Journal of Molecular Structure 480–481 (1999) 15–20

Raman microscopy: sensitive probe of pigments on manuscripts,

paintings and other artefacts 夽
Robin J.H. Clark*
Christopher Ingold Laboratories, University College London, 20 Gordon Street, London, WC1H 0AJ, UK
Received 4 September 1998; accepted 30 September 1998

Abstract
Raman microscopy is compared with other techniques from the point of view of assessing its importance in the detection and
identification of pigments on manuscripts, paintings, ceramics and papyri. Applications to the study of both Western and
Eastern artefacts are outlined, and some conservation and authentication problems are addressed. 䉷 1999 Elsevier Science B.V.
All rights reserved.
Keywords: Raman microscopy; Pigments; Manuscripts; Paintings; Archaeometry

1. Introduction connection with the restoration, conservation, dating

and authentication of artefacts. Minerals and natural
Many techniques have been employed for the dyes cannot be dated by spectroscopic techniques but
purpose of identifying pigments on manuscripts, synthetic ones clearly can, by implication, from the
paintings, ceramics, papyri and other artefacts, date of their first manufacture.
notably electronic (especially diffuse reflectance) The newest, and arguably the best, single technique
spectroscopy, infrared and Raman spectroscopy, to be applied to the area is Raman microscopy, which
optical microscopy and X-ray diffraction – all of combines the attributes of reproducibility and sensi-
which are specific to the compound – and scanning tivity with those of being non-destructive and essen-
electron microscopy (SEM), X-ray fluorescence tially immune to interference from both pigments and
(XRF), particle-induced X-ray emission (PIXE), and binders. Moreover, the technique can be applied in
particle-induced g-ray emission (PIGE) – all of situ, which makes it important for the study of manu-
which are specific to the elements present [1]. Such scripts (for which sampling is forbidden), and it has
studies are of great importance in furthering the high spatial ( ⱕ 1 mm) and spectral (c.1 cm ⫺1) resolu-
understanding of our cultural heritage, notably in tion (features of obvious value for establishing the
composition of pigment mixes).
The weakness of the Raman effect in the absence of
夽
Based on a Plenary Lecture given to the XXIV European resonance effects and the only moderate sensitivity of
Congress on Molecular Spectroscopy, Prague, Czech Republic, the early detection systems (semi-conductor or diode)
August 1998.
* Corresponding author. Tel.: 00 44 171 380 7457; fax: 00 44 171
originally available were unattractive features of
380 7463. Raman microscopy. Many of these problems have
E-mail address: r.j.h.clark@ucl.ac.uk (R.J.H. Clark) now been solved by the introduction of CCD detectors
0022-2860/99/$ - see front matter 䉷 1999 Elsevier Science B.V. All rights reserved.
PII: S0022-286 0(98)00649-8
16 R.J.H. Clark / Journal of Molecular Structure 480–481 (1999) 15–20

Fig. 1. Byzantine/Syriac Gospel lectionary (13th Century) held in a special cradle under a Raman microscope in order to identify the pigments
thereon.

to modern spectrometers which allow poorly 2. Results and discussion

scattering pigments, notably fluorescent organic
dyes, to be studied with near-infrared, low power The present article highlights and summarises the
lasers. large number of recent studies carried out at Univer-
It is also now realised that there is enormous poten- sity College London on both Western and Eastern
tial for Raman microscopy to provide information that manuscripts, on pigments and pigment sections
will assist the conservator to preserve manuscripts for taken from paintings, on pottery, majolica, and
future generations. For example, if deterioration had Egyptian faience, and on papyri, etc.
already occurred, Raman studies may lead to the iden-
tification of decomposition products and thus enable 2.1. Western Manuscripts
the conservator to consider treatments either to halt or
The pigments identified by Raman microscopy
reverse the process.
include the following:
A survey of the pigments used to illuminate manu-
scripts, paintings, ceramics and other artefacts and of • Paris bible c. 1275 Latin: white lead, vermilion, red
the technique and practice of Raman microscopy has lead, lapis lazuli, azurite, orpiment, realgar,
recently been given [1]. malachite [1,2].
 R.J.H. Clark / Journal of Molecular Structure 480–481 (1999) 15–20 17

Fig. 2. Blackening of white lead, especially on faces, when converted to lead sulfide on a 13th C Byzantine lectionary, (Ref [10]).

