscripts
in the manuscript Timur namah, and carmine in the manuscript Shah namah. Although the established
Pigment mixtures palette comprises few pigments, it was found that the illuminations were enhanced by the use of pigment
mixtures, the components of which could be identied by Raman microscopy.
2012 Elsevier B.V. All rights reserved.

1. Introduction
The Victoria and Albert Museum (V&A) holds a rich collection of
illuminated oriental manuscripts covering different geographical
locations and historical periods, the vast collection including some
of the most signicant works of Persian literature. The manuscripts
selected for analysis are examples of the skill of the Safavid dynasty
of Persia (15011732), where the art of calligraphy, illumination
and binding reached its apogee. Many rulers of this dynasty were
major art patrons and some of them were artists themselves,
such as Shah Thamasp (15291576), the son of the founder of the
dynasty (Shah Ismail I), who was both a calligrapher and a designer
[1].
In order to explore the palette of pigments used during this
period of Persian art, four illuminated Persian manuscripts from
the 16th and 17th centuries were selected. Two of them are epic
poems: Timur namah (Book of Timur) which tells the story of Timur,
the founder of the Timurid dynasty (13701405), and Shah namah
(Book of Kings), the history in 16,000 verses of the Pre-Islamic Per-
sian Kings. The other two manuscripts are books of poetry: Layla
we Majnun, Nizami (11411209), the famous adaptation of a Mid-
dle Eastern love story, and Diwan Anvari, the collected poems of the
Persian poet Anvari (11261189).
Corresponding author. Current address: Research Unit VICARTE: Vidro e
Cermica para as Artes, Faculdade de Cincias e Tecnologia, Universidade Nova de
Lisboa, 2829516 Monte da Caparica, Portugal. Tel.: +351 212947893.
E-mail addresses: solange@fct.unl.pt (V.S.F. Muralha), l.burgio@vam.ac.uk
(L. Burgio), r.j.h.clark@ucl.ac.uk (R.J.H. Clark).
Very few scientic studies of the pigments used on Persian illu-
minated manuscripts have yet been made. Raman microscopy (RM)
is a particularly appropriate technique since it allows the in situ
analysis of artefacts in a non-destructive way and is now widely
used to identify pigments on manuscripts [25]. The data obtained
are essentially immune to interference from other pigments, due
to the high spatial (ca. 1 m) and high spectral (ca. 1 cm1 ) resolu-
tion of the instrumentation. Most inorganic materials and a limited
range of organic ones can be identied in this way. However inter-
ference from uorescent binders, especially heavily bound ones,
may lead to difculties in identication.
By establishing a palette for the manuscripts analysed, a com-
parison can be drawn between the pigments employed and those
referred to in two Persian treatises on painting that have been trans-
lated into English. The rst is the Gulistan-I Hunan (Rose Garden of
Art), an appendix to a text written by Qadi Ahmad, in c. 1608, [6] and
the second is Qanun us-Suvar (Canons of Painting) by Sadiqi Bek, a
royal painter from the 16th century [7]. Both were written in what
is now Iran. Purinton and Watters [8] in 1991 compared informa-
tion about the materials used in Persian painting obtained through
scientic analyses with that available in the literature on Persian
painting techniques. They examined nineteen Persian paintings
dating from the 15th to the 17th centuries by energy-dispersive
X-ray uorescence analysis (XRF), complemented by X-ray diffrac-
tion (XRD) and polarised light microscopy (PLM). The palette of
this period was found to consist mostly of mixtures of pigments to
achieve a variety of different colours. Several more recent stud-
ies using RM as the main analytical technique for pigment and
binder analyses have contributed further to our knowledge of the

1386-1425/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2012.02.020
22 V.S.F. Muralha et al. / Spectrochimica Acta Part A 92 (2012) 2128

Figs. 13. (1) Double-page frontispiece from the manuscript Timur Namah (MSL/1876/699). Locations of the Raman analyses are indicated numerically. (2) Unwan from the
manuscript Timur Namah (MSL/1876/699). Locations of the Raman analyses are indicated numerically. (3) Unwan from the manuscript Layla we Majnum (MSL/1885/359).
Locations of the Raman analyses are indicated numerically.
 V.S.F. Muralha et al. / Spectrochimica Acta Part A 92 (2012) 2128 23

