Natural Dyes in Textile Applications
G VV Taylor
York Archaeological Trust
Conservation Laboratories
Galmanhoe Lane, Marygate
York YO3 7 0 2
INTRODUCTION
It might seem strange that a review on natural dyes
should be published in 1986,as it is many years since
these dyes were of commercial significance. In 1918,
when Perkin and Everest [l]published their still valu-
able book on the natural colouring matters, only a few
dyes of the many that were once in use 'still find
application'. Those few were as follows: logwood, old
fustic, Persian berries and catechu. Cochineal 'is no
longer used in the textile industry in spite of the fact that
no man-made dye has yet surpassed it in brilliance and
fastness, but it costs more. The use of cochineal today is
restricted to food, drinks, cosmetics, and pharmaceutical
products' [2].Sic transit gloria mundi.
However, in recent years, an upsurge in interest in
natural dyes has been manifest:
1 Reconstruction of ancient and traditional dyeing
technology
2 Study of museum textiles and textiles recovered by
archaeology
3 Conservation and restoration of old textiles
4 Growing use of natural dyes in home craft work
5 Chemical characterisation of colorants in flora and
fauna, including many of those traditionally used
as dye sources
6 Replacement of synthetic dyes by natural dyes for
food, safety, and so forth.
This review covers the work on natural dyes since the
mid-1960s under the following main headings:
1 Fastness properties of natural dyes
2 Chemistry and analysis of colorants
3 Identification of dyes on old textiles
4 New information on the history of the use of
natural dyes.
The scope of this review is limited to natural dyes in
textile applications, although interest in natural dyes is
by no means restricted to this field. For example, White
and Kirby [3]have used high-performance liquid chro-
matography (h.p.1.c.) on red lakes in old oil paintings.
Modern interest in the varnish on old violins has
prompted the study of some of the red and yellow
natural dyes [4,5]; though recent work on the medical
effects of yellow dyes on rats [6]will probably be of less
interest to readers of this review.
1. FASTNESS PROPERTIES OF NATURAL DYES
Recent work on the properties of natural dyes has been
prompted by several factors, including the following:
1 Reconstruction of traditional dyeing techniques
2 Reconstruction of the original colours of old faded
textiles
3 Use of dyes in restoration of old textiles.
The fastness properties have received particular atten-
tion.
1.1 Light Fastness
Most natural dyes have poor light stability (compared
with the best synthetic dyes), and hence the colours in
museum textiles are often different from their original
colours. The relative light stability of a range of dyes was
reviewed by Padfield and Landi [7]who also studied the
colour change in a qualitative fashion. These colour
changes were studied quantitatively by Duff, Sinclair,
and Stirling [8]who expressed the changes in terms of
the Munsell scale and in CIE units. Wool dyed with nine
dyes was exposed in a Microscal fading lamp. The
fastness ratings were similar to those found by Padfield
and Landi in daylight fading. On the grey scale, yellow
dyes (old fustic, Persian berries) had poor fastness at
1-2; reds (cochineal(tin mordant), alizarin(a1um and
tin), lac(tin)) were better at 3-4; indigo 3-4; and
logwood black(chrome) 4-5. The corresponding BS
light fastness ratings were: yellows 1-2;reds 3-6 (de-
pending on the dye); indigo 5-6; and logwood 6-7.
A large proportion of natural dyes are, of course,
mordant dyes. The influence of mordant was found to be
very important in the fading of 18 yellow dyes [9].Wool
specimens were exposed to a xenon arc for up to
80 AATCC Fading Units. Colour changes were measured
in CIE units, on the grey scale, and in light fastness rating.
Turmeric, fustic and marigold dyes faded significantly
more than any of the other yellow dyes. However, use of
tin and alum mordants resulted in significantly more
fading than was the case when chrome, iron, or copper
mordant was used. Indeed, the author concluded that
the mordant was more important than the dye itself in
determining the light fastness of coloured textiles.
Dyes that may have been used in the traditional
Scottish textile industry have been described by Grierson
[lo]and by Duff, Sinclair and Grierson [ll].The light
fastness of such dyes on wool has been compared with
those of dyeings with 'imported' dyes to similar shades,
by Duff et al. [12,13], again using a Microscal lamp. The
native/imported pairs were as follows:
Hue Native dye Imported dye
Yellow Ling (alum mordant) Persian berries (tin)
Red Lady's Bedstraw (tin) Madder (tin) and
cochineal (tin)
Red/ purple Ochrolechia tartarea Orchil
lichen
Blue Privet berries Indigo
Green Digitalis Indigo on
Persian berries
Brown Parmelia omphalodes Fustic (tin)
lichen
Black Water lily root (iron) Logwood (iron)
The colours were described in terms of the Methuen
Book of Colour and also according to the Munsell
Colour Atlas. There is no native red to match the brilliant
scarlet obtainable with cochineal on a tin mordant, and
indigo is capable of giving a rather deeper blue than the
native privet berries, but otherwise, the shades from
native and imported dyes were similar. The fastness to
light of indigo and logwood are superior to those of the
native blue and black, but otherwise there is little differ-
ence. Both the lichen purples were of very poor fastness,
as expected.