• North Italian antiphonal 13th C: lapis lazuli, mala- • German choir book 16th C: white lead, carbon,
chite [1]. azurite, vermilion, red lead, massicot, lead tin
• North Italian choir book 13th C: shown to contain yellow type I [1].
layers of lapis lazuli over azurite [1]. • Three German manuscripts, 15th C: vermilion, red
• Three Latin manuscripts 15th C: vermilion, ochre, azurite, malachite, lampblack, white lead,
kermes, azurite, malachite, ivory black (based on lead tin yellow type I, lapis lazuli [4].
amorphous carbon), white lead, lead tin yellow • Flora Danica, six folios of the unique Danish
type I. Some of the red a -form of vermilion has catalogue of plants of the Scandinavian region,
degraded to the black a 0 -form [3]. late 18th C: vermilion, red lead, massicot,
18 R.J.H. Clark / Journal of Molecular Structure 480–481 (1999) 15–20

Fig. 3. Realgar (As4S4) on the left and para-realgar (As4S4) on the right; conversion from one to the other is facilitated by radiation of
wavelengths 530–560 nm.

Prussian blue, white lead, chalk, lampblack, green vermilion identified on paper and textile fragments
earth [5]. [11].
• The Skard copy of the Icelandic Book of Law, c.
1360: vermilion, orpiment, realgar, red ochre, Four Thai and one Javanese manuscript, 19th C:
azurite, bone white, verdigris, green earth [6]. No vermilion, red lead, red ochre, litharge, indigo, ultra-
lead-containing pigments were detected on the marine blue, chalk, white lead, gypsum, anhydrite,
manuscript, possibly owing to the lack of lead baryte, orpiment, chrome yellow, chrome orange,
ores in Iceland. lampblack [12]. Indigo has also been identified on
Korean, Chinese and Uighur manuscripts. These
2.2. Eastern manuscripts extensive studies and those of other groups form a
basis for the authentication and possible dating of
• Two Persian manuscripts, “Anatomy of the Body”, artefacts.
19th C: copy of earlier manuscript, and “Poetry in As a complement to the studies of manuscripts from
Praise”, 16th C: vermilion, red lead, lampblack, many parts of the world, a library of Raman spectra of
ivory black, white lead, orpiment, hydrated c. 60 pigments, both natural and synthetic, known to
iron(III) hydroxyoxide, lapis lazuli [7]. have been used before 1850 AD has been compiled
• Qazwini manuscript “Wonders of Creation and and published recently [13]. Extensions to this
Oddities of Existence”, 16th C: copies of late library to embrace later pigments and dyes are
13th C: encyclopedic work, in Arabic but of in hand. Applications in the field of Conservation
Indian style: vermilion, red lead, white lead, Science include the study of the nature of the
lapis lazuli, carbon black, Indian yellow, verdigris serious blackening of many pigments on a
[8]. lectionary (white lead, 2PbCO3.Pb(OH)2, ! (lead(II)
• Qur’an section, Iran or central Asia, Eastern Kufic sulfide) (Fig. 2) and of the photochemical conver-
script, 13th C: white lead, lapis lazuli, vermilion, sion of realgar (orange, As4S4) to para-realgar
kermes-carmine [9]. (yellow, As4S4), optimally with radiation in the
• Byzantine/Syriac Gospel lectionary, Iraq, 13th C: range 530–560 nm [10–14]. The mechanism of
white lead, vermilion, lapis lazuli, orpiment, the light-influenced transformation of realgar into
realgar, para-realgar. Rare and valuable manu- para-realgar, the first step of which appears to involve
script, ( ⬎ £1 m) [10]. See Fig. 1. breakage of an AsAs bond (Fig. 3), is currently being
• Manuscript fragments (8) and one textile fragment, studied computationally using density functional
from Dunhuang, north-west China, 10th C: theory.
 R.J.H. Clark / Journal of Molecular Structure 480–481 (1999) 15–20 19