Figs. 46. (4) Scene from the manuscript Layla we Majnum (MSL/1885/359). Locations of the Raman analyses are indicated numerically. (5) Scene from the manuscript Diwan
Anvari (MSL/1923/169). Locations of the Raman analyses are indicated numerically. (6) Scene from the manuscript Shah Namah (MSL/1876/691). Locations of the Raman
analyses are indicated numerically.

palette used on Iranian manuscripts of the Islamic period [913].
The present work represents a detailed extension of these studies.
2. Experimental techniques
Raman microscopy (RM) was carried out using a Renishaw 1000
Ramascope spectrometer, equipped with a Renishaw HeNe laser
operating at 632.8 nm. The system was calibrated to better than
1 cm1 using a neon lamp before measurement. Different areas
on the manuscripts were located using a Leica LDLM optical (10
objective lens) microscope incorporated into the Renishaw sys-
tem. The laser beam was focused with a 50 objective lens. Since
it is an in situ technique, and to safeguard the integrity of the
manuscripts, laser power at the surface of the sample was held
to 0.4 mW.
2.1. Descriptions of the manuscripts
The manuscripts analysed (Figs. 16) are identied by their
National Library (NAL) reference number. The description consists
of the content of the manuscript, its date and provenance, and its
principal features [14].
MSL/1876/699. Timur namah written by Hati (d. AD 1520 or
1521) in Iran. Published in 994 AH (i.e. AD 1586). Description:
126 leaves, with coloured illustrations, 23 cm 14 cm. Binding of
leather. Summary: Poetical history of Timur (Tamerlane); also
called Zafar namah (Figs. 1 and 2).
MSL/1885/359. Layla we Majnun by Qasimi in Iran. Published
between AD 1550 and 1599. Description: 110 leaves (1 blank), with
coloured illustrations, 19 cm 12 cm. Decorated with gold ruled
margins, gold and painted unwan, and 5 full-page miniatures in
the style of Herat paintings. Binding of leather. It was written out
by Mir Bakharzi in Khorasan, Iran. Summary: A masnavi, or rhyming
poem, on the loves of Layla and Majnum (Figs. 3 and 4).
MSL/1923/169. The Diwan Anvari by Anvar, Awhad al-Dn,
d. AD 1189 or 1190. Published: 921 AH Rajab [i.e. AD 1515
August]. Description: 306 leaves (1 blank), with coloured illustra-
tions, 20 cm 10 cm. Decorated with an ornamental unwan and
headings in blue, with 9 half-page miniatures. Binding of leather
(Fig. 5).
24 V.S.F. Muralha et al. / Spectrochimica Acta Part A 92 (2012) 2128

Table 1 spectra was made using databases of reference materials [15,16].

Pigments mentioned on medieval Persian treatises and paintings [46]. The pig-
Table 3 contains lists of the main pigment mixtures found on the
ments are grouped by colour and are arranged in order of the most to the least
used. manuscripts.

Colour Pigment
3.1. MSL/1876/699 Timur namah (1586)
Blue Ultramarine, azurite, indigo
Red Vermilion, iron oxide earths, realgar, red lead, carmine
Yellow Orpiment, yellow ochre, organic yellows (saffron, Indian This manuscript contains a double-page illustrated frontispiece,
yellow) an illuminated unwan [17] and full-page miniatures. The double-
Green Verdigris, malachite, green earths, copper sulphates, page frontispiece is surrounded by a red and gold frame with a blue
mixtures of orpiment and indigo ground, overlaid with a oral pattern of red, yellow, white, green,
White Lead white
and black owers (Fig. 1). Raman analysis of the blue colour in sev-
Black Lamp black
eral areas of the double-page frontispiece always gives a spectrum
attributable to lazurite, with strong bands at 548 and 1096 cm1 ,
MSL/1876/691. Shah namah, or the Book of Kings by Firdaws. and weaker bands at 808, 583 and 259 cm1 (Fig. 7a). Lazurite is the
Published between AD 1650 and 1674. Description: 569 leaves (4 geological and chemical name of the blue crystalline component of
blank) with coloured illustrations, 38 cm 23 cm. Decorated with the mineral lapis lazuli, a sulphur-containing sodium aluminium
ornamental unwan and headings in gold, red, green and gold-ruled silicate mineral with general formula (Na,Ca)8 [(Al,Si)12 O24 ]Sn , the
and painted margins; 43 miniatures (1 double), some retouched, blue colour being due to entrapped sulphur radical anions [18,19];
and 1 repainted in the late 18th century. Binding of leather lazurite may contain as minor impurities pyrite, calcite and other
(Fig. 6). trace minerals. Ultramarine blue is the name of the synthetic ver-
sion of this pigment, rst made in 1828; this contains no mineral
3. Results impurities, and may be distinguishable from lazurite on this basis.
In addition factors such as particle morphology, size and unifor-
Table 1 presents the pigments and materials referred to in the mity of colour may also help in making the distinction. Lazurite was
Persian treatises of painting [6,7] and the revision paper by Purinton readily available to Persian painters from the mines of Badakhshan
and Watters [8]. Table 2 contains a summary of the pigments found in modern northern Afghanistan. These were by far the largest
on the manuscripts analysed by RM. The attribution of the Raman source of the mineral in the world [20].