REV. PROG. COLORATION VOL. 16 1986 53
 Hofenk de Graaff [14]examined the fading process of
natural dyes with a view to determining the original
colours of faded textiles. She gives advice on the use of
dyes for restoration. Cook [15]reviewed tannin-related
aftertreatments for improving the wash fastness and light
fastness of mordant dyes on cotton; some of these
treatments might be applicable to natural dyeings.
1.2 Wash Fastness
Duff et al. followed up their work on light fastness with a
corresponding study of wash fastness [16].Tests were
carried out under standard conditions (50°C)and also at
20°C with a washing formulation used in conservation
work on old textiles. Some dyes undergo marked
changes in hue on washing, shown to be attributable to
even small amounts of alkali in washing mixtures, high-
lighting the necessity of knowing the pH of alkaline
solutions used for cleaning of textiles dyed with natural
dyes. As a general rule, natural dyes (on wool) have only
moderate wash fastness as assessed by the I S 0 2 test.
Logwood and indigo are much more fast, however.
The nature of detergent solutions suitable for conser-
vation work has been discussed by Hofenk de Graaff
[17].Her suggested liquor containing 1 g/l of sodium
polyphosphate was shown by Duff et al. to result in
appreciable changes in hue with many natural dyes.
Clearly, the small increase in cleaning efficiency attribut-
able to the alkali must be balanced against possible
colour change in the dye, apart from the possible dam-
age to old protein fibres under alkaline conditions.
Duff et al. [12,13]also studied the wash fastness of
dyeings from native Scottish and imported dyes. In the
I S 0 2 test, the fastness of indigo and logwood was
superior to that of the native dyeings, privet berries and
water lily root respectively, but in the comparison of
native and imported yellows, reds, red/purples, greens
and browns, there was little difference between the two
groups.
2. CHEMISTRY AND ANALYSIS OF
COLORANTS
Among reviews of the chemistry of colorants, the pio-
neering works of Perkin and Everest [l]and Mayer and
Cook [18]are still valuable. More recent work on the
structures of quinonoid colorants is described in Thom-
son‘s books [19].Further recent reviews include those
by Farris [20]and Hofenk de Graaff [21,221.the latter
also including information on fastness properties and
history of use, while Robinson [23] provides a useful
introduction to the chemistry of red and blue colouring
matters in plants, some of which can be used as dyes.
This list of reviews is, of course, by no means exhaus-
tive.
The general analytical approach has always been to
extract the dye into solution from the textile and then to
study the solution. Over 50 years ago, the great pioneer
Pfister (e.g. [24])identified various red dyes by visual
examination of the colours of sqlutions in a range of
solvents. More recently, Schweppe [25-271 prepared
lakes from extracted mordant dyes using a range of
mordants and identified the dyes by their characteristic
colour patterns.
Such visual techniques are satisfactory in the hands of
a skilled and experienced worker, and if the dye is
present in sufficient concentration and purity to make
such visual assessment practicable. However, in many
cases, for example, the examination of textiles from
archaeological excavations, or of highly degraded dyes
on very old textiles, the visual approach may be vitiated
by either insufficient dye being available or by the dye
54 REV. PROG. COLORATION VOL. 16 1986
solution being heavily contaminated with non-dye stain.
These problems require a more objective examination of
the extracted dye solution. For example, spectroscopy in
the visual region can be used, and Saltzman and co-
workers (e.g. [28,29])have built up a library of reference
spectra. Infrared (i.r.) spectroscopy has also been used
[30,31]. The i.r. spectrum can be more informative than
the u.v.-visual, but more dye is required and purity can
be a problem. In recent years thin layer chromatography
(t.1.c.) has been used both to separate dye from non-dye
stain and also to characterise the dye itself (e.g.
[31-331).Finally, high performance liquid chromatog-
raphy (h.p.1.c) is revealing itself as a powerful tool in the
analysis of natural dyes [34].Little has been published
apart fom the work of Wouters [34]who examined dyes
such as madder, cochineal, and Polish cochineal and
demonstrated the value of h.p.1.c. in detecting minor
proportions of colorants in mixtures. A preliminary de-
scription of h.p.1.c. work on red glazes on old oil paintings
has recently been given by White and Kirby [3].
A high proportion of natural dyes are of the mordant
variety. The principle adopted for extraction is to hydro-
lyse the mordant-dye link with acid and then to dissolve
the organic part of the dye in a solvent such as alcohol
(e.g. [32,35]).The initial solution of the colorant can
then be worked up by further extraction with various
solvents, or by chromatography and so forth.
Non-mordant dyes require more specific solvents, and
indeed, solvent systems for many dyes, for example,
some of the Scottish traditional dyes, have still to be
established.
2.1 Purples
Purples are of three main varieties: (a) shellfish purples,
(b) lichen purples, and (c) purples made by mixing blue
and red; analytically, the red and blue components are
separately investigated.
2.1.1 Shellfish Purples
The main colorant derived from shellfish is 6,6’-dibromo-
indigotin, but other colorants, in particular, indigotin
itself, can also be present, depending on the shellfish
and dyebath conditions used. The history, chemistry,
and biological precursors to the purple colours derived
from shellfish have been reviewed by Baker [36], who
also describes new work on the colorants (or rather,
precursors of the colorants) in several gastropod mol-
luscs, following on from the work of Fouquet and Bielig
[37].The visible absorption spectrum (in chloroform) of
6,6’-dibromoindigotin itself is given by Saltzman et al.