2.3. Painting sections (1704), copper phthalocyanine, Cu(C32H16N8)

(1936), and organic lakes possibly involving dyes of
Pigments removed from water colour or oil paint- the quinacridone family. Moreover, further pigments
ings (samples or cross-sections) may readily be iden- were identified to be in their synthetic rather than in
tified by Raman microscopy in the absence of varnish. their mineral forms, e.g. anatase, TiO2, – pure white
Important studies of Titian and Veronese paintings at form, first synthesised in 1923, and visually different
the National Gallery in London allow the two types of from the native mineral form (black), and ultramarine
lead tin yellow Pb2SnO4 (type I, a mixed-valence Pb II/ blue, Na8[Al6Si6O24]Sn, – which when viewed under
Sn IV compound) and PbSn0.76Si0.24O3 (type II, a defect an optical microscope, has a different (rounded) form
pyrochlore structure) – both having closely similar from that of the same chemical, lazurite, extracted
shades of yellow – to be distinguished readily in from the mineral lapis lazuli [20]. Clearly, the illus-
this way [15]. trations on the papyri are modern, a conclusion which
is likely to reduce the value of each item by a factor of
2.4. Ceramics at least 10 3! The importance of proper identification of
Recently, other types of historical artefact have also pigments on artefacts for authentication purposes is
been investigated by Raman microscopy, including thus obvious to auction houses and the art world in
pottery, faience and Egyptian faience. Notable is the general.
first identification of lapis lazuli in the blue glaze of 2.6. Technical developments in Raman Microscopy
fragments of medieval items of pottery (faience/majo-
lica) excavated from an abandoned village near Important technical developments in the field of
Foggia in Southern Italy [16]. A brown-black pigment Raman microscopy involve (a) the use of a fibre-
also present in this pottery was identified by X-ray optic probe connected to a miniaturised colour video
photoelectron spectroscopy to be manganese(IV) head, which makes possible the study of pigments on
oxide [17]. The red pigments in shards of medieval wall paintings, statues, etc., in situ, and the use of a
pottery from many sites in Italy have been identified two-dimensional motorised stage to allow the
as iron oxides (red ochre, Venetian red, Indian red) mapping of surfaces and the study of the depth profiles
and from yellow shards as hydrated iron(III) oxyhydr- of pigments on surfaces.
oxide (yellow ochre, Mars yellow, etc.) [18].
A study of fragments of Egyptian faience of the
XVIIIth Dynasty and uncovered at El Amarna in the 3. Conclusion
Nile valley, Egypt, has revealed that the red fragments
are coloured with red ochre/red earth and the yellow Raman microscopy is now clearly established as a
ones with lead antimony yellow, Pb2Sb2O7 [19]. The major technique for the rapid identification of
extension of this type of archaeological work to other pigments on manuscripts, paintings, and other arte-
artefacts is very feasible since the Raman spectrum of facts. Its relevance to the identification of the compo-
each pigment is unique and now, with modern instru- nents of pigment mixes at high ( ⱕ 1 mm) spatial
mentation, readily obtainable. resolution is unparalleled [1]. The main difficulties
arise with certain organic pigments which either fluor-
2.5. Papyri esce (or their supports or binders do), are photosensi-
tive, or fail to yield a Raman spectrum owing to small
Recent studies of some beautifully illuminated particle size and/or high degree of dilution, e.g. in a
papyri, the oldest supposedly dating back to the time lake. The technique of Raman spectroscopy has, of
of Ramses II, 13th C B.C., have led to the identifica- course, a vast number of technological applications
tion thereon of several mineral pigments, e.g. chalk, other than to the identification of pigments, namely,
gypsum, and red ochre, which cannot be dated by to the identification of contaminants in microelectro-
Raman microscopy, but also of some synthetic nics, of inhomogeneities formed during the crystal-
pigments whose first synthesis is comparatively lization of polymers, the detection of inclusions in
recent, e.g. Prussian blue, Fe4[Fe(CN)6]3.14H2O minerals, the monitoring of the curing of polymer
20 R.J.H. Clark / Journal of Molecular Structure 480–481 (1999) 15–20