Table 2
Pigments identied on the manuscripts by Raman microscopy, together with the pigment locations. First digit indicates the gure number, the second the position from
which the spectrum was acquired.

Pigments MSL/1876/699 MSL/1885/359 MSL/1923/169 MSL/1876/691 Location on the

Timur namah Layla we Majnun Diwan Anvari Shah namah illuminations
(1586) (16th century) (1515) (17th century)

Lazurite 1.1, 1.2, 1.3, 2.3,
3.1, 4.2, 5.1

Indigo 3.4

Red lead 1.5, 1.6, 1.7, 2.1,
3.2, 4.2, 5.3, 5.4

Vermilion 1.8

Haematite 6.1

Orpiment 1.4, 1.9, 5.10

Realgar 1.10, 1.11

Pararealgar 1.10, 1.11

Malachite 3.3, 5.11

Atacamite 3.6

Emerald green 5.7

Lead white 1.17, 3.5

Carbon-based black 4.1

Goethite 5.8

Carmine

Table 3
Pigments mixtures found on the manuscripts by Raman microscopy. Their locations are indicated by a number, the rst digit of which is the gure number and the second
the location.

Mixture of pigments Apparent MSL/1876/699 MSL/1885/359 Layla we MSL/1923/169Diwan MSL/1876/691 Location on the
colour Timur namah Majnun (16th century) Anvari (1515) Shah namah illuminations
produced (1586) (17th century)

