Anglo-Saxon Manuscript Pigments
Mark Clarke
There has been a lack of analyses of early manuscript pigments that use reliable and unambiguous
analytical techniques. An interdisciplinary methodology for identifying which pigments were used
on Anglo-Saxon manuscripts (those from England, c. 600 - c. 1066 AD) was applied, and a pilot
series of analyses was carried out. A list of likely pigments was compiled from contemporary
written sources, from analyses of near-contemporary European manuscripts, and from
archaeological finds of raw colourants or coloured artifacts. Pigments were analysed using microRaman spectroscopy and near-infrared imaging. Results are presented. Analysis provided data
mainly on inorganic pigments, and information on organic pigments was derived principally from
other indirect sources of evidence. Preliminary patterns of pigment use were identified, correlating
with the places, dates and workshops of origin. Minium, verdigris, carbon black and orpiment were
found throughout, with indigotiu in the earliest examples, and shellfish purple and lead while in
some de luxe books. Ultramarine started to be used c. 1000 AD but apparently only in Canterbury.
'There is some late use of azurite and red ochre. The results presented arc the first reliable ones
since 1885.
INTRODUCTION
This paper addresses the materials used as pigments on Anglo-Saxon manuscripts, i.e., manuscripts
made in England between c. 600 An (the date of the earliest surviving manuscript that was made in
the British Isles) and c. 1066 AD (the Norman Conquest). Manuscripts form one of the most
abundant bodies of surviving mediaeval material. Compared with other materials — say, textiles —
a considerable quantity survives: over a thousand manuscript books, plus approximately two
thousand other written items made in the British Isles during this period. They are also well
preserved — again, compared to textiles from the same period. Very-little coloured material
survives from the Anglo-Saxons other than manuscripts: no panel paintings, only fragments of wall
paintings, very few coloured ceramics, almost no coloured glass, and extremely little textile in
which the colour remains. Given that their literature clearly shows that they had a flamboyant taste
for colour, this is regrettable. The colours in manuscripts rectify this lack.
This research was prompted by the observations that not much is known about European artists'
materials in the period from the sixth to the eleventh century AD, that even less is known about
manuscript materials, and that for Anglo-Saxon manuscripts the problem is acute. Attempts to
identify pigments on Anglo-Saxon manuscripts began in 1885 with Hartley [1], with notable
contributions by Laurie (1914, 1935) and Roosen-Runge (1960, 1967) [2-4]. However, although
many publications treating the analysis of manuscript pigments are good, before this project began
in 1998 nothing had been published on Anglo-Saxon manuscript pigments that is not questionable.
Michelle Brown (curator of illuminated manuscripts at the British Library) had already identified
the need to analyse pigments on these manuscripts, and to evaluate the results of these earlier
publications. In 1996 she wrote:
A great deal of work has still to be accomplished on all aspects of the study of pigments, ranging
through topics as varied as identification and analysis, terminology, the study of sources relating to
manufacture and use, considerations of supply and availability, painting techniques and aesthetics. .
. The primary and most complex problems facing us are those of the identification and description
of pigments. [5]
Clearly, conservators need to know about the materials of artifacts to formulate conservation
strategies and treatments, and this point need not be laboured here. Analysis of the physical
construction of manuscripts also helps art historians to understand processes and stages of
production, including restorations. One such mediaeval renovation of a manuscript will be
discussed below. Furthermore, manuscript typology is usually based on subjective visual
examination, but clearly different craftsmen may create similar effects in different ways, for
example by using different pigments to produce a given colour. One aim of analysis is to determine
correlations between groups of manuscripts and the groups of materials used in their manufacture,
as an aid to establishing origins. The use of book artists' materials has frequently been represented
as though it were uniform throughout Europe, and unchanging between the fifth and the fifteenth
centuries AD. The reductio ad absurdum would have an eighth-century illuminator on Lindis-farne
(a tiny, inaccessible British island) and another in Paris c. 1500 AD, working with the same set of
materials. While there would have been some constants, it seems obvious that these craftsmen
would have had different materials available. This research aimed to look for such differences. It
was limited to pigments; inks and media were not examined.
The preferred method of determining what pigments were used is to use the direct evidence of what
is there now, established through analysis. Should this prove impossible or inadequate, due to
logistic difficulties and the requirements for non-sampling analysis as outlined below, indirect
evidence may be used, such as contemporary written sources that describe the manufacture of
manuscripts, or the analysis of other contemporary pigmented and dyed artifacts. Such evidence
also helps to establish a list of what might be present, which is useful since many methods of
analysis require samples of known composition for use as reference materials.
Direct evidence was derived from micro-Raman spectroscopy (µRS) and near-infrared imaging
results. Results were also used from a few analyses of further Anglo-Saxon manuscripts that have
been published by other authors subsequent to this research:
• Further µRS analysis at the British Library by Brown et al. [6-9]
• X-ray fluorescence (XRF) spectroscopic identification of shellfish purple by Porter et at. [10,
11]1
Direct analysis was only able to provide results for inorganic Anglo-Saxon pigments, plus indigotin
(the colourant derived from both indigo and woad) and shellfish purple. For organic pigments it
was mainly necessary to rely on indirect evidence:
• Published analyses of other mediaeval manuscripts [2]. (This review confirmed that before
2002 there were no published analyses of Anglo-Saxon manuscripts by unambiguous techniques.)
• The Anglo-Saxon archaeological record, including analysis of other contemporary coloured
material remains, and also the archaeobotanical and zoo-archaeological record.
• Contemporary written sources.