[29];the spectrum is very like that of indigotin, but the
wavelength of the absorption maximum in the visible
region is at about 10 nm shorter wavelength than that of
the blue colorant. The actual wavelengths of the maxima
depends on the solvent [38,39],Saltzman [28] has
shown that the spectra of the two compounds in sul-
phuric acid differ markedly. Analytically, the spectro-
scopic technique is sensitive partly because of the high
extinction coefficients, and partly because the peaks lie
in the region of 600 nm where interferencefrom non-dye
stain tends to be small.
Dibromoindigotin can be extracted from a textile by
heating with pyridine [39]or acetic acid [40].
2.1.2 Lichen Purples
Purple dyes based on the reaction of certain lichens in
dilute ammonia and air have been known since classical
times; an historical review is given by Kok [41],and
commercial methods of production of the dye, until as
recently as 1950,are described by Richardson [42].The
chemistry involved is complex, and the most recent work
seems to be that of Musso et al. [43]. The chromophores
appear to contain the following structures:
Colour
neutral red violet red orange deep violet
acid red red deep violet
base deep violet deep violet red brown
The purple dyes produced (by Grierson) from six
Scottish lichens have been studied by Taylor and Walton
[44]. Dyed wool was extracted with warm pyridine/
water solution (1/1 by volume). All the lichens gave
similar spectra, with a peak at 580-590 nm. The posi-
tions of the peaks were very pH sensitive, as expected for
dyes related to litmus. The extractability of the colorant
from the initial pyridine/water solution by ether varied
widely among the six dyes, suggesting that, though the
chromophores of all six were similar, other structural
factors, affecting solubility but not colour, such as side
chains, showed considerable variability.
For analytical purposes, the preferred solvent system
for extracting lichen purples from textile samples is the
pyridine/water system [44]. The dye solutions are
scanned spectroscopically in the visible region, and
because of the poor ether extractability of some lichen
purples, the aqueous phase should also be examined,
even though this can be heavily contaminated in the
case of dyes from excavated textiles.
2.2 Blue Dyes
The principal blue dye encountered is indigotin, whose
main sources are woad (/saris rincroria L.) and indigo
(Indigofera rincroria L.). It is more readily extracted from
textiles than its purple dibromo derivative, and warming
with pyridine/water (1 /1 by volume) is satisfactory [35].
Dimethyl formamide [25] or acetic acid [40] can be
used. In a test specific for indigotin, it is reduced to its
leuco base, which is then extracted with ethyl acetate; a
blue colour slowly develops as the base reoxidises [40].
It is claimed that this test does not apply to dibromoindi-
gotin. As little as five micrograms of indigotin can be
detected.
As stated above, the spectroscopic test for indigotin is
very sensitive. There is a shoulder on the main peak
(whose maximum is around 600 nm), because of the
isomer indirubin, whose maximum is at about 540 nm
[351.
lndigotin was sourced from either woad or indigo, and
unfortunately, it is not yet possible to decide analytically
between the sources. However, Schweppe [26] found
that the greenish tinge in some woad dyeings, extracted
with acetic acid, was attributable to up to 12% of indigo
yellow (kaempferol, a flavonol, not an isomer of indigo-
tin) being present.
In the 18th century, a blue dye was made by reacting
indigo with sufphuric acid [45]. This dye, called Indigo
Extract or Indigo Carmine, is essentially indigodisul-
phonic acid. It was much used, particularly in the 19th
century. Like indigotin, it is extracted from a textile by
warm pyridine/water mixture and its spectrum (in this
solvent in the visible region) is very similar to that of
indigotin. Unlike indigotin, it is not extracted from pyri-
dine/water by ether and this property can be used to
distinguish between the two dyes [46].
2.3 Red Dyes
2.3.1 Insect Red Dyes
The kermes insect (Kermes vermilio Planchon) has been
used as a source of red dye for millenia; its colorant is
kermesic acid. In the Old World, kermes was superseded
by cochineal (Dacrylopius coccus Costa) with the ex-
ploitation of the resources of the New World from the
16th century onwards. The colorant is essentially car-
minic acid.
The correct structures of kermesic and carminic acids
have finally been established except for the stereochemi-
cal configuration of the glycosyl linkage in carminic acid.
Hmcw
CH, Q OH
HO OH
0 OH
Kermesic acid
Carminic acid
The work leading to these structures has been recently
summarised in Rodd [47] and the original references
given.
Though the colorant in cochineal is essentially car-
minic acid, Wouters [34] has recently shown (by
h.p.1.c.) that traces of kermesic acid are also present. It
seems unlikely that this was generated from carminic
acid during the extraction of the colorant from the insect,
as the glycoside group should be resistant to hydrolysis.
Insects of the Dacrylopius group other than cochineal
have been used as dye sources in America. For example,
Thomson [19a] states that 'the same, or a similar pig-
ment (to carminic acid) is produced by D. confusus
Cockerell, D. rornentosus Lamarck, and D. indicus
Green', without citing the original work. Recent work by
the present author [48] using spectroscopy and t.1.c.
supports Thomson's view.
Another insect prized by the ancients is that providing
Armenian coc hineaI, Porphyrophora hameli Brandt. Here
again, the pigment is carminic acid [48] and Whiting
[49] has shown that kermesic acid is undetected by
h.p.1.c.
