JOURNAL OF RAMAN SPECTROSCOPY J. Raman Spectrosc. 2006; 37: 235239 Published online in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/jrs.

1473

Identication of the pigments on a sixteenth century Persian book of poetry by Raman microscopy
Robin J. H. Clark and Sigrid Mirabaud
Christopher Ingold Laboratories, University College London, 20 Gordon St, London WC1H 0AJ, UK
Received 6 June 2005; Accepted 16 September 2005

rza A Persian book of poetry a poetic history of Shah Isma il by M Ka sim, dating to A.D. 1541, has been studied by Raman microscopy in order to explore the palette used at this time in Persia. The palette was found to include lazurite, indigo, red lead, vermilion, haematite, carbon black, orpiment, lead white and gold. The palette thus differs from that of another contemporary book of Persian poetry, most notably by the inclusion of indigo, and from that of a 15371538 Persian codex by the use of an intimate orpiment/indigo mixture for green rather than the copper-based mineral malachite. The palette also differs in a few respects from that of a Persian Herati manuscript of A.D. 1530 in that the latter uses an intimate mixture of orpiment and lazurite for green and does not include either haematite or indigo. Copyright 2006 John Wiley & Sons, Ltd.

KEYWORDS: pigments; Raman microscopy; sixteenth century Persian palette

INTRODUCTION
It is of considerable interest to establish the palette of Persian manuscripts of the sixteenth century1 as much less is known on this subject than on contemporary AngloSaxon and European manuscripts and codices.2,3 To this end, the technique of Raman microscopy has been embraced, since it has been shown to be highly effective for the identication of pigments, not only on manuscripts but also on paintings, enamels, ceramics, icons, polychromes, plaster, papyri and other artwork. This is because of its high spatial (<1 m) and high spectral (<1 cm 1 ) resolution, its excellent specicity, and its high sensitivity via chargecoupled device (CCD) detectors. A valuable book of Persian poetry was made available for Raman study in 2003 by the British Library, which holds an important collection of such N A-I N QASIM N N material. The book studied, called SHAHNAM I, N h Isma N il written by M N Ka N zim is a poetic history of Sha rza and considered to date from A.H. 948 (A.D. 1541). Its British Library accession number is Add. 7784. The Shahnama is a book of 184 folios, of dimensions 25.8 cm by 16.0 cm, containing 13 miniatures in fair Persian style. The text is handwritten in a ne Nestalik script, with

two gold-ruled columns. The book is from the collection of Claudius James Rich, who wrote on the rst page: This book. . .is a relic of the great Seviyan library. It was presented to me as a token of friendship by Fethullah Khan, son of the heroic and unfortunate Luft Ali Khan, who spent some days at my house on the way to Mecca, etc. Baghdad, December 29, 1819, C. J. Rich. Rich was a British diplomat, archaeologist, collector and linguist (17861821). N Ka N sim, surnamed Ka N sim N bad in M rza , was born in Juna present-day Iran, of a noble family. He left the hereditary ofce of chief magistrate of the town to his brother, to become a fakir devoting himself to poetry. He wrote the N hna N ma, Laila N Majnun N also four following Masnav s: a Sha N h Isma N il, Ka N r Namah, written at the same dedicated to Sha Shahs desire and Khusrau Sh r n, all of them before A.H. 957. In A.H. 979, he was said to be still alive and the date of his death is not known. The poem studied was commenced N h Isma N il (A.D. 15021529), but was not at the time of Sha nished until after his death.4 The present research adds to the very small body of pigment information made available by Raman microscopy studies on Persian manuscripts.5 7

EXPERIMENTAL
The spectra were recorded on a Renishaw System 1000 with 632.8- and 514.5-nm excitation obtained from heliumneon and argon ion lasers, respectively. The spectrometer was equipped with a CCD detector, which enabled Raman spectra

Presented as part of a commemorative issue for Wolfgang Kiefer on the occasion of his 65th birthday.