INDIRECT EVIDENCE FOR PIGMENTS AVAILABLE TO THE ANGLO-SAXONS
Anglo-Saxon England was far from isolated. It is known that chain networks allowed the transport
of prestige goods over enormous distances. Books were certainly transported widely, and imported
luxuries such as spices, ceramics, precious metalwork, silks and ivory were all known in AngloSaxon England. It follows that any colouring material, however exotic, might in principle be found
on an Anglo-Saxon manuscript. While not all colourants are suitable for all purposes, there are
materials common to the various polychroming crafts. For example, ochres may be used for
parietal art, ceramic glazes, furniture, sculpture, miniatures, body painting, and animal marking. It is
also common to prepare dyes in such a way as to make them into pigments, e.g., madder, weld or
kermes. Evidence for colouring materials that may have been available was collated. Since it may
not yet be possible to determine
1
Although unsupported by analysis, it has often been suggested that the purple used on early
mediaeval manuscripts is shellfish purple (6-6'-dibromo-indigotin), and it has equally often been
stated that it is not. It has at last been identified on a late eighth-century Anglo-Saxon manuscript,
Vatican City, Biblioteca Apostolica Vaticana, MS Barb. lat. 570, known as the Barherini Gospels.
Using non-sampling XRF, in two different attempts separated by several years, bromine was
detected in purple-coloured text, which almost certainly indicates the use of shellfish purple [10,
11]. (Minium, orpiment, vergaut and organic reds and blues on chalk substrates were also found
[11].)
exactly by analysis what pigments are present, particularly in the case of organic pigments, this
indirect evidence is in some cases the only clue. In this study, indirect evidence was all that could
be used for the majority of organic pigments. A considerable body of evidence was unearthed, and
it is only possible to summarize it here; the reader is referred to the unpublished report [12], and is
invited to contact the author.
The Anglo-Saxon archaeological record
A number of analyses of Anglo-Saxon remains have been published that report the presence of
colourants on textiles, ceramics and wall paintings. Given the difficulty of analysing organic
pigments without sampling, particular attention was paid to organic colourants. Archaeobotanical
and zooarchaeological records were searched for evidence of the raw materials usable tor dyes, and
therefore for organic pigments. Anglo-Saxon and Anglo-Scandinavian finds are clearly the most
relevant, but possible precursors to the technology of the Anglo-Saxons were also considered,
including Romano-British finds, as were its possible continuation in the form of finds from
immediately post-Anglo-Saxon England.
First, it may be concluded that recent re-evaluation of the evidence (both the exact translation of
classical literary references and recent archaeological finds) shows that the precursors of the AngloSaxons, i.e., the ancient Britons, were indeed using woad, and very probably using it as a body paint
[13]. Based on fragments of Anglo-Saxon wall paintings, and on late Romano-British examples,
pigments certainly used by the Anglo-Saxons included carbon black, lime white, red ochres and
yellow ochres [12, 14]. Anglo-Saxon ceramics were generally unglazed, and so had no pigments
used in their manufacture, until the tenth century, when there is evidence for use of lead pigments.
Dyes detected on Anglo-Saxon textiles are indigotin, madder (R. tinctoria L. and R. peregrina L.),
kermes (presumably imported), weld (Reseda luteola L.), Galium verum L., lichen purples and
some unidentified purple [15, 16]. Residues were also detected on several Anglo-Saxon ceramics,
indicating that they were used for preparation or storage of madder [17, 18].
The archaeobotanic evidence for dyeplants in the British Isles, up to c. 1100 AD, was reviewed for
evidence that suggested human exploitation (farmed or gathered) rather than merely a presence
(growing wild and unexploited), in which case they might have been used for pigments. The
survival of plant remains is uneven: woody remains may survive, but much delicate plant material
will not (e.g., mosses, lichens, milled woad, saffron stigmas). Archaeological evidence for
dyeplants in the British Isles was extracted from the Archaeobotanical Computer Database
maintained at the Environmental Archaeology Unit, University of York [19]. In Anglo-Saxon
contexts there is evidence for Calluna vulgaris L., Galium verum L., Genista tinctoria L., Isath
tinctoria L., Moms nigra, Myrica gale L., Prunus spinosa L., Reseda luteola L., Rhamnus
catharticus L., Rubia tinctorum L. and Sambucus nigra L. Evidence for the exploitation of the
dogwhelk, Nucella lapillus L., has been found [20], but it is possible that it was used for food or
bait, and not for dye.
Contemporary written sources
The archaeological evidence for Anglo-Saxon craft practices and available raw materials may be
supplemented by reference to contemporary texts, although the reliability of these as accurate
descriptions of Anglo-Saxon practice is open to question. Sadly, there is no text written by an
Anglo-Saxon author in which the processes and materials of making pigments are described.
However, many other mediaeval artists' paint recipes do survive (from outside England within this
period, and from England but outside this period) [21], and may be supplemented by numerous
other Anglo-Saxon references to pigment and dye materials, e.g., farming treatises, place names and
riddles. These include literature written by the Anglo-Saxons and also that definitely known to
them, including classical texts (where these can be demonstrated to have been available in AngloSaxon England, by the evidence of quotations or by surviving copies, such as Vitruvius, Pliny and
Dioscorides, and extracts from Theophrastus), and books by early mediaeval and contemporary
authors.
