JOURNAL OF RAMAN SPECTROSCOPY

J. Raman Spectrosc. 2004; 35: 600–604

Published online in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/jrs.1208

Identification by Raman microscopy of pigments on

early postage stamps: distinction between original
1847 and 1858–1862, forged and reproduction postage
stamps of Mauritius
Tracey D. Chaplin,1 Alicia Jurado-López1† Robin J. H. Clark,1∗ and David R. Beech2
1
Christopher Ingold Laboratories, University College London, 20 Gordon Street, London WC1H 0AJ, UK
2
Philatelic Collections, The British Library, 96 Euston Road, London NW1 2DB, UK

Received 16 January 2004; Accepted 21 March 2004

An extremely rare used 1847 1d orange–red Mauritian stamp, a rare 1847 2d deep blue unused stamp, a
1913 reproduction 2d stamp, early forgeries and 1858–1862 Britannia-type Mauritian stamps were analysed
using Raman microscopy in order to determine the identities of the pigments on the stamps. That in
the printing ink of the 1d stamp was identified to be lead(II,IV) oxide (‘red lead’), with a cancel mark
composed of carbon-based black. Prussian blue was identified as having been used in the genuine and
reproduction 2d issues, these being distinguished only by the presence of crystals of ultramarine blue
dispersed between the paper fibres of the genuine issues. The 4d green Britannia-type stamp is pigmented
with ‘chrome green’, a mixture of Prussian blue and chrome yellow, and the 6d ‘vermilion’ Britannia-type
stamp is pigmented with vermilion. Raman microscopy was shown to be a rapid, highly specific and
non-destructive technique for the expertising of stamps whose authenticity is in question via the precise
identification of the pigments used on the surface of each stamp and dispersed between the paper fibres.
Copyright  2004 John Wiley & Sons, Ltd.

KEYWORDS: pigments; postage stamps; Mauritian stamps; forgery; reproduction

INTRODUCTION printed in Mauritius one at a time, to a total of approximately

500 of each; these were known as the ‘‘Post Office’’ issue
In 1847, Mauritius became the first British Colony and the
as they had these words printed on the left margin of the
fifth country in the world, along with the USA, to issue
stamp. In 1848 one further issue was engraved and printed by
postage stamps. The postal system, which had previously
Barnard (the ‘‘Post Paid’’ issue). The 1d and 2d stamps were
existed under French rule, was reorganised and the Post
replaced in 1860 by new issues from London (De la Rue’s
Office Ordinance was passed, which led to the introduction
of stamps in denominations of one penny (1d) for letters typographed series). Other issues after 1848 were engraved
posted at the central post office for delivery in Port Louis, on copper by J. Lapirot (Lapirot issue, March–November
and two pence (2d) for delivery elsewhere on the island. 1859), successor to Barnard; in October 1848 the 2d stamp
The stamps were printed in 1847 by Joseph O. Barnard was re-issued using the original 1847 (‘‘Post Paid’’ issue)
(1816–65), who engraved the two values on a single copper plate, re-engraved by R. Sherwin (Sherwin issue); on 12
plate containing one example of each value; the stamps were December 1859, the lithographed issue by Dardenne came
into use (a listing of the early types of Mauritian stamps is
Ł Correspondence to: Robin J. H. Clark, Christopher Ingold given in Table 1).
Laboratories, University College London, 20 Gordon Street, Only 14 examples of the 1847 1d stamp are known still
London WC1H 0AJ, UK. E-mail: [email protected] to exist and only 12 of the 1847 2d stamps. One used 1847
† Present address: Analytical Chemistry Department, University of
Córdoba, Annex C-3, Campus Rabanales, E-14014 Córdoba, Spain. 1d stamp on an envelope and one unused 1847 2d stamp
Contract/grant sponsor: DGICyT. are held at the British Library as a part of the Tapling
Contract/grant sponsor: EU; Contract/grant numbers: 95-0270-OP; Collection, which is considered to be the only major collection
1FD97-0653.
Contract/grant sponsor: EPSRC; Contract/grant number: of stamps put together in the 19th century to remain intact.
GR/M82592. The rarity and hence great value of these Mauritian stamps,

Copyright  2004 John Wiley & Sons, Ltd.