Correspondence to: Robin J. H. Clark, Christopher Ingold Laboratories, University College London, 20 Gordon Street, London WC1H 0AJ, UK. E-mail: r.j.h.clark@ucl.ac.uk

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to be obtained with excitation lines of low power (5 mW at the laser, 0.050.5 mW at the sample). Where possible, the laser beam was focussed onto a single grain of pigment through the 50 objective of a Leica optical microscope coupled with the spectrometer. The microscope was used both for illuminating the sample and for collecting the scattered light. The spectrometer was calibrated to 1 cm 1 by reference to the spectrum of silicon. As the manuscript was in a very poor state of conservation, it was only possible to choose several single plates, notably 70, 72, 107v and 160 for examination; these could be held without difculty under the microscope. To avoid any vibrations, glass slides were placed around the areas to be analysed.

reported by Bell et al.8 for their Raman Library of Pigments together with, where useful, that of the University of Florence, Italy.9 Other papers were sometimes consulted in order to solve certain identication problems that arose during the analysis. Most of the pigment analysis was conned to a single plate, number 107v, owing to the richness of its palette. Other plates notably 70, 72 and 160 were also analysed when corroboration was deemed to be important.

Blue pigment
Two tones of blue are distinguishable on plate 107v (Fig. 1), a grey-blue and a deep blue; the former is seen on the horse on the right-hand side of the painting, while the latter is seen on the clothes of the riders. Each gives the identical Raman spectrum, and so the colour difference probably arises from the effects of particle size on the diffuse reectance of the pigment grains.10 This pigment is readily identied as lazurite, the blue component of the mineral lapis lazuli; the latter is chemically

RESULTS AND DISCUSSION

The identication of the pigments used on this illuminated manuscript was made by comparison with the spectra

Figure 1. Illumination on plate 107v of the book of poetry.

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Identication of the pigments on a sixteenth century Persian book of poetry

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identical to its synthetic equivalent, ultramarine blue, known since A.D. 1828. Note that although each consists of an aluminosilicate matrix, approximating to Na8 [Al12 x Six O24 ]Sn , lazurite contains an ordered distribution of Al and Si framework atoms, whereas ultramarine blue contains a disordered distribution of these atoms.11 The chromophores in each are the radical anions S3 and S2 , as established by resonance Raman and electron spin resonance spectroscopy.12 The Raman spectra of the lazurite obtained from appropriate blue regions of plate 107v (Fig. 1) using the 632.8 nm excitation line have bands at 256, 545, 584, 803, 1090, 1123 and 1353 cm 1 (Fig. 2(a)). The spectrum of ultramarine blue was also acquired under the same conditions and on the same spectrometer because of slight differences between these spectra and those given in the Raman Library and that in the paper by Bicchieri et al.13 The slight differences are considered to arise because lazurite, if impure, may contain minor appendages of other minerals (e.g. pyrites, FeS2 , and calcite, CaCO3 ), whereas the synthetic equivalent does not. The blue on the ground depicted on plates 72 and 79 (not shown here) seemed at rst sight to be different visually from that identied on the horses and clothes. However, analysis with green excitation (514.5 nm) revealed bands at 545, 581 and 1093 cm 1 , again characteristic only of lazurite.

(a)

Lazurite

(b)

Red lead

Vermilion

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1000

1400

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1000

(c)
Raman Intensity

Hmatite

(d)
Orpiment

Carbon black
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(e)
Indigo

(f)
Indigo

Orpiment Orpiment

Red and red/orange pigments

The red/orange pigment used on the clothes of the different characters in the painting was identied8 to be red lead, dilead(II) lead(IV) oxide Pb3 O4 (Fig. 2(b)). It has an easily recognisable Raman spectrum, which is very similar to that given in the library. However, because of the notch lter, the signal is cut-off below c. 150 cm 1 in the present study (the library spectra were recorded on a scanning spectrometer); the spectrum recorded here thus failed to include two signicant bands of that pigment, at 122 and 149 cm 1 . In all other respects, the match is nearly perfect, the red/orange pigment in the Persian manuscript giving rise to bands at 223, 313, 390, 479 and 548 cm 1 , whereas the Library values are 223, 313, 340 (very weak), 390, 480 and 548 cm 1 . The red pigment used for the accessories, such as the ags, was found to be vermilion, mercury(II) sulde, HgS (Fig. 2(b)). Vermilion gave rise to three bands at 251 cm 1 (vs), 283 cm 1 (m) and 343 cm 1 (s), which is a very good match to the bands listed for vermilion in the Library8 at 252, 283 and 343 cm 1 . Plate 107v depicts a battle scene in which the blood from the injured, notably that from the person cut in two, is painted in vermilion a result which is far from obvious from visual inspection. The pigment used for the esh tones on the arms and faces seems to be a mixture of lead white,8 basic lead(II) carbonate, 2PbCO3 . Pb(OH)2 (characteristic band at 1051 cm 1 ) and a red pigment with bands at 254 and 549 cm 1 . The rst of