Several Old English riddles describe book materials and production, but sadly none gives
information regarding pigments. Only one actual Anglo-Saxon recipe was found which describes
the use of a pigment. It is in Old English and is a medical recipe that only mentions a pigment in
passing, as an analogy: 'For hare lip, pound mastic very small, add the white of an egg, and mingle
as you do teafor [to make a salve]' [22]. 'Teafor' is some red mineral pigment, although it is unclear
which. The recipe is interesting as it suggests that this pigment was used by grinding it finely and
adding egg white. Certainly egg white, 'glair', is known to have been a common medium for
mediaeval painting. An eleventh-century treatise on practical farming (Corpus Christi College
Cambridge MS 383) advises that in spring one should set out madder and woad. In an often-cited
passage Bede refers to shellfish dye in England [5, 11]. A ninth-century letter requesting pigments
survives, which lists orpiment, indigo, minium, 'lazur' and 'prasinum' (literally 'leek-green') [3, 5],
but the identity of the last two items is uncertain [5, 12]. Old English plant names (found in various
texts) that have been identified include the dye plants Calluna vulgaris L., Crocus sativus L.,
Galium verum L., Genista tinctoria L., Isatis tinctoria L., Moms nigra, Myrica gale L., Prunus
spinosa L., Reseda luteola L., Rhamnus catharticus L., Rubia tinctorum L., and Solarium nigrum L.
[23].2 Place names, too, can provide evidence for the existence of plants grown there; a case has
been made for saffron but this is disputed, and the only plausible evidence is for a number of place
names including 'wad', i.e., woad [24]. Given the very small amount of technical information
deducible from literature that was demonstrably known in Anglo-Saxon England, it is clearly
necessary to look at further sources. A search was made for mediaeval recipe books written for
painters and illuminators, and the results (cataloguing more than 400 manuscripts that contain such
recipes) have been published elsewhere [21]. Although none is from England, 20 such 'recipe
books' survive from before c. 1100 AD (several of these repeat one another), and there are four later,
Anglo-Norman examples.3 There are also several intriguing pieces of evidence that suggest that the
well-known early mediaeval craft treatise Mappae clavicula passed through England at some point
before the twelfth century [25], and it has also been suggested that De coloribus faciendis by Petri
de Sancto Audemaro (Paris,
2
Identification is being continued by the Anglo-Saxon Plant Name Survey, headed by Dr C.P.
Biggam, University of Glasgow: http://
www2.arts.gla.ac.uk/SESLL/EngLang/ihsl/projects/plants.htm (accessed 5 April 2004).
3
For details of these manuscripts, and of their published editions and translations, see the following
catalogue entries in [21]: 3rd-4th century: 1335, 1340, 3190 (Leiden and Stockholm papyri); 9th
century: 1045, 1105, 1270, 2020 (Lucca MS), 2155, 3020, 3216; 9th-10th century: 3100, 1310,
1320 (Mappae clavicula portions), 3280; 11th century: 125, 140 (De Clarea), 1222, 1305, 2730
(portions of Theophilus and of the Mappae clavicula); 11th century: 3030 (Heraclius extracts);
Anglo-Norman llth-13th century: 1480, 1630, 1900, 1490. For the Mappae clavicula see [25], and
for item 1490 see [26]. Roosen-Runge used the Mappae clavicula and Heraclius as a basis for his
study of Anylo-Saxon manuscript pigments [4].
Bibliotheque Nationale MS latin 6741, ff. 52-64) includes Anglo-Saxon recipes which had been
handed on to the Normans [27].
In these early 'recipes' there is actually very little that can be used directly as a recipe for
reproducing the materials of Anglo-Saxon scribes and illuminators. Many are vague in their
procedural details and in the identification of materials. Furthermore, the recipe texts are not always
reliable indicators of actual workshop practice, and some discretion must be exercised when using
them [21]. What the texts can give us, in addition to a few clues as to likely practice, is a list of
potential paint materials. If all recipe books prior to f. 1100 AD are taken together, there are many
clearly identifiable materials: artificial copper blues, azurite, animal galls, bistre, bone and horn
white, brazil, chalk, indigo and woad, kermes, lac, lead white, madder, malachite, ochres, orpiment,
red lead, saffron, elderberry (Sambucus nigra L.), sloe (Prunus spinosa), black nightshade
(Solanum nigrum L.), terre verte, Tyrian purple, ultramarine, verdigris, vermilion/cinnabar and
weld. A few materials are difficult to identify with certainty based solely on the texts. Translating
mediaeval technical terminology is controversial and difficult. For example 'dragonsblood' is not
necessarily always what we now call dragonsblood (i.e., the red resin), 'prasmus' ('leek green') is
unidentified, and there are a couple of candidates for 'lead yellow'. 'Folium' has been identified from
certain descriptions as being Chrozophora tinctoria Jussieau, and the purple produced by this plant
has indeed been identified on mediaeval manuscripts more than once, but in other texts 'folium'
clearly means indigo or even minium [12, 21].
DIRECT EVIDENCE: ANALYSIS OF PIGMENTS ON MANUSCRIPTS
In the last few years, increasingly sensitive, reliable, unambiguous and non-invasive techniques
have become available that can be used on paint that remains in place on the manuscripts, i.e.,
without the need to take samples, and consequently analysis of manuscripts has become more
common. A historical literature review of the analysis of mediaeval manuscript pigments, its issues
and problems, suitable and unsuitable techniques, was carried out, together with a tabulation of
published results [2].
Historically, the main obstacle to the analysis of manuscripts has been technical. Since the
pigmented area of a manuscript is so small, and so thinly applied, it is difficult to remove sufficient
material for analysis without leaving a visible loss. Non-sampling, nondestructive techniques are
therefore required.
For many years, to avoid damage, only visual examination or colorimetry was used. (Not everyone
was concerned to avoid damage. Antonio Fabroni '. . . tore out pages, dampened them and set them
under a glass dome in order to expose them to gaseous reagents' [28].) Much has been published
using identifications based on these techniques, but they can often be unreliable. A comparison of
the conclusions of six authors from 1885 to 1994 who used these techniques on the Book of Kelts
(Irish, c. 800 AD) showed that they agreed only on the presence of orpiment [8], and as will be seen
below, for two of the manuscripts in this study, visual examination and uRS give very different
results.
