Microchim Acta (2008) 160: 477–483

DOI 10.1007/s00604-007-0774-4

Printed in The Netherlands

Original Paper

High-performance liquid chromatographic determination of colouringmatters in historical garments from the Holy Mountain of Athos

I. Karapanagiotis1, A. Lakka1, L. Valianou1;2, Y. Chryssoulakis2

1 Ormylia Art Diagnosis Center, Sacred Convent of the Annunciation, Ormylia, Chalkidiki, Greece2 Department of Chemical Engineering, National Technical University of Athens, Athens, Greece

Received 28 December 2006; Accepted 21 March 2007; Published online 6 June 2007

# Springer-Verlag 2007

Abstract. This work is probably the first attempt

to identify the organic colouring materials contained

in post-Byzantine textiles, from the Holy Mountain

of Athos. Samples extracted from seven ecclesiasti-

cal garments (15th–19th century) are investigated by

high performance liquid chromatography with UV-

Vis diode array detection. The detection limits for

alizarin, purpurin, carminic acid, laccaic acid A, luteo-

lin, apigenin, genistein, fisetin, sulfuretin, ellagic acid,

indigotin and indirubin are found to be within 0.002–

0.029mg mL�1. The following organic dyes are iden-

tified in the extracts: dyer’s broom (Genista tinctoria

L.), young fustic (Cotinus coggygria Scop.), an indi-

goid dye source either indigo (Indigofera species) or

woad (Isatis tinctoria L.), madder, cochineal and lac

dye (Kerria lacca Kerr). Furthermore, the identification

of a brazilein derivative indicates the presence of a

Caesalpinia dye source in the samples.

Keywords: Dye; colorant; liquid chromatography; textile; cultural

heritage.

The goal of the present investigation is the identifi-

cation of the colouring materials found in ecclesiasti-

cal garments (sakkoi) from Mount Athos, the eastern

peninsula of Chalkidiki (Greece) which according to

the World Heritage Committee it is considered to have

outstanding universal value. The investigated objects

are of extreme importance not only due to their prov-

enance (Holy Mountain of Athos has been an auton-

omous spiritual center since the 10th century) but also

because according to their records they belonged to

important figures of the Byzantine and post-Byzantine

history. To the best of our knowledge the identity and

the origin of the colouring materials contained in such

historical textiles (garments from Mount Athos), has

never been investigated and=or reported so far. Prior

to the investigation of the historical samples, a prelim-

inary validation of the analytical methodology is

provided by calculating the limits of detection of sev-

eral anthraquinones, flavonoids and indigoids; ellagic

acid is also included. These compounds are primary

colouring ingredients of natural organic dyes. Some of

the latter appear to have interesting medical properties

and they are currently investigated=exploited by the

pharmaceutical industry. The use of several natural or-

ganic dyes either as colouring materials for textiles and

artworks or as medicines was known since antiquity.

For example, the Greek doctor and philosopher Hip-

pocrates (4th and 5th cent. B.C.) described the use of the

plant Alkanna tinctoria for treatment of ulcers [1]. The

roots of the same plant were used to produce deep red

pigments, utilized to decorate fabrics and textiles [2].

Correspondence: Ioannis Karapanagiotis, Ormylia Art Diagnosis

Center, Sacred Convent of the Annunciation, Ormylia, GR-63071

Chalkidiki, Greece, e-mail: g.karapanagiotis@artdiagnosis.gr

The identification of the colouring materials in

textiles of great archaeological value (clothes, carpets,

furniture, decoration, etc.) is a challenging subject for

analytical chemistry and therefore has received signif-

icant attention [2–16]. A few difficulties in the anal-

ysis of painted extracts from historical textiles are:

(i) the usually small available sizes of samples, (ii)

the lack of commercially available pure compounds,

used as standards in a typical analytical procedure and

(iii) the degradation of dyestuffs developed because of

ageing effects and=or extensive use of the historical

object. Degradation processes can result in a decrease

of the amount of dyes contained in an investigated

sample and therefore the identification of the re-

maining colouring materials (dyes) becomes difficult.