Indigo + orpiment Dark green 1.12, 1.13, 2.4,
6.3

Lazurite + red lead Light green 1.14

Lazurite + vermilion Purple 1.15, 1.16

Malachite + indigo Green 3.3

Carbon-based black + indigo Bluish-black 3.4

Vermilion + orpiment Orange 2.2

Indigo + vermilion Dark red/dark 5.2, 5.5, 5.9
blue

Lazurite + indigo Dark blue 5.1

Indigo + goethite Dark green 5.7

Indigo + vermilion + orpiment Bright deep red 6.2
 V.S.F. Muralha et al. / Spectrochimica Acta Part A 92 (2012) 2128
Fig. 7. Raman spectrum of (a) lazurite (MSL/1876/699, Fig. 1, position 1), (b) red
lead (MSL/1876/699, Fig. 1, position 7), (c) vermilion (MSL/1876/699, Fig. 1, position
8), (d) orpiment (MSL/1876/699, Fig. 1, position 10); 0.35 mW laser power at the
sample.
The gold ruled frames and the gold ground in the frontispiece
were also analysed by RM but did not yield a Raman spectrum. The
Persian treatises on painting techniques refer to gold as being used
as paint, i.e. as gold particles dispersed in a medium consisting typ-
ically of dry glue and saffron or honey [8]. As is the case for most
metals, gold does not give a rst-order Raman spectrum, so it is
not detectable by RM. Alternative golden pigments such as mosaic
gold (SnS2 ) or micas (aluminosilicate minerals) would almost cer-
tainly have yielded an identiable Raman spectrum had they been
present.
There are two types of red in the frontispiece: an orange red
in the owers, rocks, the red frame and some of the vests, and a
bright red in other vests and the outlines of the horses. The orange
red pigment was identied to be red lead (Pb3 O4 ), with the bands
at 548, 390, 223, 149 and 122 cm1 (Fig. 7b). Red lead, also called
minium, was one of the earliest synthetic pigments, its usage dat-
ing back to the fth century BC in China [21]. The bright red was
identied as vermilion, mercury(II) sulphide, HgS (Fig. 7c), with
bands at 343, 285 and 253 cm1 . Vermilion occurs in certain vol-
canic and hot spring environments and has been used as a natural
pigment since antiquity [22]. Both the appendix to Qadi Ahmads
treatise and Sadiqi Beks Canons refer to two ways of obtaining this
pigment, from the mineral cinnabar and from reaction between
mercury and sulphur [6,7].
Orpiment was the pigment selected for the yellow hue appear-
ing in some vests and owers. This yellow arsenic sulphide (As2 S3 )
has been used since antiquity as a pigment both in its natural and
synthetic forms [22]. Purinton and Watters refer to the existence
of a wealth of sulphide ores in Iran and so orpiment was available
from the local sources [8]. Fig. 7d shows a spectrum of orpiment
with the characteristic bands at 353, 309, 292, 154 cm1 .
Of the non-human gures in the frontispiece, two horses can be
seen on the second page, one brown and the other mustard yel-
low. Raman analysis on the brown horse reveals red lead as the
main pigment, probably admixed with another which did not yield
a Raman spectrum. That of the mustard yellow ink has some bands
in common with orpiment, realgar (an arsenic(II) sulphide, As4 S4 ),
and pararealgar, the light-induced polymorph of realgar (Fig. 8). It
is known that exposure of red-orange realgar to light changes it into
yellow pararealgar at the surface. Both compounds consist of cova-
lently bonded As4 S4 molecules held in a lattice by van der Waals
forces. Transition between the two phases involves breaking the
As-As bonds and rearrangement of the As4 S4 structure through an
intermediate phase referred to as the -phase [2326]. Trentelman
et al. recorded the Raman spectra of realgar and pararealgar and
25
Fig. 8. Raman spectra of the yellow mustard ink on MSL/1876/699 (Fig. 1, posi-
tion 11) compared with those of the reference realgar, pararealgar and orpiment
(reference spectra from Ref. [12]).
also of the intermediate phase alone and with pararealgar [25].
The study was complemented by XRD data to conrm the species
present. When the intermediate phase is present with pararealgar,
the Raman spectrum resembles that obtained for the Timur namah
manuscript. A similar nding was made for the non-gurative illu-
mination of a 16th-century Persian manuscript, named Chihil Hadis
[13]. The spectra obtained for the mustard yellow ink show bands
of both realgar and pararealgar. Realgar was certainly used by Per-
sian artists since it was often mentioned in the treatises [6,7] but
pararealgar was not.
A very dark green was used in the vegetable decoration, i.e. the
bushes and the grass. This tone was realised by a mixture of indigo
and orpiment (Fig. 9a), the characteristic bands of indigo being at
1584, 1575, 599, and 546 cm1 . Indigo (C16 H10 N2 O2 ) is an organic
blue pigment and dye produced from the leaves of the indigofera
plant species [27,28]. According to some authors it was introduced
into Iran in the middle of the 6th century [8]. The use of this mixture
is mentioned in Persian treatises on painting [6,7], and Purinton
and Watters refer to these pigments as the ingredients of an arti-
cial verdigris [8]. Another green, lighter in hue, was applied in
the vests. Under a microscope mainly blue crystals can be seen but
also some orange-red and green ones. The blue crystals were iden-
tied as lazurite and the orange-red crystals as red lead. The green
crystals did not render a Raman spectrum due to their considerable
uorescence. A mixture of lazurite and red lead to produce a green
pigment is not mentioned anywhere in the treatises (Fig. 9b). It is
most likely that a green pigment was mixed with lazurite and red
lead to obtain that particular hue.
Another pigment mixture was identied by RM for the purple of
the cave, the blue components being lazurite and the red ones ver-
milion, each recognised by its characteristic Raman bands (Fig. 9c).
Finally, for the white on the turbans and owers, lead white was
identied from its bands at 1052 and 1049 cm1 (Fig. 9d).
The unwan has large areas of a blue and gold ground, overlaid
with a oral pattern of red, yellow and white owers (Fig. 2). The
arrangement also includes stylised leaf motifs in black. A set of gold,
blue, red and green lines frame the unwan.
Again the blue pigment chosen was lazurite, while the red, yel-
low and white owers were painted with red lead, orpiment and
lead white, respectively. The black ink was identied as a carbon-
based black pigment by two broad bands at ca. 1580 and 1325 cm1
(Fig. 9e). RM does not readily allow discrimination between the dif-
ferent carbon-based black pigments other than bone black. In the
appendix to Qadi Ahmads treatise [6], four recipes are mentioned
for preparing black inks, two of which relate to lamp black. This
carbon-based black pigment is also mentioned in the published
literature on Persian painting techniques [7]. For the frames, RM
identied the pigments as follows: lazurite for the blue, red lead
26 V.S.F. Muralha et al. / Spectrochimica Acta Part A 92 (2012) 2128