It was decided not to use UV-visible spectroscopy for pigment identification. UV-visible
spectroscopy has been found to work in transmission for certain dyes and pigments. However, when
used in reflection it suffers from poor specificity. Spectral features tend to be broad, non-unique,
and not always consistent. Mixtures of pigments cannot be resolved. Several different pigments
have very similar spectra [29, 30]. Indeed, mediaeval treatises rely on this, and contain many
recipes for imitating expensive colours such as ultramarine or Tyrian purple [21]. Conversely, any
one pigment may exhibit different colours under different conditions, for example due to particle
size [31], degradation, or differences in preparation method, medium or pH [2, 12, 29]. In some
cases the differences between the spectra of pairs of different organic pigments can be less than the
differences between different samples of the same pigment. Example spectra demonstrating these
phenomena have been published by the author [29].
It is notable that (at the time the project began) every published analysis of Anglo-Saxon
manuscripts had been based solely on visible-light reflectance spectroscopy and/or visual
examination. In the summary of published manuscript analyses given in [2], the results based solely
on these techniques were omitted due to their unreliability. The columns for analysis of manuscripts
from the eighth century and earlier are consequently blank. The present research, therefore,
produced the first reliable, unambiguous analyses of Anglo-Saxon manuscripts.
With non-sampling techniques of analysis, a common problem has been that of bringing equipment
and manuscripts together: the equipment is generally too large or too fragile to transport to the
library, and many curators are reluctant to allow valuable manuscripts to be taken to a laboratory.
This is due to the risks — real or perceived — of accidental damage in the laboratory, or of loss or
damage in transit. Libraries have been charged extremely high extra insurance costs to take even
one manuscript to a laboratory for a single day. The choice of technique is therefore often restricted
to instruments that can be moved without too much difficulty.
Recently, Raman micro-spectrometers have been made sufficiently 'portable' to permit their
relatively widespread use for manuscript pigment analysis. Either fibre-optics or a microscope can
be used to guide the laser light to the surface of the manuscript [2, 31, 32]. µRS was therefore
suitable for this study. Raman spectroscopy is, however, at present only well suited to inorganic
pigments, in part due to the intense fluorescence of organic pigments, which masks any Raman
signal, and the problem of analysing organic pigments using non-sampling techniques remains
largely unsolved. For this project an attempt was made to analyse organic pigments by using 'threedimensional' fluorescence reflectance spectroscopy but this was unsuccessful, due partly to broad,
variable and non-specific spectral peaks, but mainly to the fluorescence of the parchment support
[33]. An additional simple portable method of identifying certain blue pigments using near-infrared
imaging techniques was developed, with some success [34].
MANUSCRIPTS EXAMINED
Two collections were used: the Parker Library of Corpus Christi College, Cambridge (CCCC),
which holds about 10% of all surviving Anglo-Saxon manuscripts, and the British Library, London
(BL), which holds about 20%.
Ideally, every pigment on every manuscript would be identified, using whatever techniques are
necessary. In practice, resources, apparatus and time are all limited. Two complementary strategies
were employed, based on available equipment:
1 A large number of manuscripts at CCCC were examined using the limited but simple technique
of near-infrared imaging (NIR), which was used to distinguish between blue pigments. Exclusive
use of the NIR instrument, and unlimited time, meant that every folio of every manuscript that had
blue paint could be examined. This selection included all 75 Anglo-Saxon manuscripts in the
collection, plus 16 from the twelfth century or borderline twelfth/ thirteenth century.
2 At the BL, a small amount of time was available on a Raman micro-spectrometer, so only
seven manuscripts were examined, but in greater detail, to identify a wider range of pigments than
NIR allows.
EXPERIMENTAL PROCEDURE
Ideally, every coloured area, however small, would be examined, even when these areas are
apparently the same colour. Imaging techniques are particularly suitable for this type of
comprehensive examination, and for NIR this was done, so that every use of blue on every page
was examined. Common practice, however, is to analyse only one or two examples of each area of
colour that may be distinguished by eye, and for uRS analysis this practice was followed. All
analysis was carried out without sampling.
Visual examination
The manuscripts were first examined by eye to determine the range of colours (as opposed to
pigments) used. This preliminary step identified areas for analysis and suggested a possible shortlist
of pigments.
Near-infrared imaging
Near-intrared imaging for wavelengths 700-950 urn (using either false-colour infrared photography
or electronic cameras) has been shown to be useful for distinguishing certain pigments. While it is
ambiguous for some sets of pigments, it seems to be reliable for distinguishing between the blue
pigments found on early mediaeval manuscripts [34].
A small reference swatch was made up with painted squares of indigo, azurite, ultramarine and
smalt, which could be imaged alongside the manuscript, as a control for colour, processing and
lighting variations. Smalt is not to be expected on such early artifacts, but it was added to the
swatch so that it could be used for examining later manuscripts. A modified night-vision sight was
used: a simple, inexpensive, hand-held battery-operated device, superficially resembling a video or
cine camera (SM 2-P, Abris, Minsk, Belarus), and fitted with a Hoya filter R72, which transmits
only NIR (wavelengths >730 nm). Azurite appears dark (because it absorbs strongly in this region)
while ultramarine and indigotin (and smalt) appear light. Two assumptions were made: first, that
smalt is not a possible candidate for manuscripts between the sixth and twelfth centuries; second,
that of the two other pigments that appeared light or transparent in NIR, the opaque blue pigment
was ultramarine and the transparent grey-blue pigment was indigotin. A possible criticism is that
there do exist contemporary recipes that have been interpreted as being for organic blues [e.g., 25,
35]. Furthermore, a few exceptional, late finds of Egyptian blue on English sculpture show that this,
too, may have been a possibility |36|. However, although it does not exclude the possibility that
other blues were used, the NIR identifications ot the blues on the BL manuscripts were confirmed
by uRS and in all cases found to agree, so these assumptions did seem to be justified.