resins, and of pesticides in tissues of organisms in the [4] L. Burgio, D.A. Ciomartan, R.J.H. Clark, J. Mol. Struct. 405
food chain, together with other applications in medi- (1997) 1.
[5] L. Burgio, R.J.H. Clark, H. Toftlund, Acta Chem. Scand., in
cine, jewellery studies, polymer science, and forensic press.
science [21–23]. It should be emphasized, however, [6] S.P. Best, R.J.H. Clark, M.A.M. Daniels, C.A. Porter, R.
that the most effective studies on pigment identifica- Withnall, Studies in Conservation 40 (1995) 31.
tion as well as in the other areas of science mentioned [7] D.A. Ciomartan, R.J.H. Clark, J. Braz. Chem. Soc. 7 (1996)
are usually carried out by use of Raman microscopy in 395.
[8] R.J.H. Clark, P.J. Gibbs, J.Archaeolog. Sci. 25 (1998) 621.
conjunction with one or more other techniques. In this [9] R.J.H. Clark, K. Huxley, Science and Technology for Cultural
way the weaknesses of the one may be complemented Heritage 5 (1996) 95.
by the strengths of another [24]. In this context, it has [10] R.J.H. Clark, P.J. Gibbs, Chem. Commun. (1997) 1003; Anal.
emerged that one of the best complementary techni- Chem. 70 (1998) 99A.
ques is that of PIXE, and several recent studies have [11] R.J.H. Clark, P.J. Gibbs, J. Raman Spectrosc. 28 (1997) 91.
[12] L. Burgio, R.J.H. Clark, P.J. Gibbs, J. Raman Spectrosc.
demonstrated this most effectively [25–29]. In other (1998) in press.
cases, different combinations of techniques are best [13] R.J.H. Clark, P.J. Gibbs, Spectrochim. Acta. 53A (1997) 2159.
employed, viz. SEM, EDX and PIXE in the case of [14] D.L. Douglas, C. Shing, G. Wang, Am. Mineral. 77 (1992)
investigating the deacidification of paper by ethoxy- 1266.
magnesium ethylcarbonate, C2H5OCO2MgOC2H5, [15] R.J.H Clark, L. Cridland, B.M. Kariuki, K.D.M. Harris, R.
Withnall, J. Chem. Soc. Dalton Transactions (1995) 2577.
and its depth of penetration when sprayed in hexam- [16] R.J.H. Clark, M.L. Curri, C. Laganara, Spectrochim. Acta 53A
ethyldisiloxane onto only one side of the paper [30]. (1997) 597.
In conclusion, there is no doubt that museums and [17] R.J.H. Clark, M.L. Curri, G.S. Henshaw, C. Laganara, J.
libraries will need to use in the future a much wider Raman Spectrosc. 28 (1997) 105.
range of techniques than in the past in order to probe [18] R.J.H. Clark, M.L. Curri, J. Mol. Struct. 440 (1998) 105.
[19] R.J.H. Clark, P.J. Gibbs, J. Raman Spectrosc. 28 (1997) 99.
the host of conservation, authentication and dating [20] L. Burgio, R.J.H. Clark, to be published.
problems which await solutions. [21] J. Corset, P. Dhamelincourt, J. Barbillat, Chem. Brit. (1989)
612.
[22] G. Turrell, J. Corset (Eds.), Raman Microscopy Academic
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I am grateful to all the students and post-doctoral [24] R.J.H. Clark, Proc. Royal Institution 69 (1998) 151.
fellows associated with this work, most recently [25] T. Tuurnala, A. Hautojärvi, K. Harva, Studies in Conservation
Dr P.J. Gibbs and Miss L. Burgio. The research has 30 (1985) 93.
been supported by the EPSRC, The Leverhulme Trust, [26] L. Busotti, M.P. Carboncini, E. Castellucci, L. Giuntini, P.A.
The Royal Society and the ULIRS. Mandò, Studies in Conservation 42 (1997) 83.
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