Fig. 9. Raman spectrum of (a) mixture of indigo and orpiment (Fig. 2, position 4), (b) mixture of lazurite and red lead (Fig. 1, position 14), (c) mixture of lazurite and vermilion
(Fig. 1, position 16), (d) lead white (Fig. 1, position 17), (e) carbon-based black (Fig. 4, position 1), (f) malachite (Fig. 3, position 3), (g) mixture of carbon-based black and indigo
(Fig. 3, position 4), (h) atacamite (Fig. 3, position 6). Each spectrum collected using 632.8 nm excitation, a 50 objective and 0.35 mW laser power at the sample surface.

for the red and a mixture (not fully identied) of lazurite and lead
white for the green. Purinton and Watters found that some colours
needed an addition of white for brilliance and opacity, so lead white
may have been added for this reason [8].
The other full-page miniatures were also analysed by RM but
the palette employed was similar to that found for the frontispiece.
3.2. MSL/1885/359 Layla we Majnun (second half of 16th
century)
The illumination of the epic love story of Layla we Majnun has a
gold and painted unwan and ve full-page miniatures. The unwan
was painted in a blue and gold ground, and is completely covered
with spiral scrolls in gold-bearing owers in a variety of colours
(blue, red, green, white and black). In the centre of the decoration,
the title of the poem is written with a white ink (Fig. 3).
Again the blue ground and the blue motifs were painted with
lazurite, while the red pigment for the owers is red lead. Analysis
of the green owers showed that green colour is formed from a
mixture of the green malachite and dark blue indigo. Malachite is a
basic green copper carbonate, CuCO3 Cu(OH)2 , with characteristic
bands at 1086, 1051, 433, 354, 268, 217, 178, 155 cm1 (Fig. 9f).
This mineral is often found together with the chemically similar
mineral azurite as well as calcite. The dark owers surrounding the
title of the poem were painted with indigo (Fig. 9a).
The white lettering and also the white owers show the charac-
teristic bands of lead white (cf. Fig. 9d). The bluish-black ink used
in the text was identied by RM as a mixture of a carbon-based
black and indigo (Fig. 9g). On this page the unwan and text are
surrounded by a set of gold frames and an inner green frame; the
latter shows the characteristic bands of atacamite at 974, 911, 513,
149, 122 cm1 (Fig. 9h).
On the rst miniature, Layla and Majnun at school (Fig. 4), the
blue colours were always painted with lazurite, but the richness of
the other colours was largely achieved by use of different pigment
mixtures. In addition some yellow motifs such as the oral ones or
the vest were obtained with orpiment.
On the right side of the page there is an orange wall overlaid with
a red oral pattern. Raman analysis on the orange paint revealed the
characteristic bands of vermilion and orpiment (Fig. 10a). However,
when the orange is examined under a microscope, red crystals can
be detected whose Raman spectra show the characteristic bands of
red lead (cf. Fig. 7b).
There are large areas of pink walls and a roof all painted with
a mixture of vermilion and lead white. The lead white softens the
bright red of vermilion, and this mixture was often used by Persian
miniaturists [8].
Two hues of green were analysed, a dark green and a yellowish-
green, and both showed the characteristic bands of orpiment and
indigo (cf. Fig. 9a).
A further mixture was identied by RM as indigo with vermilion
(Fig. 10b) to produce a dark red (fourth miniature) and a dark blue
(third miniature).
3.3. MSL/1923/169 Diwan Anvari (1515)
This collection of poems from the poet Anvari is the oldest
manuscript studied. The illumination of the opening page has a
 V.S.F. Muralha et al. / Spectrochimica Acta Part A 92 (2012) 2128 27