Commonly used in Europe particularly before the
advent of cochineal from America was Polish cochineal,
the insect being Porphyrophora polonica L. (sometimes
also called margarodes polonicus or Coccus polonicus).
The pigment in this has been variously reported as
carminic acid, or carminic and kermesic acids (e.g.
[25]). Using solvent extraction procedures, Whiting
[49] has shown that both colorants are indeed present,
in the approximate ratio 1O:l. Very recently, Wouters
[50] has analysed the pigment from insects supplied by
the author; carminic and kermesic acids were present in
the ratio 15:l. It is established, therefore, that the princi-
pal colorant from the insect is carminic acid, but possibly
dyeings extracted from textiles could have a higher
proportion of kermesic acid if uptake of this acid from the
dyebath was preferred.
The structures in the complex range of pigments in lac
REV. PROG. COLORATION VOL. 16 1986 55
dye (from Indian insects such as Kerria lacca Kerr) have
been elucidated. The formulae of laccaic acids A, B, C
and D are described in Rodd [47], and that of E by
Thomson [19b]:
R aqueous extract is extracted with pentan-3-one, the
A CH,NHCOCH,
B CH,OH
C CH(NH,)COOH
E CH,NH,
CH3 0 OH
HOOC
no OH
0 tra, with a main peak (in methanol) at about 480 nm.
Laccaic acid D
The lac insect apparently produces a yellow mutant,
which is a source of yellow dye. The pigment appears to
contain at least five components [51]; they were separ-
ated by chromatography, but the structures of the col-
oured species have not been investigated.
Other insects have been used as sources of red dye.
For example, the colorant in the Russian insect, Anthra-
coccus uvae-ursi L. has recently been shown to be
carminic acid or something very similar; the thin layer
chromatography (t.1.c.) results were identical with those
of cochineal [48]. The pigments in other insects have
also been studied; a review is given by Brown [52].
Thus, Banks and Cameron [53] showed that the pig-
ment in Eriococcus coriaceus Maskell contains a group
of seven compounds based on emodin and 7-hydroxy-
emodin. The latter two compounds are found in Erio-
coccus confusus Maskell, according to Chan and Crow
[54]. Brown [52] reports the presence of ceroalbolinic
acid in the Mexican insect Ceroplastes albolineatus
Cockerell and the Japanese C. rubens Maskell (and
gives original references).
HO 0 on “HO o0 mC Y
Ceroalbolinic acid -
7 hydroxyemod in
The information on the insect red dyes is summarised in
the following table.
The insect reds are mordant dyes and they may be
removed from the textile by warming with dilute acid
and alcohol. In Whiting’s procedure [55], methanol and
dilute sulphuric acid are used. The methanol is evapo-
rated from the initial extract, which can then be extracted
with a variety of solvents. For example, kermesic acid is
completely extracted with ether. Carminic acid and the
laccaic acids are extracted only to a limited degree. If the
distribution coefficients for lac and cochineal dyes differ;
lac gives a value (solvent/water) around 1.4 and cochi-
neal about 0.9. Whiting also showed that the shapes of
the absorption curves for lac and cochineal are usefully
different, and in particular, the spectrum of cochineal (or
rather, carminic acid) has a sharply defined shoulder at
about 535 nm, whereas that for the colorant in lac is
much more gradual; this test gives unambiguous results.
All these insect red dyes give somewhat similar spec-
Infrared spectroscopy [30,31] and t.1.c (e.g. [25,33])
can also be used. The chromatograms can be examined
directly, or developed with uranyl acetate solution [25].
H.p.1.c. may also prove a powerful tool.
2.3.2 Vegetable Red Dyes
The main recent work on red dyes of vegetable origin has
been concerned with separating and identifying the
colorants in madder root and related plants, and is
largely attributable to Thomson and his school.
It has been known for many years that the colorants in
madder (Rubia tinctorum L.) are hydroxyanthraqui-
nones, of which alizarin, purpurin, and pseudopurpurin
(purpurin-3-carboxylic acid) are the main ones. An
exhaustive study of the root by Burnett and Thomson
[56] revealed no less than 19 anthraquinone pigments.
A parallel study [57] of the bedstraws (Galium species,
several of which were used as dye sources) revealed up
to 13 anthraquinones, much the same as those found in
common madder, including alizarin. In both cases, pig-
ments were isolated by column chromatography.
In contrast, colorants extracted from wool dyed with
Lady’s Bedstraw (Galium verum L.) were examined by
spectroscopy and paper chromatography [35]. Alizarin
was absent, in contrast with the work of Burnett and
Thomson. The disagreement presumably arises from the
relative availabilities of the colorants in the dyebath
compared with the exhaustive procedure of Burnett and
Thomson.
Schweppe [25] reports that madder and wild madder
(Rubia peregrina L.)dyeings differ in that only the former
contains alizarin. With present knowledge, therefore, it
would be difficult to distinguish between dyeings from
wild madder and Lady’s Bedstraw, both possible con-
tenders in traditional craft dyeing.