Consequently, the use of techniques with enhanced

analytical capabilities is necessary for the investiga-

tion of samples extracted from archaeological threads.

In particular chromatographic techniques have been

primarily employed for the separation and identifica-

tion of the individual colouring components i.e. the

active ingredients of the organic dyes. Historically,

thin-layer chromatography (TLC) has been used. How-

ever, nowadays, TLC has been replaced almost en-

tirely by high performance liquid chromatography

(HPLC) combined with spectrophotometric UV-Vis

detection [2–5, 7, 9, 11–15]. Liquid chromatography

combined with mass spectrometric (LC-MS) detec-

tion has been rarely used [6, 8, 10, 16].

In the present study HPLC-UV-Vis is employed

for the identification of the colouring materials in

samples extracted from the objects of Table 1. Iden-

tification is based on comparison of the retention

time and absorption spectrum recorded for each col-

ouring compound of an unknown sample with corre-

sponding data of known reference materials, stored

in a database. Reference materials can be either dye-

stuffs and organic pigments of known origin or pure

colouring compounds (standards) which are con-

sidered as markers for the identification of the or-

ganic dyes.

Experimental

Chemicals

The following standard materials were used to evaluate the lin-

earity and the precision of the method: alizarin obtained from

Aldrich, fisetin, ellagic acid, genistein, carminic acid, natural red

25 (laccaic acid A), indigotin and apigenin purchased from Fluka

Chemie (Sigma-Aldrich, www.sigmaaldrich.com), luteolin and

purpurin obtained from Sigma-Aldrich, sulfuretin purchased

from Wako Chemicals (www.wako-chem.co.jp) and finally in-

dirubin which was kindly donated by P. Magiatis (University of

Athens) [17].

For liquid chromatography the following solvents were used:

HPLC grade acetonitrile (CH3CN, Merck, www.merck.de), trifluor-

oacetic acid (TFA, Merck) and type I reagent grade water. The latter

was produced by a Barnstead EASYpure water purification sys-

tem and had resistivity up to 18.3 M� cm�1 and organic content

<5 ppb. Type I reagent grade water was also used for solution and

sample preparations along with HPLC grade dimethylformamide

(DMF, Riedel-de Ha€een) and HPLC grade methanol (MeOH,

Merck). Archaeological threads were treated with pro-analysis grade

hydrochloric acid 37% m=m (HCl, Riedel-de Ha€een). Solvents uti-

lized in the HPLC instrumentation were filtered through a 0.2mm

filter prior to use.

Standard solutions

Stock solutions of standard materials in DMF were prepared at

concentration of 0.1 mg mL�1 in volumetric flasks (type A) and

were stored in darkness at 4 �C. Five working solutions were pre-

pared for each standard material by appropriate stepwise dilutions of

stock standards. Concentration ranges of these working solutions

were between 1.3 and 20.0mg mL�1.

Reference materials of young fustic and sappanwood

Raw material of young fustic (Cotinus coggygria Scop.) was

kindly provided by R. Karadag (University of Marmara, Turkey).

Raw redwood samples (Caesalpinia trees) were provided by

Kremer Pigmente (www.kremer-pigmente.de) and Incense

Magic (www.incensemagic.co.uk). Also, pigment of sappanwood

(Caesalpinia sappan L.) and pieces of silk and wool dyed with this

dyestuff within two COST G8 scientific missions were kindly pro-

vided by I. Petroviciu (National Research Laboratory for Cultural

Heritage, Romania) I. V. Berghe (Royal Institute for Cultural

Heritage, Brussels) and J. Kirby (National Gallery, London). Pig-

ment and dyed yarns were distributed to several laboratories within

the activities of the EU-ARTECH project. Redwood samples were

treated and analyzed according to the procedure described below for

the historical extracts.