Fig. 10. Raman spectrum of (a) mixture of vermilion and orpiment (Fig. 2, position 2), (b) mixture of vermilion and indigo (Fig. 5, position 2), (c) mixture of lazurite and
indigo (Fig. 5, position 1), (d) goethite (Fig. 5, position 8), (e) emerald green (Fig. 5, position 7), (f) carmine (not shown), (g) mixture of indigo, orpiment and vermilion (Fig. 6,
position 2), (h) haematite (Fig. 7, position 1). Each spectrum collected using 632.8 nm excitation, a 50 objective and 0.35 mW laser power at the sample surface.

blue and gold ground, covered by owers of several colours. The
blue pigment is invariably lazurite for the blue ground and the blue
owers. The remaining red, white and yellow owers were painted
with red lead, white lead and orpiment, respectively. Malachite was
the green pigment used for the spiral scrolls. For the frames that
enclose the illuminated heading, the red frame was painted with
red lead and the black frame with a carbon-based black.
On the nine half-page miniatures the blue pigment chosen was
again lazurite, except when the artist wanted to create a darker
blue in which case indigo was used, sometimes in admixture with
lazurite (Fig. 10c). As an example, in Fig. 5, the dark blue sky was
obtained with a mixture of lazurite and indigo, the dark blue ground
with indigo, and the light blue rug with lazurite.
The orange colour was made with red lead, the bright red and
pink with vermilion and the black with a carbon-based pigment.
The purple and the brown were obtained by mixing indigo and
vermilion.
There are two distinguishable shades of green used in the
miniatures, a dark green for the trees and a bright green for the
clothes and human accessories. By observing the dark green under
a microscope, it is possible to distinguish yellowish-orange crystals
together with different shades of blue crystals. RM analysis on the
blue crystals identied them as indigo and the yellowish-orange
ones as goethite, an iron hydroxide (FeOOH), known as yellow ochre
(Fig. 10d). Its usage is mentioned in Persian treatises on painting [8].
The lighter green was identied by RM as emerald green, a
copper acetoarsenite (Cu[C2 H3 O2 ]3Cu[AsO2 ]2 ) with characteris-
tic Raman bands at 951, 539, 492, 371, 242, 217, and 154 cm1
(Fig. 10e). Emerald green is a synthetic pigment introduced into
Europe between 1800 and 1814 and discovered while trying to
improve another popular green, Scheeles green (a copper arsenite
of varying composition) [29]. There is no naturally occurring cop-
per acetoarsenite, and so it is presumed that this pigment must
have been added to the manuscript at some early stage by way of
restoration, as there is no record of there having been any such
intervention while the manuscript was in the museum. Emer-
ald green was a very popular green pigment due to its brilliant
colour.
3.4. MSL/1876/691 Shah namah (second half of the 17th
century)
This 17th century copy of the Shah namah (Book of Kings) is the
largest manuscript studied. It contains an illuminated heading with
a gold ground decorated with a oral pattern in blue, red, yellow,
white, and purple. The blue ground is lazurite, the pale blue owers
and the markings are indigo, the red pigment is red lead, and the
white pigment is lead white. The black pigment is a carbon-based
pigment and the dark bright red is vermilion.
Analysis of the purple colour gave a complex Raman spectrum
with bands at 1691, 1481, 1316, 1294, 1104, 1004 and 542 cm1
(Fig. 10f), very similar to the reference ones for carmine (carminic
acid, C22 H20 O13 ) [16]. Organic reds such as carmine and madder [8]
have been identied previously on some Persian paintings.
On the 43 miniatures of the Shah namah, the chosen blue pig-
ment is again lazurite. Indigo was only found in a bright deep-red
mixture made with indigo, orpiment, and vermilion (Fig. 10g)