 Identification of pigments on early postage stamps 601

Table 1. List of the early Mauritian postage stamps surface on irradiation with light of different wavelengths.1
Raman microscopy is shown here to offer a unique, rapid
Stamps
and very effective non-destructive way of assisting in the
1847 Post Office Barnard issuea
expertising of stamps, and it has recently been applied
1d orange–red
to distinguish between a Hawaiian Missionary stamp of
2d deep blue
1851–52 and a forgery.2 The present analyses led to the
1848–59 Post Paid Barnard issuea
identification of the pigments used on 1847 1d orange–red
1d orange–red
and 2d deep blue stamps, on 1858–62 4d green and 6d
2d deep blue
‘vermilion’ stamps, and to a basis for distinguishing genuine
1858–62 Britannia Perkins Bacon issueb
from forged stamps.
4d green
6d vermilion
9d dull magenta EXPERIMENTAL
No specified value, red–brown (prepared for issue but not Instrumentation
issued) All of the stamps were analysed using a Renishaw System
No specified value, blue (prepared for issue but not issued) 1000 Raman spectrometer coupled to a Leica optical micro-
1859 (March–November) Lapirot issuea scope and equipped with two laser excitation sources:
2d blue a helium–neon laser (
0 D 632.8 nm) and an argon
1859 (October) Sherwin issuea ion laser (
0 D 514.5 nm). The spectrometer is equipped
2d deep blue with a holographic notch filter and a dispersive grating
1859 (12 December) Dardenne issuec (1800 grooves mm
1 ). The analysis of the stamps was per-
1d red formed by directing the laser light on to the surface of the
2d blue item through the microscope objective, the inelastically scat-
Reproductions tered Raman light being collected through the same lens and
1913 reproduction made in France by A. Perrin of the 1847 1d transmitted via the notch filter to the spectrometer and on
and 2d stamps of the Post Office issue to a thermoelectrically cooled charge-coupled device (CCD)
a
detector operating at
70 ° C. The Raman spectra collected by
Engraved and printed in Mauritius
b
this method were compared with those included in the pub-
Engraved and printed in England
c
lished libraries of spectra obtained from reference samples
Lithographed in Mauritius
of pigments.3,4

the rarest realising up to about £1 million at auction, is Materials

such that they are often known as the ‘Crown Jewels of The Mauritian stamps studied were as follows:
Philately’ and, consequently, they have been copied and ž 1847 1d orange–red stamp, consisting of a central figure of
reproduction stamps are available. The so-called ‘Britannia- Queen Victoria on an orange–red background [Plate 1(a)]
type’ issues (1858–62), were printed in London by Perkins with text printed along each side of the stamp (the words
Bacon using the intaglio or line-engraving process, and have ‘POSTAGE’ at the top, ‘ONE PENNY’ at the base, ‘POST
their denominations indicated not by any printed number on OFFICE’ on the left-hand side and ‘MAURITIUS’ on the
the face but by the colours of the stamps. Examples of these right-hand side);
issues also form part of the Tapling Collection. ž 1847 2d deep blue stamp, with the same central figure
Here the first Raman spectroscopic analysis of the 1847 and wording, but printed on a blue background, with
1d and 2d stamps is presented, in which the identities of the words ‘TWO PENCE’ printed along the base [Plate
the pigments used in the manufacture are established. The 1(b)]; such 1d and 2d stamps are the only Mauritius ones
results are compared with those obtained for a reproduction to include the wording ‘POST OFFICE’ (the ‘Post Office
2d stamp (also held in the British Library, and printed in 1913 issue’);
by A. Perrin), and for two forgeries of the 1859 2d Lapirot and ž a 1913 reproduction of the 1847 2d stamp by A. Perrin;
Sherwin issues (held at the Royal Philatelic Society London). ž a set of five 1858–62 Britannia-type stamps, printed in
In addition, examples of 1858–62 Britannia-type Mauritian different colours to indicate denomination; 4d green;
stamps were studied for comparison, and the similarities 6d ‘vermilion’; 9d dull magenta; the remaining two,
and differences between the pigments used on these stamps red–brown and blue, were prepared for use but not issued;
and those used on the original issue are discussed. Previous all five consist of a central figure of Britannia within the
scientific analysis of stamps has focused on surface analysis coloured background [Plate 2];
to detect cleaned areas, postmark or cancel mark removal and ž two forged 1859 2d blue Lapirot and Sherwin (‘Post Paid’)
overprints using a CS-16 Crimescope light source to examine issues produced by photogravure (a semi-photographic
the reflection, absorption or luminescence of the stamp technique); the forgers are not known.