Preparation of historical samples

Threads of around 1 cm, extracted from the ecclesiastical garments

of Table 1, were provided by C. Karydis. The samples were treated

following a four step process: (i) Samples were immersed in 400mL

of H2O: MeOH: 37% HCl (1:1:2, v=v=v) kept at 100 �C to extract

the organic dyes. (ii) Then samples were evaporated (50–60 �C)

under gentle nitrogen flow. (iii) The dry residues were dissolved

in DMF. (iv) Samples were finally centrifuged and submitted to

HPLC. It is known that the above hydrolysis procedure is successful

for anthraquinones and flavonoids but its efficiency is not so good

for hydrophobic indigoids (usually blue=purple dyes) for which

alternative routes have been suggested [15, 17, 18]. For this reason,

each sample which according to its colour could contain blue=purple

indigoids, was divided in two sub-samples. One sub-sample was

treated with the above described acid hydrolysis procedure and

the remaining part was treated with hot DMF (80 �C) for 15 min.

Both sub-samples were analyzed then to ensure that all colouring

compounds contained in the initial sample had been extracted

and identified.

478 I. Karapanagiotis et al.

HPLC equipment and analysis

The HPLC system (Thermoquest, Manchester, UK) consisted of

P4000 quaternary pump, SCM 3000 vacuum degasser, AS3000 auto

sampler with column oven, Reodyne 7725i Injector with 20mL sam-

ple loop and Diode Array Detector UV 6000LP. The latter collected

spectra from 191 to 799 nm. A reversed phase Alltima HP C18 5mm

column with dimensions 250 mm�3.0 mm (Alltech Associates,

Inc., USA) was utilized for separation. The temperature of the col-

umn was 33 �C. Gradient elution was performed using two solvents

consisted of A: 0.1% (v=v) TFA in H2O and B: 0.1% (v=v) TFA in

CH3CN. The flow rate was 0.5 mL min�1 and the following elution

program was applied: 0–1 min 95% A isocratic; 1–15 min linear

gradient to 70% A; 15–20 min linear gradient to 40% A; 20–23 min

40% A isocratic; 23–33 min gradient to 5% A; 33–35 min 5% A

isocratic. Data were received and analyzed using an XcaliburTM

(Thermoquest) data system.

An analytical run was always followed by the injection of a blank

sample, to ensure that no endogenous peaks or carryover effects that

might interfere with the identification of the colouring compounds

are detected.

Results and discussion

Linearity

Calibration curves were generated to investigate the

linear relationship between the peak area and the con-

centration of the standard materials. Data were collect-

ed at 275 nm for alizarin, purpurin, carminic acid and

laccaic acid, at 254 nm for luteolin, apigenin, genistein,

fisetin sulfuretin, ellagic acid and at 288 nm for indi-

gotin and indirubin. Five solutions (1.3–20.0mg mL�1)

of each standard material were injected six times

(n¼ 6) and the measured peak areas were plotted as

a function of the concentrations. Good linear correla-

tions between peak areas and concentrations were ob-

tained; the mean value of the correlation coefficient

for any standard was R2>0.9944. The limit of de-

tection (LOD) which corresponds to a signal-to-noise

ratio of 3 was calculated for each standard material.

The lowest value LOD was calculated for indigotin

(0.002mg mL�1) while the highest value corresponded

to sulfuretin (0.029mg mL�1).

Precision

Precision was calculated for each standard material at

three concentrations. Each solution was analyzed five

times (n¼ 5). In all cases the % relative standard de-

viation (% RSD) for the area measurements was found

to be lower than 1.2. The maximum % RSD (¼1.2)

was calculated for purpurin at 5 mg mL�1 and the

minimum value of % RSD (¼0.1) was recorded for

luteolin at 4 mg mL�1.

Analysis of standards

Table 2 summarizes the absorbance maxima of the

standard materials. As it was expected, highest char-

acteristic absorbance maxima were recorded for the

blue-purple indigotin (605 nm) and indirubin (539 nm)

while the lowest values correspond to the yellow fla-

vonoids and ellagic acid. Intermediate values of char-

acteristic absorbance maxima were recorded for the

reddish anthraquinones.

Analytical results of historical objects

The results of the identifications performed on the his-

torical extracts are summarized in Table 3. According

Table 1. Data of the garments based on object records and Byzan-

tine tradition

Object

no.