and, for the green and brown colour, in admixture with orpiment.
Another brighter brown (Fig. 6), was identied as haematite, with
characteristic bands at 613, 411, 292, and 226 cm1 (Fig. 10h).
28 V.S.F. Muralha et al. / Spectrochimica Acta Part A 92 (2012) 2128
Haematite (-Fe2 O3 ) is an iron oxide widely used as a pigment
throughout the centuries. It is found as ochre, a natural earth con-
sisting of silica and clay but owes its colour to iron(III) oxide. Ochres
are known to be used by Persian painters and there are extensive
deposits of iron oxide in the island of Ormuz in the Persian gulf [8].
4. Discussion
Raman analysis of the pigments shows that the palette is rela-
tively small for the range of colours observed and also for the time
span of the manuscripts. Several of these primary pigments were
mixed to obtain the different ranges of colour observed, in agree-
ment with other published analyses of Persian paintings [8]. Five
pigments were identied on all the manuscripts analysed: lazurite,
orpiment, red lead, vermilion, and a carbon-based black pigment.
It is not surprising to nd lazurite as the blue pigment par excel-
lence in the Persian palette, since it is almost the only blue pigment
mentioned in the treatises; similarly orpiment is the only yellow
discussed [68] and the same can be said for orpiment. Red lead,
on the other hand, is seldom cited in the published literature, so it
was surprising to nd that it was the dominant red pigment iden-
tied in this study. The manuscripts have different provenances so
a geographical factor is ruled out. Vermilion is often reported as
the most widely used red pigment in Persian painting, and in fact it
was identied in all the manuscripts analysed. However vermilion
usually appears on diacritics or the text itself, rather than on the
decoration [30]. The carbon-based black identied is most likely to
be lampblack, as this is the only black pigment mentioned on the
treatises.
Other pigments also add to the palette though they do not
appear on all the manuscripts, viz. haematite, carmine, mala-
chite, and atacamite. The green pigments deserve a brief comment
[31,32]. According to the treatises, the preferred green pigment
of Persian artists was verdigris, a copper ethanoate of various
chemical compositions e.g. Cu(CH3 COO)2 , called the raw verdigris,
and several recipes exist for the preparation of other such greens
with different chemical compositions. However some green crys-
tals analysed did not reveal a Raman spectrum because of their
associated, more intense, uorescence.
An interesting nding in this study was a light-induced transfor-
mation product of realgar on MSL/1876/699. This product, known
as pararealgar, has already been characterised by RM, and so has
the intermediate phase of this degradation process. However the
Raman spectra obtained did not correspond fully to that of any
of the arsenic sulphides mentioned, but were very similar to that
of the degradation phase, probably mixed with some pararealgar.
Realgar is a red pigment referred to in the treatises, but seldom
identied on Persian illuminations, possibly due to its degrada-
tion.
Finally, of all the pigment mixtures identied, that consisting of
indigo and orpiment was the most used on all the manuscripts. In
addition, a mixture of indigo and vermilion was found on three of
the manuscripts to make hues of brown and dark red.
5. Conclusions
Four Persian manuscripts have been analysed by RM, revealing
that the palette consists of lazurite, red lead, vermilion, orpi-
ment, a carbon-based black pigment, lead white and malachite.
Other pigments identied on only a single manuscript comprise
haematite, atacamite, indigo, carmine and pararealgar. Although
the manuscripts belong to different periods the palette remains