Copyright  2004 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2004; 35: 600–604
602 T. D. Chaplin et al.

a b

Intensity
Intensity

200 400 600 800 500 1000 1500 2000

Wavenumber/cm-1 Wavenumber/cm-1

c d

Intensity
Intensity

500 1000 1500 2000 2500 500 1000 1500 2000

Wavenumber/cm-1 Wavenumber/cm-1

e f
Intensity

Intensity

500 1000 1500 2000 2500 3000 200 300 400 500 600
Wavenumber/cm-1 Wavenumber/cm-1
Figure 1. Raman spectra of (a) red lead obtained from the 1847 1d stamp, (b) carbon-based black from the postmark or
cancellation on the 1d stamp, (c) Prussian blue obtained from the printing inks of the 1847 2d stamp and the reproduction stamp of
1913 (A. Perrin), (d) ultramarine blue obtained from the blue crystals detected between the paper fibres of the genuine stamps,
(e) Prussian blue–chrome yellow mixture from the green pigment used in the printing of the 4d Britannia-type stamp and (f) vermilion
used on the 6d Britannia-type stamp.

RESULTS AND DISCUSSION Original and reproduction 1847 2d stamps

The original and reproduction stamps are printed in
different shades of blue ink. Raman analysis of the inks
Original 1847 1d stamp yields the spectrum of Prussian blue, a synthetic iron(III)
The orange–red pigment used in the printing of the 1d hexacyanoferrate(II) pigment (Fe4 [Fe(CN)6 ]3 Ð 14–16 H2 O)
stamp was determined to be lead(II,IV) oxide (Pb3 O4 or ‘red first made in 1704 by the German alchemist Diesbach.5,6
lead’), which has been used as a pigment since antiquity. This compound gives rise to characteristic Raman bands at
The spectrum of this material yields characteristic bands at 2154 vs, 2128 sh, 2092 m, 1873 w, 1012 w, 953 w, 527 s and
548 s, 390 w and 315 w cm
1 [Fig. 1(a)]. The used stamp also 271 s cm
1 [Fig. 1(c)]. By comparison, the Raman spectra
possesses a black cancel mark which is shown by Raman obtained from the forged 1859 2d stamps (produced by
analysis to be composed of a carbon-based black material, photogravure) are characterized by intense fluorescence
with two characteristic bands in the spectrum at 1591 and which obscures the response from the pigments. The stamps
1334 cm
1 [Fig. 1(b)]. have a glossy film over them, which prevents the pigments

Copyright  2004 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2004; 35: 600–604
 Identification of pigments on early postage stamps 603