Micro-Raman spectroscopy (µRS)
A Renishaw system 1000 Raman spectrometer (a dispersive instrument) was coupled to a Nikon
microscope. 632.81 nm (He-Ne), 514.5 nm (argon ion) and 780 nm (diode) lasers were available.
The 632 nm and the 514 nm lasers were used with the microscope, and the 632 nm and 780 nm with
a remote fibre-optic probe. This probe also incorporated a video camera enabling the user to aim
and focus the exciting laser. A 20x microscope objective lens was used, with a spot diameter of
about 10 µm and a working distance of about 12 mm. The vibration of the system made focusing
problematic. As a result, only a 20x lens could be used, compared to 50x on the normal Raman
microscope. The laser power is also reduced by the fibre-optics to about 50%. Published reference
spectra of historical inorganic pigments were used to interpret the results [37]. The points analysed
were documented by marking colour prints of the manuscript pages.
RESULTS
Visual examination
Every folio of the 98 manuscripts was inspected, as were a number of BL manuscripts that it was
not possible to analyse. This preliminary visual examination showed that the Anglo-Saxon palette
was initially quite limited but gradually became more varied with time. In general, the range of
colours in each manuscript was small. Apart from a few exceptionally lavish examples, manuscripts
typically contain one or two reds, one yellow and one green, rather than a range of hues or shades of
red, yellow or green, and they generally contain no intermediate shades. Each occurrence of a red,
yellow or green within a given manuscript appears to be roughly the same hue, saturation and
brightness (although this was not measured). Although more rigorous analysis would be needed to
prove it, this suggests that — for the earlier manuscripts at least — only one pigment was
used per manuscript for each primary colour, and that mixing pigments to obtain intermediate
colours was not common. The range of colours and pigments increases with time. Seventh- to
eighth-century manuscripts have a particularly restricted range of colours: purple, orange-red (the
colour normally associated with minium), green and a brownish-yellow. These all have the
appearance of thick, opaque inorganic pigments. Some translucent purple is also occasionally
present. In the ninth century a more saturated, intense, opaque yellow appears, as does blue (which
is somewhat grey and translucent). In the tenth and eleventh centuries this range of colour expands,
with the introduction of blues that are more intense and saturated, a second red colour (which is less
orange than the first) and a transparent pale yellow-brown. The colouring material of pages that are
fully coloured purple (e.g., BL Royal 1 E.vi) varies from thin to thick, but is usually quite dark.
Near-infrared imaging
The NIR imaging device used is a real-time instrument, so work could progress very quickly — as
fast as manuscript pages could be turned and the results written down. Of the 75 Anglo-Saxon
manuscripts examined, only 18 contained blue. The results are summarized in Table 1. The use of
blue pigments was observed to vary with period. The earliest manuscripts contained no blue at all.
In the ninth century manuscript, only indigotin was found. The earliest examples of ultramarine
were in the late tenth century, in a few de luxe manuscripts. Ultramarine was used in most eleventhcentury manuscripts. Azurite was found in a very small number of eleventh-century manuscripts.
(One limitation of NIR is the possibility that, if azurite were present as an under-layer to an
ultramarine top layer, the azurite would absorb the NIR, so giving no indication of the presence of
ultramarine. It would be interesting to test this in these few occurrences by analysis of the top
surface using µRS.) Two manuscripts gave ambiguous results, i.e., where the reflection fell between
the possibilities and it seemed unsafe to decide one way or the other. The blue colour of CCCC 183
was neither clearly ultramarine nor clearly indigotin, and CCCC 356.ii absorbed only slightly. All
the twelfth-century manuscripts examined contained only ultramarine (these are not included in
Table 1).
Micro-Raman spectroscopy
Pigment identifications of BL manuscripts are summarized in Table 2.4 The uRS results for blues
agreed with
Table 1
Blue pigments identified on CCCC manuscnpts by near-infrared analysis
4
Some of these results were presented at the IIC Congress in Baltimore 2002 \9\.
Table 2 Pigments positively identified on BL manuscripts (micro-Raman spectroscopy and nearinfrared analysis)
the NIR results. Several pigments could not be identified. These included brown, red, pink, green,
purple, yellow, orange, blue, black and white examples. This lack of match could be due to the
incompleteness of the set of reference spectra. Alternatively, it could be due to the presence of
organic pigments. Many of the painted areas on the manuscripts exhibited fluorescence, suggesting
that they contain organic pigments.
DISCUSSION
The pigments that were identified with confidence during this research as being present on AngloSaxon manuscripts are summarized in Table 3. This table shows, for comparison, which pigments
were identified on other European manuscripts in published analyses (marked 'e'), with summary
data; full details are provided in [2].
Table 3 Pigments positively identified on Anglo-Saxon manuscripts*
*Pigments identified on other European manuscripts are included for comparison.
Key
A
A*
I
B
L
e
()
!
Anglo-Saxon
late tenth-century Anglo-Saxon
Insular
Barberini Gospels
Lindisfarne Gospels
other European (adapted from [2])
probably added later
exceptionally early
The use of blue pigments was observed to vary with period. Furthermore, this agrees with practices
just across the English Channel. Coupry analysed pigments from nine Norman manuscripts dating
from the late tenth century to c. 1 139 AD using µRS [38]. She found that indigotin was used in one
manuscript from the late tenth century, and that ultramarine was introduced c. 1000 AD. (Coupry
also found that vermilion did not appear until c. 1000, after which it gradually replaced minium.
This agrees with the presence of minium and absence of vermilion in the BL manuscripts.)