very consistent. Several pigment mixtures involving realgar and
pararealgar were used to obtain the range of colours observed.
Acknowledgements
V.S.F. Muralha acknowledges the support of the Fundaco para
a Cincia e Tecnologia (Grant SFRH/BPD/16519/2004). The authors
also thank Tim Stanley, Senior Curator in the V&A Asian Depart-
ment for his assistance and expertise, and the Victoria and Albert
Museum and Renishaw plc. for support.
References
[1] T. Rice, Islamic Painting, Edinburgh University Press, Edinburgh, 1971.
[2] R.J.H. Clark, CR Acad. Sci. Chim. 5 (2002) 7.
[3] K. Trentelman, N. Turner, J. Raman Spectrosc. 40 (2009) 577.
[4] C. Miguel, A. Claro, A.P. Goncalves, V.S.F. Muralha, M.J. Melo, J. Raman Spectrosc.
40 (2009) 1966.
[5] L. Burgio, R.J.H. Clark, R.R. Hark, Proc. Natl. Acad. Sci. 107 (2010) 5726.
[6] V. Minorsky (trans. 1959), in: Calligraphers and Painters: A Treatise by Qadi
Ahmad, Son of Mir Munshi (circa A.H. 1015/A.D. 1606), Smithsonian Institution,
Freer Gallery of Art, Occasional Papers, Washington, DC, 1959, p. 195.
[7] M.B. Dickson, S.C. Welch, The Houghton Shahnameh, Appendix 1: The Canons
of Painting by Sadiqi Bek, Harvard University Press, Cambridge, MA, 1981, p.
259.
[8] D.A.N. Purinton, M. Watters, J. Am. Inst. Conserv. 30 (1991) 125.
[9] D.A. Ciomartan, R.J.H. Clark, J. Braz. Chem. Soc. 7 (1996) 395.
[10] S. Bruni, F. Cariati, F. Casadio, V. Gugliemi, J. Cult. Herit. 4 (2001) 291.
[11] V. Hayez, S. Denoel, Z. Genadry, B. Gilbert, J. Raman Spectrosc. 35 (2004)
781.
[12] R.J.H. Clark, S. Mirabaud, J. Raman Spectrosc. 37 (2006) 235.
[13] L. Burgio, R.J.H. Clark, V.S.F. Muralha, T. Stanley, J. Raman Spectrosc. 39 (2008)
1482.
[14] D. Haldane, Islamic Bookbindings in the Victoria and Albert Museum, World of
Islam Festival, London, 1983, p. 85.
[15] I.M. Bell, R.J.H. Clark, P. Gibbs, Spectrochim. Acta [A] 53 (1997) 2159.
[16] L. Burgio, R.J.H. Clark, Spectrochim. Acta [A] 57 (2001) 1491.
[17] B.W. Robinson, E.J. Grube, G.M. Meredith-Owens, R.W. Skelton, Unwan is a large
and elaborate illumination, often covering a whole double-page opening, in:
Islamic Painting and the Arts of the Book, Faber and Faber Limited, London,
1976.
[18] R.J.H. Clark, D.G. Cobbold, Inorg. Chem. 17 (1978) 3169.
[19] R.J.H. Clark, T.J. Dines, M. Kurmoo, Inorg. Chem. 22 (1983) 2766.
[20] J. Plesters, Ultramarine Blue, Natural and Articial in Artists Pigments
A Handbook of their History and Characteristics, vol. 2, National Gallery
of Art and Oxford University Press, Washington, DC, Oxford, 1993,
p. 37.
[21] (a) E.W. Fitzhugh, Red Lead and Minium in Artists Pigments A Handbook of
their History and Characteristics, vol. 1, National Gallery of Art and Oxford
University Press, Washington, DC, Oxford, 1986, p. 109;
(b) R.J.H. Clark, M.L. Curri, J. Mol. Struct. 440 (1998) 105.
[22] E.W. Fitzhugh, Orpiment and Realgar in Artists Pigments A Handbook of their
History and Characteristics, vol. 3, National Gallery of Art and Oxford University
Press, Washington, DC, Oxford, 1997, p. 47.
[23] L. Bindi, P. Bonazzi, Am. Miner. 92 (2007) 617.
[24] R.J.H. Clark, P.J. Gibbs, Chem. Commun. (1997) 1003.
[25] K. Trentelman, L. Stodulski, M. Pavlosky, Anal. Chem. 68 (1996) 1755.
[26] L. Burgio, R.J.H. Clark, J. Raman Spectrosc. 31 (2000) 395.
[27] C.L. Huart, Les Calligraphers et les Miniaturistes de lOrient Musulman, Proff &
Co.KG, Osnabruck, 1972.
[28] R.J.H. Clark, C.J. Cooksey, M.A.M. Daniels, R. Withnall, Endeavour 17 (1993)
191.
[29] R.J. Gettens, G.L. Stout, Painting Materials a Short Encyclopedia, Dover, New
York, 1966.
[30] R.J.H. Clark, K. Huxley, Sci. Technol. Cult. Herit. 5 (1996) 95.
[31] S.P. Best, R.J.H. Clark, M.A.M. Daniels, C.A. Porter, R. Withnall, Stud. Conserv. 40
(1995) 31.
[32] T.D. Chaplin, R.J.H. Clark, A. McKay, S. Pugh, J. Raman Spectrosc. 37 (2006)
865.