The main dyes encountered in analytical work are the

Insect Dye Where used Colorant

Dactylopius coccus Costa Coc hineaI America, then Europe Carminic acid
Kermes vermilio Planchon Kermes Middle East, Kermesic acid
N. Africa, etc.
Porphyrophora polonica L. Polish cochineal Middle East, Europe Carminic and
Kermesic acids
Porphyrophora hameli Brandt Armenian Middle East Carminic acid
cochineal
Kerria lacca Kerr Lac India, Middle East, etc. Laccaic acids
D. confusus Cockerell America Carminic acid
D. indicus Green America Carminic acid
D. tomentosus Lamarck America Carminic acid
Anthracoccus uvae-ursi L. Russia Carminic acid

56 REV. PROG. COLORATION VOL. 16 1986

madder-type dyes, and certain dyewoods such as brazil-
wood and logwood. All are mordant dyes, extractable
with acid and alcohol. With the madder-type dyes, the
main problem in identifying an unknown dye is in
determining the pattern of hydroxyanthraquinones pre-
sent and in particular the presence or absence of alizarin.
This can be achieved by chromatography, or by modify-
ing the spectrum of the dye by addition of magnesium
acetate. The magnesium addition technique is helpful in
the analysis of many dyes and is described in section 2.5.
2.4 Yellow Dyes
The formulae of a range of yellow dyes have recently
been collected [32]. The same authors describe the
performance of many of these colorants in t.1.c. [32,60].
Whiting [55,58]recommends that both polyamide and
cellulose plates be used for t.l.c., in order to utilise for
identification purposes the small differences in structure
of many related colorants of the flavonoid type and now
advocates h.p.1.c. Some preliminary work using h.p.1.c.
on yellow dyes has been published [59].
The analysis of yellow dyes on old textiles presents a
problem because the dyes tend to be much decayed.
Many of these dyes are of the mordant type and are ex-
tracted by acid/alcohol mixture. A few yellow dyes, not
of the mordant variety, such as saffron and turmeric, are
sufficiently coloured in themselves to be detectable by
spectroscopy in the visible region, saffron in particular
having a very characteristic spectrum. However, these
dyes are particularly prone to fading and hence are
unlikely to survive on old textiles.
2.5 The Magnesium Acetate Test
The spectra in the visible region of most mordant dyes
respond to the addition of magnesium acetate to a
solution of the dye (in a polar solvent) in a similar way,
the absorption being shifted to longer wavelengths [35].
The combination of the pair of spectra, with and without
magnesium present, can be a useful fingerprint in iden-
tifying an unknown dye and, in some cases, the sensi-
tivity of dye detection is enhanced.
For example, the spectra of the dyes from madder and
related dye sources are profoundly changed by the
presence of magnesium acetate, in methanol. The ab-
sorption is shifted to longer wavelengths, the extinction
attributable to the dye is increased and the spectrum is
easier to analyse, particularly in terms of the presence or
absence of alizarin. Alizarin appears at about 630 nm as a
shoulder on the main absorption from the anthraquinone
mixture. Apart from helping identification, the magne-
sium technique increases the sensitivity of dye detection
which is particularly useful with archaeological textile
samples where non-dye stain is a problem.
The mechanism of the action of the magnesium is not
entirely clear, It is well known that addition of a base to
an hydroxyanthraquinone profoundly changes the col-
our. Superficially, magnesium acetate has the same
effect. However, the spectra are not the same in detail as
those obtained in the presence of potassium hydroxide,
for example, and it is possible that a soluble complex,
analogous with a mordant-dye lake, is formed. An
additional advantage of magnesium acetate over potas-
sium hydroxide is that the latter tends to give a cloudy
solution with dye extracts from archaeological textiles,
whereas the former gives clear solutions more amenable
to spectroscopy.
With yellow mordant dyes, the spectra are generally
shifted, but more work is required to determine the
usefulness of the magnesium technique in analysing for
such dyes.
3. IDENTIFICATION OF DYES ON OLD TEXTILES
In recent years, there has been an increasing interest in
the dyes and dyeing recipes used in the past. The factors
prompting this interest include the following: (a) the
increasing sophistication of methods of conservation
and repair of historic textiles, (b) the finding of extensive
collections of textiles in recent archaeological investiga-
tions, (c) new interest in reconstructing the home dyeing
procedures of the past and (d) the authentification of
valuable old textiles.
Problems arising in the conservation of old textiles are
only peripheral in the present review. However, the
finding of textiles in a number of archaeological excava-
tions has led to analytical work with regard to dyes that
may still remain on the textiles. Noteworthy collections
which have been investigated include those from various
sites in Egypt from dynastic to medieval times [61];the
collection from 1st century Vindolanda (a fort near
Hadrian's Wall) [62,63]; the textiles from Anglo-Scandi-
navian York [35];and other important collections to be
touched on.
The reconstruction of traditional dyeing practices
could be dismissed as part of the current nostalgic craze,
but that would be unjust to a number of workers (for
example, Grierson) who is reconstructing traditional
Scottish home dyeing practices (e.g. [lo]).Much of this
work is in the hands of amateurs, but, in the case of the
Scottish study at least, that does not preclude a very
thorough and painstaking investigation not only experi-
mentally but also in the research of documentary evi-
dence.
The interest in authenticating old textiles, is of course,
not new. Obviously, only the smallest analytical samples
can be taken from the possibly valuable textiles, and the
development of techniques such as spectroscopy, t.1.c.
and most recently, h.p.1.c. has led to rapid advances in
the investigations of such problems.