Interesting results can be obtained by comparing individual manuscripts with even such a simple
pattern as that of blue pigment use. For example: in the past it has been suggested that the late tenthcentury manuscript CCCC 23.i (Figure 1) was made at Canterbury Christ Church Cathedral |39]. It
was found to contain ultramarine. According to the pattern of use described above, it is rare to find
ultramarine this early. The only contemporary Anglo-Saxon manuscript examined which also had
such early use ot ultramarine was BL Cotton Cleopatra C.viii, for which a Canterbury Christ
Church origin is more certain [39]. These illustrations are line drawings, and it is impossible that the
blue is a later addition. From text and image it is clear that these two manuscripts were in fact
copied from a common example, and they are known to be closely related. While finding
ultramarine in a late tenth-century manuscript is not sufficient evidence for a common origin, or a
Canterbury Christ Church origin, clearly its presence is exceptional and so adds weight to the
suggested link.
Patterns of pigment use also allow us to detect intrusive elements, present due to later
improvements, additions, repairs or forgeries. The pattern ot blues determined by examination of
the CCCC manuscripts suggests that if, for example, ultramarine is present in an eighth-century
manuscript, then it is likely to be a later addition. (This interpretation should not be made by an
analyst alone, but in cooperation with an art historian or codicologist.)
Ultramarine was indeed found in an early manuscript that should, if these patterns are correct, be
too early to contain it: BL Add. MS 40618. This is an 'Insular' manuscript (i.e., an early one from
somewhere in the British Isles, either Ireland or Anglo-Saxon England), originally written and
decorated in the eighth century. If this ultramarine is original, it would be the earliest known use as
a pigment on a manuscript from the British Isles. However, in addition to these eighth-century
pages where ultramarine was found (f. 23r and
Figure 1 CCCC MS 23.i, folio 8, detail. Probably Canterbury, Christ Church Cathedral, c. 1100
AD. Note that the ultramarine must have been part of the original design. (This image is reproduced
in colour on the front cover of this journal.)
f. 50r), there are some additional pages of later, tenth-century illustrations, which also contain
ultramarine, that have been pasted in (f. 22v and f. 49v). Our new knowledge of the typical pattern
of pigment use suggests that ultramarine may have been added to enhance the original decoration at
the same time as the new pages of illustrations were added. And, on close inspection, so it seems.
The miniature that is clearly an unretouched eighth-century example (f. 21v) has no ultramarine.
The ultramarine-containing eighth-century pages (f. 23r and t. 50r) can be seen to have been heavily
overpainted, in one case (f. 50r) also with gold.5
The presence of lead white on two eighth-century manuscripts, the Litidisfarne Gospels and BL
Cotton Vespasian Al, was reported by Brown ct al. [6-8]. This is particularly surprising. It has not
been found on other manuscripts (Anglo-Saxon or from elsewhere) until the eleventh century.
Indeed, close inspection seems to indicate that in general no white paint was used on British
manuscripts before the eleventh century. White fields are reserved rather than painted, and no white
is used for highlights. White is found on occasional de luxe Anglo-Saxon manuscripts prior to the
eleventh century, e.g., the late ninth-century BL Royal 1 E.vi (on f. 43r), and on the late eighthcentury Barberini Gospels (t. 51r). There are also white highlights on the sixth-century
5
For the dating of the different pages and for observations on the overpainting see, e.g., \39\.
Italian CCCC 286 (f. 129v). This may have been a stylistic choice, rather than a consequence of
unavailability. Dormer has made a case for a hierarchy of importance for drawn (with whites
reserved) and fully painted (with white paint) English manuscript illustrations from the tenth
century onward [40].
Both lead white and chalk were found on the Lindisfarne Gospels only in mixtures with organic
colourants [6, 8]. The Lindisfarne Gospels is, however, an exceptional and experimental manuscript
[41], with unusually lavish illustrations, and its palette is particularly rich. (Being so
unrepresentative, it has therefore been shown separately in Table 3.) Elsewhere — in the
unretouched eighth-century miniature of Add. MS 40618 and in the early ninth-century Royal 1
E.vi — gypsum was found in red areas. XRF also detected some calcium-containing mineral
(perhaps gypsum, but perhaps chalk) mixed with organic reds and blues in the contemporary and
equally lavish Barberini Gospels [11]. These may be simple pigment mixtures. Alternatively, they
may represent some unusual form of lake pigment or dyed white substrate, or coloured washes over
the opaque white. A similar faded red was noted in the tenth-century CCCC 422, e.g., f. 99r.
Although it is perhaps unsafe to speculate in the absence of analysis, the pale appearance of many
painted areas in Anglo-Saxon manuscripts suggests that they contain faded organic pigments
(Figure 2). In particular, a tew have a pale, transparent yellow-brown paint which is almost the
same colour as the parchment. The paint can be extremely thin. In other cases the paint can be as
Figure 2 CCCC MS 69, folio 1r, detail showing the faded yellow and red pigments. Northumbria,
eighth century.
thick as the other paints present, but with a brown, pale or almost colourless hue. This thick paint,
when examined under a microscope, is very shiny and translucent, and has a pronounced
craquelure. Generally Anglo-Saxon manuscript paints are all strong and bright, and a subtle or drab
yellow-brown seems out of place. In the case of the more transparent yellow, the contrast with the
parchment is negligible. Even allowing for some darkening and yellowing of the parchment, if this
'yellow' paint had always been approximately this colour, it would have made no decorative sense
to apply it, especially given that the other colours used are so strong. The colours of these faded
pigments would surely originally have been similar in saturation and brightness to the other colours
that remain. This suggests that organic pigments were used, as stains in a clear adhesive medium.6
For a strong colour, this would need to have been applied thickly. That it contained a yellow dye,
now faded, is a plausible explanation for the thick, yellowed, glassy, cracked 'paint' that is found,
surely more plausible than the suggestion that it was always this colour. While organic pigments of
several colours may discolour to pale buff-yellow, where these pale yellows are found it can usually
be seen that a strong yellow would make decorative sense. Organic yellows are particularly prone to
fading, often to the point of indetecta-bility. The most likely candidates for this faded yellow-are
saffron (Crocus sativa L.), safflower (Carthamus tinctorius L.) and weld (Reseda luteola L.),
although, of these, only weld is known with certainty to have been available in Anglo-Saxon
England. Roosen-Runge suggested that on the Lindisfarne Gospels the yellow might be animal gall,
probably ox gall [3].