User of the garment Provenance

of the artwork

Date (century)

1 Emperor Ioannis Monastery 15th–16th (?)

Tsimiskis� Iveron

2 St. Nifon Monastery 16th

St. Dionysiou

3 Patriarch Dionysiou Monastery second half

Mouselimi �0 Iveron of 17th

4 Bishop Velegradon Monastery 18th

Ieremiou St. Dionysiou

5 Bishop Nilou Monastery 18th

Simonos Petra

6 Patriarch Kirylou E0 Skete middle of 18th

St. Anna

7 Patriarch of

Alexandria

Mathews �0

Monastery

Koutloumousiou

18th–19th

� The emperor Ioannis Tsimiskis lived in the 10th century.

Stylistic examination of the garment, however, done by the con-

servator C. Karydis suggests that the object is probably of a much

later date.

Table 2. UV-Vis absorbance maxima of the investigated standard

materials

Compound Absorbance maxima (nm)

Carminic acid 275, 309, 493

Ellagic acid 253, 367

Laccaic acid A 285, 491

Fisetin 221, 247, 359

Sulfuretin 257, 397

Luteolin 221, 251, 345

Apigenin 221, 267, 337

Genistein 217, 259

Alizarin 247, 277, 429

Indigotin 285, 331, 605

Purpurin 255, 293, 479

Indirubin 289, 363, 539

High-performance liquid chromatographic determination 479

to the reported results luteolin appeared to be the most

common colouring compound as it has been detected

in 10 samples (of 16 total). In 8 samples, which were

yellow, green or orange luteolin was found in mixture

with genistein (and apigenin) leading thus to the con-

clusion that Genista tinctoria L. was used during dye-

ing [19]. Luteolin was also found in two red samples,

3.1 and 3.2 along with several other colouring com-

pounds, none of which, however, can be used to specify

a particular dye source which can explain the presence

of this flavonoid compound. Apparently, the red col-

our of these two samples suggests that the use of a

luteolin-based yellow dyestuff was limited in the dye-

ing procedure of these threads (samples 3.1 and 3.2)

and therefore the identification of a secondary com-

pound which could determine the plant source of

luteolin (like for example genistein found in the 8

non-red samples) is difficult and at least not possible

with our analytical methodology.

Sulfuretin was found in mixture with fisetin in 6

samples, indicating the use of Cotinus coggygria

Scop., known also as young fustic. The major com-

pound of the latter is sulfuretin, as it has been con-

cluded after analyzing young fustic (a generous gift

from R. Karadag). In particular, the chromatogram of

young fustic showed that the area ratio of sulfuretin

peak versus the fisetin peak is around 4 by using

254 nm as a detection wavelength. Consequently, this

could may be the reason for not detecting fisetin, in

samples 5.1 and 6.2 in which sulfuretin was found in

small quantities.

A similar argument can be applied on the results ob-

tained for 3 samples (1.1, 3.4 and 6.2) in which indi-

gotin was identified, but indirubin was not detected.

Both compounds are contained in woad (Isatis tinctoria

L.) and indigo (Indigofera species, e.g. Indigofera

tinctoria L.) which cannot be distinguished by chemi-

cal means as their composition appears to be similar

[2]. In both dyestuff sources indigotin is contained in

considerably larger quantities than indirubin [2]. The

latter was detected only in samples 3.1 and 3.3 along

with indigotin.

At least 4 different sources of red natural dyestuffs

have been found in the archaeological extracts, ac-

cording to the results of Table 3 which suggests the

presence of plant origin dyestuffs such as madder and

redwood and the presence of animal origin colouring

matters such as cochineal and lac dye. In particular,

alizarin and purpurin were detected in 2 samples (1.2

and 3.2) indicating the presence of a madder source

such as Rubia tinctorum L., Rubia peregrina L., Rubia

cordifolia L. and other species [2, 20]. In some inves-

tigations the presence of alizarin is used as a criterion

to exclude Rubia peregrina L., also known as wild

madder [13], based primarily on the observation that

extracts from this plant contains only a small (or none)

amount of alizarin. However, in the case of samples ex-

tracted from a textile, dyed with Rubia peregrina L.,

alizarin does occur according to another study [21].