The results of much of this recent work on dye
investigation have increased the knowledge of the his-
tory of the use of natural dyes.
3.1 Dyes on Textiles from the Middle East
Masschelein-Kleiner and Maes [30]examined textiles
dating from the first 600 years of our era, from Nubia,
Palestine and Egypt. Local plants seem to have been
used in Nubia; a red dye much like madder but with a
higher purpurin content, and a bixin-containing dye
were found. Coptic textiles were characterised by the
frequent presence of zinc (mordant?) and the use of
luteolin (the main colorant in dyes such as weld) for the
yellow dyeings. A red dye mordanted with tin, which
was more like cochineal than kermes, may have been
Armenian cochineal; kermesic acid was absent.
Eastwood [61]summarised recent findings on Egyp-
tian textiles from several sites dating from the fourteenth
century B.C. to the late medieval period. The changing
pattern of dye use was summarised as follows:
1400 8.C. At Tel el-'Amarna, on flax; madder and
ocherous earth
100 A.D. Although the range of fibres had increased,
only madder was used as a red dye. At Quseir al-Qadim
it has been found only on wool (no flax or cotton textiles
had been dyed red, while silk has not been found in any
of the appropriate archaeological contexts)
1500 A.D. With the expansion of the Islamic empire
came a notable increase in the availability of both
different dyes and fibre types. The increased range of
dyes also represents a greater sophistication in the
dyeing techniques. The red dyes kermes and lac were
found on wool rather than on cotton, the most common
REV. PROG. COLORATION VOL. 16 1986 57
fibre, or silk which was regarded during the period as a
luxury fibre. More textiles are becoming available for
analysis which should increase the understanding of
Egyptian dyeing practices.
3.2 Blue and Purple on Old Jewish Textiles
A blueish purple was used to colour the four tassels in
the corners of the Tallit, the Jewish ritual garment and
prayer shawl. Elliott [64] deduced that the dye was
made from shellfish. Ziderman [65] showed that the
shellfish was probably Murex frunculus (alternative
Trunculariopsis frunculus), use of which would result in
a mixture of dibromoindigotin and indigotin colorants on
the textile. However, Elsner and Spanier [66], while
accepting that M. frunculus could result in both indigo-
tin and its dibromo derivative being present, believe that
the latter is absent in the dyeing because of its debromi-
nation in the dyebath; but this view has been refuted
[67]. McGovern and Michel [68] suggest that indigotin
precursors can be removed from the vat by dark oxida-
tion before dibromoindigotin is developed and that,
when the importance of a reducing environment in the
vat was not well understood, this may have resulted in
variability in the colour of ancient dyeings.
3.3 Dyes on t h e Vindolanda Textiles
These textiles, all wool fragments, date from about
90A.D. [62] and represent a high proportion of the
known Roman textiles. About 100 fragments, from over
50 separate textiles, have been analysed [63].
Some of the wool was pigmented, but much was
originally white and suitable for dyeing. However, all
textiles were brown or black when excavated. Evidence
for dye was found on nine textiles. In eight cases, the
dye was madder or a close relative. In three of the eight,
the dye was indeed madder but in the other five, not all
the hydroxyanthraquinone components survived. So in
two cases only alizarin survived, in another, only pur-
purin, and so forth. The ninth dyed textile appeared to be
coloured with a lichen purple, surviving only sporadi-
cally on the cloth.
These results reveal the skill with which the (presum-
ably) British dyers had taken over the dyeing practices of
the ancient world within a few years of the Roman
invasion of the province. The dyes (and alum mordant?)
had probably been imported by the Roman army so that
a clothing contract could be fulfilled by the British.
Lichen purple based on Rocella fincforia D.C. was well
known (the plebeian equivalent of the prestigious Tyrian
Purple); though it is possible that lichens local to
Vindolanda had been used.
3.4 Dyes on Saxon Textiles from London
This work was reported by Pritchard [69], the analyses
having been done by Penelope Walton of the York
Archaeological Trust. The wool textiles dated from the
ninth to eleventh centuries. Eleven of the 27 fragments
yielded identifiable dye, using spectroscopic and chro-
matographic techniques. The dyes were madder, indi-
gotin, and lichen purple. Two fabrics gave evidence that
dyeing was sometimes done before weaving; on one, a
fourshed twill, every third weft had been dyed with
madder, while the rest of the cloth used yarn dyed with
indigotin. In a second cloth, dyed and undyed yarns were
interwoven. On one textile, blue was overdyed with
madder to give a purple.
3.5 Dyes on Viking Textiles from Dublin
Walton (reported by Pritchard [70]) has also examined
wool textiles from Dublin dating from the tenth and
58 REV. PROG. COLORATION VOL. 16 1986
eleventh centuries. Again, the dyes found were madder,
indigotin and lichen purple, with some evidence for
yellow or orange dye.