200

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750

1250 1750 2250 2750

Wavenumber / cm-1

Figure 2. Raman spectra (excitation wavelength 632.8 nm; ordinate, intensity; abscissa, wavenumber/cm 1 ) of the pigments on plate 107v. (a) blue pigment identied to be lazurite, (b) red pigments identied to be red lead (clothes, spectrum 1) and vermilion (accessories, ags, blood, spectrum 2), (c) pigments identied to be haematite and carbon black, respectively, (d) yellow pigment identied to be orpiment, (e) green pigment, zoom, (left) and (f) wide scan (right) identied to consist of a mixture of orpiment and indigo. In 2(e) the upper spectrum was taken with 514.5 nm excitation, which enhances the indigo bands, whereas the lower spectrum was taken with 632.8 nm excitation, which allows the orpiment bands to dominate.

these corresponds to the most intense band of vermilion, while the second corresponds to the most intense band of red lead. Careful microscopic examination suggests that the esh tone is developed from an intimate mixture of all three of these pigments, there being no evidence for layering.

Brown and black pigments

The black pigment used to depict the hair of the persons in plate 107v yields broad intense bands at 1347 and 1590 cm 1 , which are characteristic of carbon black; the spectrum

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(Fig. 2(c)) is closely similar to those shown in all Raman libraries. The brown pigment used on this plate for the body of the horse is haematite, alpha-Fe2 O3 , as evident from the very close match between the wavenumbers and intensities of the bands detected at 226, 245, 292, 411, 522, 609, 1322 cm 1 (Fig. 2(c)) and those reported previously from studies by Bikiaris et al.14 on ochre differentiation, de Faria et al.15 and van der Weerd et al.16 on iron oxides notably the haematite bands at 227vs, 246w, 293vs, 412m, 500w and 613m cm 1 .

uorescence. It is unlikely that the grey pigment consists of lazurite ash since no peak characteristic of this material, viz. the silicate band at 466 cm 1 , could be detected. Gold was identied in certain areas visually under an optical microscope. However, along with most other metals, it does not yield a Raman spectrum and so cannot be identied by Raman microscopy.

CONCLUDING REMARKS
The palette used in this manuscript is rich, containing lazurite, indigo, red lead, vermilion, brown ochre, carbon black, orpiment, white lead and gold. Each pigment is used in a variety of tones, either by being mixed with others of different colour or by being ground to particles of different size. Others failed to reveal a Raman spectrum, either by being poor Raman scatterers or by being present at concentrations too low to be detectable. The palette differs from that of a contemporary book of Persian poetry5 only on account of its inclusion of indigo, and from that of an A.D. 15371538 Persian codex6 by the use of an intimate mixture of orpiment and indigo for green rather than the mineral malachite. The palette of a further Persian manuscript of A.D. 1530 from Herat7 is also similar to that of the manuscript studied here, except that it involves the use of an intimate mixture of orpiment and lazurite for green and lacks both haematite and indigo. A contemporary Turkish manuscript recently studied had a slightly richer palette;18 it not only involves an intimate mixture of orpiment and indigo for green but also includes malachite, realgar and pararealgar.

Yellow pigment
The bright yellow colour that was used on plate 107v is identied to be orpiment, arsenic(III) sulde, As2 S3 , on the basis of the ve distinct bands detected at 202w, 292m, 310s, 356vs and 381w (Fig. 2(d)). The golden brown shade of the quivers is also painted in orpiment, as is the beige oor depicted in plate 70. Although it is possible that these slightly different tones may have been generated by forming mixtures of orpiment with traces of other pigments, there is no evidence that this is the case, and it seems more likely that they are all composed of orpiment, differing only in particle size.