There are several places on the CCCC manuscripts where a pale red or red-purple may be seen.
Like the pale dull yellows, their pale appearance makes no decorative sense, and it seems more
likely that these, too, are faded organic pigments. What red pigment they contain is uncertain.
Certainly madder was known to the Anglo-Saxons, and both madder and kermes have been
identified on Anglo-Saxon textiles [12, 15, 16]. We have seen that Brazil was apparently known to
6
The twelfth-century BL manuscript Cotton Titus D.XXIV contains Anglo-Norman colour recipes on
ff. l27r-130v [26]. Most arc for tempering, including an interesting recipe for the use of brazil
scrapings added directly to glue size. The mention of size as an illuminator's medium is unusual in
mediaeval recipe books, although parchment size was one of the media the author observed being
used by scribes in Axum, Ethiopia.
illuminators in England by the twelfth century [26|, and that shellfish purple was used, at least in the
eighth century [10, 11] .
Comparison of results: µRS versus visual examination
Roosen-Runge (in the 1960s) [3. 4| and Dormer (in 1991) [40] both used visual examination to
identify pigments on several Anglo-Saxon manuscripts. Both expressed clear warnings as to the
limitations of visual examination, but nevertheless this technique continues to be used. When
selecting BL manuscripts for u.RS analysis, those examined by Roosen-Runge were prioritized,
partly because they are important and much-decorated examples, but also as a way of testing the
accuracy of the pigment identifications [12]. On BL Arundel MS 155 f. 133r the µRS results agree
with the conclusion that minium was present but disagree on every other pigment. The µRS results
agree with that on Lindisfarne: there is minium, verdigris, indigotin, orpiment and vergaut (a green
mixture of orpiment and indigotin). µRS also showed that lead white is mixed with an organic red
in some pink areas, and with indigotin in some blue areas [8]. The most notable disagreement
concerns ultramarine. Roosen-Runge and Dormer concluded quite firmly that it was present
throughout, but lazurite was not found in any of the µRS analyses [8, 41]. Although it is unfair to
dismiss visual examination as a technique on the basis of only a few µRS analyses, it does appear
that reported deductions based on visual examination have been incorrect. In consequence, the
analytical results presented here are probably the first reliable ones published since analysis of
Anglo-Saxon manuscript pigments began with Hartley in 1885.
CONCLUSIONS
Although not many full analyses were performed, already it can be clearly seen that such analyses
are useful, and that the results suggest useful patterns. One issue to emerge is that there is a problem
with selecting areas for spot analysis. However densely packed the sampling areas, pigments can be
missed. During the collaborative µRS work, only ultramarine was identified in the hair of St
Benedict in Arundel MS 155 f. 133r [12], but the subsequent recent publication by Brown and
Clark reports indigotin as well [7|. This is where imaging techniques can be so helpful, as they
cover all areas. Unfortunately they are not yet capable of distinguishing a very wide range of
pigments. Conversely, µRS found indigo where present in the mixed pigment vergaut, whereas the
imaging technique could not. (The author was disappointed to read of the presence of indigo in this
eleventh-century manuscript, as until then there was a satisfyingly simple pattern for blues: indigo
in early manuscripts, replaced by ultramarine c. 1000 AD. The pattern is now more complex.)
Clearly, much remains to be done. Organics in particular remain a problem, and micro-sampling
techniques seem at present to be the only satisfactory solution. While the micro-Raman
spectroscopy and near-infrared analysis were useful for identifying the inorganic pigments, at
present the only evidence we have for which organic pigments might have been used (other than
indigotin) is the indirect evidence. Compared to the analysis of, for example, easel paintings,
manuscript analysis is in its infancy. What is needed, for decorated manuscripts of all periods and
countries, is an extensive programme of analyses, to establish firmly the sequence and spread of
material use. The study of Anglo-Saxon manuscript pigments has already produced surprises such
as the earliest uses of lead white and ultramarine on European manuscripts.
ACKNOWLEDGEMENTS
This paper is based on interdisciplinary research carried out between 1998 and 2001, based at the
University of Cambridge Department of Archaeology. It was funded by the Natural Environment
Research Council, the Department of Archaeology, Cambridge, and by Corpus Christi College,
Cambridge (CCCC). The analytical work was carried out from December 2000 to February 2001 in
the Parker Library of CCCC and in the British Library (BL). These institutions were kind enough to
permit, facilitate and encourage analysis and, in the case of the latter, to arrange for µRS analysis
and infrared reflectography to be carried out in their laboratories on my behalf. The author would
like to thank Christopher de Hamel and Gill Cannell (CCCC) and Michelle Brown and David
Jacobs (BL) for making these analyses possible, and for discussion as to their codicological
interpretation. The author was very fortunate to be able to collaborate with the joint project for the
analysis of the materials of manuscripts and incunabula being carried out by the BL and University
College London (UCL), based in the conservation department of the BL. Michelle Brown was
curatorial consultant, and decided which of the chosen manuscripts should be analysed. For µRS at
the BL, the spectrometer was provided by
Professor Robin Clark, Department of Chemistry, Christopher Ingold Laboratories, UCL. It was
operated on behalf of the author by one of Professor Clark's students, Katherine Brown, who also
suggested some interpretations. The author is particularly grateful to the Cambridge Department of
Archaeology for their substantial contribution towards the funding of these uRS analyses. The
photographs of manuscripts are reproduced by permission of the Master and Fellows of Corpus
Christi College, Cambridge.