3.6 Dyes on Anglo-Scandinavian Textiles from
York
These textiles, dating from the ninth to eleventh centu-
ries (with a few perhaps later) were recovered from the
excavations in York between 1972 and 1982. They are
described by Walton [71]. Most were of wool, with a
few of silk. The first phase of the dye investigation has
been reported [35]; further work has indicated the
presence of lichen purple on a number of textiles. The
finding of this dye on these and other fragments from the
England of a thousand or more years ago confirms the
view of Kok [41] that this dye did not, in fact, fall out of
use during the early medieval period in North West
Europe as held by many authorities. In view of the
Scandinavian and Scottish tradition of the use of lichen
dyes, it would have been surprising if lichen purple had
indeed gone out of use.
Evidence of dyes was found on over half the textiles,
suggesting that dyeing was a normal practice. The main
dyes were madder and indigotin (apart from lichen
purple) and there was evidence of kermes on one or two
high quality textiles that may have been imports.
Subsequent to the analytical work, a number of dye-
plant residues were found in the soil contexts associated
with the textiles [72,73]: woad (the probable source of
indigotin), madder root, Dyer’s Greenweed (Reseda
lufeolaL.) which is a source of yellow mordant dye but
also has other uses and a clubmoss, Diphasium compla-
nafum L., known to have been used for dyeing purposes
(yellow dye? mordant?) in Scandinavia.
3.7 Yellow Dyes on Textiles of 1500-1850 [32]
This period was chosen because a great many changes
in dye type might be expected, because of the varying
patterns of trade. About 500 textile samples were re-
ceived from museums in Europe and America, and dyes
were examined by t.1.c. Remarkably, 80% of the samples
were dyed with weld, a result similar to findings on a
group of northern Dutch textiles of the 17th century
[74]. The dyes on the remaining 20% of the textiles
remained unidentified. The authors conclude that part of
the difficulty is attributable to the instability of yellow
dyes and that in many such dyes, the main component is
luteolin. It is necessary to identify the trace components,
which may have decayed, before such dyes can be
positively identified.
3.8 Red Dyes on Textiles from 1450-1600 [75,76]
This is a further period of change, particularly with the
introduction of American cochineal. A large number of
wool and silk textiles from many museums (arranged
through ICOM) dated within the period of interest were
studied. Dyes were identified by t.1.c. As expected, the
use of kermes (and of Polish cochineal) had declined,
and was essentially replaced by cochineal by 1600. Many
textiles dating before 1450 were dyed with brazilwood,
but the use of this had fallen to a low level by 1500,
rising to a new peak in the latter part of the 16th century
before falling away again. The decrease after 1450 is
attributed to eastern supplies being cut off by the fall of
Constantinople in 1453 and the subsequent rise to
imports of South American supplies. The prominence of
madder fluctuated somewhat during the 16th century
and declined late in the period as cochineal took over.
These results can be compared with those of a study
of Tournaisian tapestries of the 15th and 16th centuries
[77]. Although new dyes were available in the latter, the
dyers in the famous Flemish tapestry-weaving centre of
Tournai kept to the medieval tradition. Only indigotin,
madder and weld were used. Kermes and cochineal were
absent, although the latter was imported into Antwerp at
the start of the 16th century. Old fustic (Morus rincroria
L.) was found in natural and brown shades which may
be caused by restorations. In an earlier paper [78], the
authors found orchil, a lichen purple, but only mixed
with more stable colours such as indigotin and madder
in 15th century textiles. It occurred alone in a 16th
century textile, however, which is most unusual because
the regulations controlling the operations of the dyers'
guilds at the time imposed high financial penalties for
using such a fugitive dye by itself.
The same workers examined pieces of Netherlands'
tapestry from the 15th and 16th centuries [79]. Again,
indigotin, madder and luteolin were found. Use of other,
less stable, dyes such as brazilwood and lichen purple,
was exceptional. Mordants were aluminium and iron.
3.9 Dyes from Textiles Excavated at Newcastle
The first group of textiles, dating from the 15th and 16th
centuries, has been described [80], the dye analyses
being reported by Walton, who has summarised her
findings elsewhere [81]. Thirty-five textiles were tested,
twelve giving positive dye results. The predominant dye
was madder, with kermes on a textile that was probably
imported. A further series, from the 17th century, is
described in another report [82], with a preliminary
account of the dye test results being given by Walton
[83]. Forty-five textiles were examined, 23 giving posi-
tive results. The predominant dye was indigotin, mostly
used on its own, but in one case combined with a yellow
and in another with a dye resembling brazilwood. Mad-
der was found only on the cheaper woollens, whereas
brazilwood and an insect dye, probably kermes, were
found on more expensive worsteds and silks. The pre-
dominance of indigotin may be a reflection of the darker
shades required for Puritan dress.
3.10 Dyes on the Baynard Castle Textiles [80]
These textiles, excavated from the Baynard Castle site,
London, date from the early 14th to mid 16th centuries.
Ninety-two textiles were tested and dye was found on
61. In the earliest group, madder predominated, with
some evidence for kermes and brazilwood. Around
1400, madder was still the main dye, but there was some
sign of yellow dye, lichen purple and kermes. Three
samples showed madder combined with indigotin to
give a purple and another combined madder with yellow
to give orange. The later textiles showed a similar
pattern, perhaps with rather more evidence for yellow.
Unfortunately, it was not possible to identify the yellow
dye.