Green pigment
The green pigment appeared to be homogeneous under a microscope, and not a mixture. Moreover, the Raman spectra of all tones of green are identical (Fig. 2(e)) albeit not matchable to that of any single pigment. The spectrum can, however, be well matched to that of an intimate mixture of orpiment (yellow, see preceding text) and indigo, C16 H10 N2 O2 (blue), which is characterised17 by mediumstrong bands at 549, 599 and c. 1578 cm 1 . The orpiment spectrum is better dened using red excitation (632.8 nm), while the indigo spectrum is better dened with green excitation (514.5 nm) (Fig. 2(e)). Organic dyes frequently uoresce under laser excitation and this is presumably the reason for the intense background in this gure.

Acknowledgements
The authors thank Drs. S. Firth, T. Chaplin, D. Jacobs and J. van der Weerd for their assistance in different aspects of this work, and the British Library for access to the artwork and for permission to publish the colour plate.

REFERENCES
1. 2. 3. 4. 5. 6. 7. 8. 9. Purinton N, Watters M. J. Amer. Inst. Conserv. 1991; 30: 125. Clark RJH. Chem. Soc. Rev. 1995; 24: 187. Clark RJH. CR Acad. Sci. Chimie 2002; 5: 7. The British Library Catalogue of Islamic Poetry, AH 9001000, 660. Ciomartin D, Clark RJH. J. Brazil. Chem. Soc. 1996; 7: 395. Bruni S, Cariati F, Casadio V, Guglielmi V. J. Cult. Heritage 2001; 4: 291. Hayez V, Denoel S, Genadry Z, Gilbert B. J. Raman Spectrosc. 2004; 35: 781. Bell IM, Clark RJH, Gibbs PJ. Spectrochim. Acta, Part A 1997; 53: 2159. University of Florence Library of Raman Spectra of Pigments and binders, 2003; http://www.chim.uni.it/raman/lista pigmen. html., accessed September 2003. Clark RJH. J. Chem. Educ. 1964; 41: 488. Tarling SE, Barnes PF, Klinowski J. Acta Crystallogr. 1988; B44: 128. Clark RJH, Franks ML. Chem. Phys. Lett. 1975; 34: 69.

Other colours
The violet pink of the ground in plate 107v failed to give a Raman spectrum with 632.8-nm excitation, it just uoresces. This may imply that an organic pigment or dye was used, one with a high absorption coefcient in the visible region of the spectrum such that only a minute amount was necessary to provide the colouration, but insufcient to yield a Raman spectrum. None of the white areas of the plate 107v clearly revealed the characteristic band of white lead at 1050 cm 1 , despite the fact that it could be identied in admixture with vermilion in various esh tone areas, as described earlier. The ground on plate 160 is grey. Several pigments were probably used here in admixture since not only were bands characteristic of lazurite and white lead detected (a very weak band was detected at 1048 cm 1 ) but also much ill-dened

10. 11. 12.

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13. Bicchieri M, Nardone M, Russo PA, Sodo A, Corsi M, Cristoforetti G, Palleschi V, Salvetti A, Tognoni E. Spectrochim. Acta, Part B 2001; 56: 915. 14. Bikiaris D, Daniila Sister, Sotiropoulou S, Katsimbiri O, Pavlidou E, Moutsatsou AP, Chryssoulakis Y. Spectrochim. Acta, Part A 1999; 56: 3. 15. de Faria DLA, Venancio Silva S, de Oliveira MT. J. Raman Spectrosc. 1997; 28: 873.

16. van der Weerd J, Rehren T, Firth S, Clark RJH. Mater. Characteriz. 2004; 53: 63. 17. Brown KL, Clark RJH. J. Raman Spectrosc. 2004; 35: 4. 18. Jurado-Lopez A, Demko O, Clark RJH, Jacobs D. J. Raman Spectrosc. 2004; 35: 119.

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J. Raman Spectrosc. 2006; 37: 235239