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AUTHOR
MARK CLARKE received a BA in paper conservation from Camberwell College of Arts, London; a
MSc in conservation science from De Montfort University-Leicester; and a PhD from the
Department of Archaeology, University of Cambridge. Recently he has been working in The
Netherlands at FOM-AMOLF on the MolArt and de Mayerne projects on the aging of painted
works of art, and he is now working on the nineteenth-century archive of recipes for artists'
materials belonging to Winsor &• Newton. Address: Instituut Collectit Nederland, Gabriel
Metsustraat 8, 1011 EA Amsterdam, The Netherlands. Email: mark@dericus.org
Resume — Peu d'analyses des pigments des manuscrits anciens ont été réalisées à l'aide de
techniques analytiques fiables. Une méthodologie interdisciplinaire pour identifier les pigments
utilisés dans les manuscrits anglo-saxons (Angleterre, env. 600 -1 066 après J. C.) a été mise en
œuvre, et une série pilote d'analyses a été entreprise. On a établi une liste de pigments probables à
partir de sources écrites contemporaines, à partir d'analyses de manuscrits européens d'époque
proche, et à partir de découvertes archéologiques de colorants naturels et fabriqués. Les pigments
ont été analysés par spectroscopie Raman et imagerie proche infrarouge. Les résultas sont
présentes dans l'article. Les analyses ont fourni des données principalement sur les pigments
minéraux, tandis que l'information sur les pigments organiques provenait de sources indirectes.
Des patrons préliminaires de l'utilisation des pigments ont été identifiés en corrélation avec les
lieux, dates, et ateliers d'origine. Le minium, le vert de gris, le noir de carbone et l'orpiment ont été
trouvés à toutes les époques, et l'indigo dans les manuscrits les plus anciens, de même que de la
pourpre et du blanc de plomb dans quelques livres « de luxe ». L'outremer a commencé à être
utilisé vers l'an 1000 mais apparemment uniquement à Canterbury. On constate un usage tardif de
l'azurite et de l'ocre rouge. Les résultats présentés sont les premiers vraiment fiables depuis 1885.
Zusammenfassung — Bisher gab es zu wenige Untersuchungen der in früher Buchmalerei
verwendeten Pigmente, bei denen unzweifelhafte analytische Methoden eingesetzt wurden. Zur
Untersuchung, welche Pigmente in der angelsächsischen Buchmalerei (aus England, ca. 600- 1066
n.Chr.) verwendet wurden, wurde eine interdisziplinär arbeitende Methode entwickelt und in einer
Pilotstudie angewendet. Dabei wurde zunächst eine Liste der zu erwartenden Pigmente erstellt, und
zwar anhand zeitgenössischer Quellenschriften, den Daten der Pigmentanalyse zeitgenössischer
europäischer Manuskripte und anhand von archäologischen Funden von Rohpigmenten sowie von
farbigen Artefakten. Die Pigmente wurden durch Microramanspektroskopie und Messungen im
nahen Infrarotbereich analysiert. Die Ergebnisse werden präsentiert. Die Analysen erlaubten
vornehmlich Daten zu den anorganischen Pigmenten, Informationen über organische Farbmittel
konnten nur indirekt gewonnen werden. Ein vorläufiges Muster der Verwendung von Pigmenten in
Bezug auf den Verwendungszeitraum und die Werkstatt konnte erstellt werden. Mennige, Grünspan,
Kohlenstoffschwarz und Auripigment wurden überall und, zusammen mit Indigotin, auch in den
frühsten Beispielen gefunden, während Purpur und Bleiweiß in einigen „luxuriösen" Handschriften
auftauchten. Ultramarin wurde ab ca. 1000 n.Chr. verwendet, aber augenscheinlich nur in
Canterbury. Darüber hinaus fanden sich Azurit und roter Ocker in späteren Handschriften. Diese
Ergebnisse sind die ersten seit 1885, die auch verlässlich erscheinen.
Resumen — Los análisis de pigmentos empleados en manuscritos tempranos basados en técnicas
analíticas fidedignas y precisas son escasos. Se empleó una metodología multidisciplinar para
identificar los pigmentos empleados en manuscritos anglosajones (Inglaterra, 600 - 1.066 d. C),
realizándose una serie de análisis piloto. Se compiló una lista de pigmentos probables extraída de
fuentes escritas contemporáneas, del análisis de otros manuscritos europeos contemporáneos o
casi-contemporáneos, y de los hallazgos arqueológicos de colorantes puros y en objetos. Los
pigmentos se analizaron por medio de espectroscopia micro-Raman y por técnicas de imagen en el
infrarrojo cercano. Se presentan aquí los resultados obtenidos. Los análisis suministraron datos,
sobre todo, de pigmentos inorgánicos, y la información sobre los colorantes orgánicos se obtuvo
principalmente por otras fuentes, como evidencias indirectas. Se obtuvieron e identificaron
modelos preliminares de uso de determinados pigmentos, en relación con ciertas ubicaciones,
fechas y talleres de origen. Se detectaron, deforma genérica, minio, verdigris, negro de carbón y
oropimento, junto a la indigotína en las muestras más tempranas; el colorante púrpura de
crustáceo y el blanco de plomo fueron detectados en algunos de los libros 'de más lujo'. El ultramar
se comenzó a usar hacia el 1000 d. C. pero aparentemente sólo en Canterbury. Se ha detectado un
uso tardío de la azurita y del ocre rojo. Los resultados que aquí se exponen son los únicos
obtenidos de forma precisa y consistente desde 1885.