3.11 Dyes on Early William Morris Embroideries
[MI
The embroideries dated from about 1860, early in Morris'
textile progress. Later, he would have advocated the use
of natural dyes, but the view was that, when these
embroideries were produced, Morris would have had to
use wools dyed with the new synthetic dyes [84]. In
fact, the dyes found were mostly natural (cochineal,
madder, probably weld, probably tannin). The blue
appeared to be indigodisulphonic acid, commonly used
at that time. However, Morris later would have used
indigotin, preferably from woad.
3.12 Dyes on Oriental Carpets
Work in this area is described by Whiting in a series of
publications (e.g. [55,85,86]). The results show the
gradual introduction of synthetic dyes in Middle Eastern
carpets towards the end of the 19th century. The main
natural dyes encountered were indigotin, madder (the
commonest red), lac and cochineal (but not kermes) and
weld. On occasion, both natural and synthetic dyes
were combined in one shade, presenting analytical prob-
lems. Whiting also encountered the problem of analysis
of yellow dyes previously touched on (Section 3.7) and
indeed, this is why he advocated the use of h.p.1.c. for
examining such dyes. A preliminary general conclusion
was that the main yellow dye used in the 19th century by
the nomadic peoples of Persia, the Caucasus, Turkestan
and (after export) much of India was the plant Del-
phinium sulphuraeum, which is scarcely discussed in the
literature of natural dyeing.
Boehmer [87] analysed a mid 19th century Anatolian
rug with a view to developing dye recipes to match the
colours. Analysis was by t.1.c. Schweppe [88] described
techniques for distinguishing natural from synthetic dyes
on carpets.
3.13 Use of Tannins as Dyes
It is well known that tannin-containing substances were
used to obtain browns and blacks and to 'sadden' bright
colours. The analytical problems are formidable, but a
start has been made by Masschelein-Kleiner et al. [89],
who also attempted to identify the tannins on a series of
tapestries dating from the 15th to the 18th centuries.
Because the uptake of tannins by wool is small, it was
difficult to characterise the minor components (which
define the individual tannins) even though both t.1.c. and
h.p.1.c. were used.
3.14 Miscellaneous Dye Investigations
In the analysis of textiles from Peru [go] t.1.c. and U.V.
visible spectroscopy were used to show the presence of
carminic acid (attributed to cochineal) and blues and
greens matching indigotin. Whites, yellows, and brown
were the natural fibre colours. Interest in the blue (?)
sewing thread used in American Civil War uniforms led
Cordy and Yeh [91] to develop techniques to distin-
guish among the likely contenders, indigotin, Prussian
blue and logwood (iron mordant). However, difficulty
was encountered with faded logwood dyeings. The
kinetics of fading of alizarin lake pigment were found to
be first order by reflectance spectroscopy [92]. Adrosko
[93] summarised the natural dyes most commonly used
in the USA.
Japanese workers are also active, though many of
their publications are accessible only in abstract form.
Mention should be made of the work of Nasu et al. [94]
in which emission and excitation spectra were used to
identify natural dyes on silk before and after colour
fading.
Dalrymple [95] identified dyes on a 17th century
Scottish mummer's costume. The dyes were indigotin
(generally with a yellow dye), cochineal, lichen purple
and brazilwood. An exception was indigosulphonic acid,
not invented until 1740 and probably used in the repair
of the costume in the 19th century. The use of dyes such
as cochineal at this early period in Scotland is interest-
ing; cochineal was also found on a plaid accurately
dated to the early 18th century [96]. Dalrymple [97] has
summarised commercial dyeing practices in Scotland in
the late 18th century and early 19th centuries. Celoria
[98] has similarly considered the files of the dyer Joshua
REV. PROG. COLORATION VOL. 16 1986 59
Wardle and reconstructed a list of dyes and recipes used
in the late 1830s.
3.15 Historical Surveys
No review which is concerned with the history of the use
of natural dyes would be complete without mention of
Brunello's monumental book [99],which covers not
only natural dyes, but also carries the reader into the
early period of synthetic dyes. Other surveys on aspects
of the history of the use of natural dyes may be men-
tioned. Vogler [loo] reviews the craft of dyeing in
ancient Egypt, although some of his conclusions may
need modifying in view of Eastwood's recent work [61].
Lillie [lo13 summarises classical references to the red
(and purple) dyes used in ancient times, while Donkin
reviews the history of Middle Eastern red insect dyes
[lo21 and surveys cochineal itself [103].Ponting re-
views the history of madder [lo41 and surveys the
commercial natural dyes yielding red, yellow and blue
[105].Hofenk de Graaff has recently summarised her
work on red dyes in medieval and early modern Europe
[lo61 and in the same book, Munro [lo71 gives an
interesting historical account of medieval scarlet. Men-
tion should be made of Celoria's index [lo81 to the
series of papers by Bolton in the 1930s on aspects of the
history of dyeing [log].As Celoria points out, Bolton
seemed to have read most of the relevant literature 'and
offers the nearest thing we have to a systematic history
of post-medieval dyeing'.
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Note:
DHAT stands for Notes of Annual Meeting on Dyes on Historical and
Archaeological Textiles, edited by H E Dalrymple, National Scottish Museum,
Edinburgh.
DHAT1 = First Meeting, York 1982
DHAT2 = Second Meeting, Edinburgh 1983
DHATI = Third Meeting, York 1984
DHAT4 = Fourth Meeting, London 1986
REV. PROG. COLORATION VOL. 16 1986 61