from being accessed by the laser beam. These stamps are numerical value was expressed, are known to have been
readily distinguished from the original printed stamps on altered into the much rarer and therefore much more valuable
the basis of this behaviour. green 4d stamp. Experiments on paper showed that this
Examination of the paper fibres of the stamps under a conversion could easily have been accomplished by painting
microscope showed that the original 1847 stamp contains the undenominated blue stamp with a slurry of chrome
blue crystals (ca 1–30 µm across) between the fibres, yellow (PbCrO4 ) in water and then allowing the stamp to
crystals which are unrelated to the printing ink. Analysis dry. Optical subtraction results in the same colour being
of these crystals yields the Raman spectrum of lazurite produced as when Prussian blue and chrome yellow are
(or more probably its synthetic analogue, ultramarine intimately mixed and used as the pigment ‘chrome green’.
blue, first made around 18285,7 ), a sodium aluminosilicate Such a fake can easily be detected by microscopic or Raman
mineral (Na8 [Al6 Si6 O24 ]Sn ) containing as its chromophores microscopic examination of the stamp edges; the faked 4d
the sulfur radical anions S3
and S2
.8 The Raman spectrum stamps reveal colour misalignments resulting from minutely
of this material is characterized by bands at 2181 w, separate regions of distinct pigments, whereas this is not the
1642.5 m, 1363 w, 1121 sh, 1093.5 s, 811 w, 583 w, 546 vs case for the genuine stamp formed directly from the pre-
and 261 w cm
1 [Fig. 1(d)]. The lazurite or ultramarine blue mixed chrome green pigment. The latter had been known
particles may have been deliberately added to the paper since the early–mid-1800 s, and has recently been discovered
fibres during manufacture to enhance the brightness of the on late 19th century overpaintings of a 16th century Greek
paper and/or to counteract the yellowing of paper fibres icon.9,10
with time. A similar examination of the 1913 2d reproduction
stamp of A. Perrin and the 1859 2d forgeries demonstrated
that they were devoid of blue crystals interleaved between
the paper fibres and hence could be differentiated from CONCLUSIONS
genuine stamps on this basis.
The analysis of these highly valuable Mauritian stamps
1858–62 Britannia type shows that the genuine 1847 2d stamp, its 1913 reproduction
The pigments on five Britannia-type stamps (Plate 2; 4d and the 1858–62 Britannia-type undenominated blue stamp
green; 6d vermilion; 9d dull magenta; undenominated were printed using the same pigment, Prussian blue. This
red–brown; and undenominated blue; the last two prepared may be due to the limited selection of blue pigments available
for use but not issued) were examined in order to determine for printing inks at this time. The more recent introduction
their identity. However, only three of the stamps yielded of synthetic blue compounds (e.g. the phthalocyanine and
Raman spectra suitable for this purpose. The blue pigment aniline blues) could provide invaluable date markers and
used for one of the unissued stamps was identified to be thus a useful means of detecting later forged or reproduction
Prussian blue, yielding the same spectrum as that shown items. The major difference between the original and the
in Fig. 1(c). Analysis of the green pigment on the 4d stamp reproduction stamps actually studied lies in the presence
yielded a Raman spectrum containing bands attributable to of an optical brightener, ultramarine blue, between the
Prussian blue, with additional bands at 336 w, 358 s, 374 m, paper fibres of the former. The two stamps forged using
401 w and 838 vs cm
1 [Fig. 1(e)], attributable to lead(II) photogravure are readily distinguished from the genuine
chromate (PbCrO4 ), commonly known in a pigment context stamp by the fluorescent response of their surfaces to the
as ‘chrome yellow’. The red pigment used on the 6d stamp incident laser. The ink used in the printing of the 1847
was identified to be vermilion, mercury(II) sulfide (HgS), 1d stamp is lead(II,IV) oxide (‘red lead’), with an applied
characterized by bands at 252 vs, 282 w(sh) and 343 m cm
1 postmark or cancellation composed of a carbon-based black.
[Fig. 1(f)]. However, the pigments used in the manufacture The 4d stamp is pigmented with ‘chrome green’, a mixture
of the 9d dull magenta and red–brown stamps could not of Prussian blue and chrome yellow, and the 6d stamp
be identified by this technique, high fluorescence completely is pigmented with mercury(II) sulfide. This study clearly
obscuring any Raman bands. shows that the Raman technique can now provide a precise,
A microscopic examination of the paper fibres of the rapid and non-destructive means of assisting philatelists in
five Britannia-type stamps showed that they all contain blue the expertising of stamps whose authenticity is in question.
crystals, as observed in the 1847 2d stamp. Raman analysis
of these particles shows that they are likewise composed of
ultramarine blue and that the spectra they yield are identical Acknowledgements
with that shown in Fig. 1(d). The crystals may in these cases A.J.-L. acknowledges the DGICyT (Spain) and the EU for financial
support (projects 95-0270-OP and 1FD97-0653) while on leave at
have been deliberately added to the paper fibres during
UCL and T.D.C. acknowledges the support of the EPSRC (grant
manufacture and used therein as optical brighteners. GR/M82592). Mr Patrick Pearson (The Royal Philatelic Society
Many of the 1858–62 undenominated blue stamps London) is thanked for the provision of certain stamps and for
produced by Perkins Bacon, i.e. the version on which no useful comments.

Copyright  2004 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2004; 35: 600–604
604 T. D. Chaplin et al.

REFERENCES 7. Plesters J. Artists’ Pigments: a Handbook of their History and

Characteristics 2. National Gallery of Art: Washington, DC, and
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and McCrone Research Institute: Chicago, IL, 2001; 55–65. 8. Clark RJH, Franks ML. Chem. Phys. Lett. 1975; 34: 69.
2. Chaplin TD, Clark RJH, Beech DR. J. Raman Spectrosc. 2002; 33: 9. Daniilia Sister, Bikiaris D, Burgio L, Gavala P, Clark RJH,
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3. Bell IM, Clark RJH, Gibbs PJ. Spectrochim. Acta, Part A 1997; 53: 10. The terminology used is that a forgery is regarded as a complete
2159. fabrication purporting to be something else whereas a fake is
4. Burgio L, Clark RJH. Spectrochim. Acta, Part A 2001; 57: 1491. something which has been altered to appear to be something
5. Wehlte K. The Material and Techniques of Painting. Van Nostrand else.
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Oxford University Press: Oxford, 1997; 191–217.

Copyright  2004 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2004; 35: 600–604
 Identification of pigments on early postage stamps

(a)

(b)

Plate 1. Photographs of (a) used 1d orange–red and (b) unused 2d deep blue Mauritian stamps of 1847.

Copyright  2004 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2004; 35
T. D. Chaplin et al.

Plate 2. Photographs of the Britannia-type 4d green, 6d vermilion, 9d dull magenta, unissued blue and unissued red–brown stamps
of 1858–62 (Perkins Bacon) for which the face value was determined by the colour.

Copyright  2004 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2004; 35