Therefore, the detection of alizarin in a sample recov-

ered from a dyed textile by acid should not exclude

the possibility that the dyeing was executed with Rubia

peregrina L. [21].

The presence of cochineal in samples 4.3, 4.4 and

6.1 can be determined by the identification of carmi-

nic acid. In principle, the identification of the specific

Table 3. Analytical results of the artworks. Compounds RW(1) and RW(2) are contained in soluble redwood (see text)

Object no. Sample (colour) Detected compounds

1 1.1 (brown) RW(1), RW(2), Sulfuretin, Fisetin, Indigotin

1.2 (red) Laccaic acid A, Alizarin, Purpurin

2 2.1 (yellow) Sulfuretin, Fisetin, Ellagic acid

3 3.1 (red) RW(1), RW(2), Sulfuretin, Fisetin, Indigotin, Indirubin, Luteolin

3.2 (red) Purpurin, Alizarin, Luteolin, Ellagic acid

3.3 (green) Luteolin, Apigenin, Genistein, Indigotin, Indirubin

3.4 (green) Luteolin, Apigenin, Genistein, Indigotin

3.5 (yellow=green) Luteolin, Apigenin, Genistein, Sulfuretin, Fisetin

4 4.1 (yellow) Luteolin, Apigenin, Genistein, Sulfuretin, Fisetin

4.2 (yellow) Luteolin, Apigenin, Genistein, Sulfuretin, Fisetin

4.3 (yellow) Carminic acid, RW(1), Luteolin, Apigenin, Genistein, Ellagic acid

4.4 (red) Carminic acid, Kermesic acid, Flavokermesic acid, RW(1), RW(2)

5 5.1 (yellow) Sulfuretin, Ellagic acid

6 6.1 (orange) Carminic acid, RW(1), RW(2), Luteolin, Apigenin, Genistein

6.2 (yellow) RW(1), RW(2), Sulfuretin, Luteolin, Apigenin, Genistein, Indigotin

7 7.1 (red) RW(1), RW(2)

480 I. Karapanagiotis et al.

source of cochineal (Dactylopius coccus Costa,

Porphyrophora hameli Brandt, Porphyrophora

polonica L.) can be performed on the basis of the

relative composition of the minor constituents of co-

chineal, accompanied by a detailed statistical analysis

[22]. However, in the present study minor cochineal

ingredients such as kermesic and flavokermesic acid

were detected only once, as traces (sample 4.4). The

absence of the minor cochineal compounds can be at-

tributed either to ageing effects or to the small amount

of cochineal contained in the samples. Under these

circumstances any effort to determine the exact cochi-

neal source is not possible.

Laccaic acid A and several other laccaic acids,

which are ingredients of the lac dye prepared from

the scale insect Kerria lacca Kerr, were identified in

sample 1.2.

Two unknown compounds, labelled as RW(1) and

RW(2) were detected as exclusive colouring matters

in red sample 7.1 and in 5 more samples in mixtures

with other colouring compounds. In addition, only

RW(1) but not RW(2) was detected in sample 4.3.

The two unknown compounds have been detected, by

our chromatographic method, in silk and wool fibers

dyed with Caesalpinia sappan L., in pigment samples

prepared with the same plant source (EU-ARTECH)

and also in redwood raw materials found in the market

(Kremer Pigmente and Incense Magic). We note that

according to our (private) database which contains

chromatographic data of several reddish dyestuffs

such as cochineal, madder, hena, alkanna, lac dye

and kermes, RW(1) and=or RW(2) are not contained

in any of the above major dyestuffs. Therefore, these

two compounds can be considered as markers for the

Fig. 1. (a) Chromatogram corresponds to sample 6.1. Carminic acid (CA), luteolin (LU), apigenin (AP), genistein (GE) and two com-

pounds of soluble redwood, indicated as RW(1) and RW(2), are identified. (b) Spectrum of RW(1). (c) Spectrum of RW(2)

High-performance liquid chromatographic determination 481

presence of a Caesalpinia dyestuff source (also known

as ‘‘soluble’’ redwood [5]). This is confirmed by the

literature as follows. Figure 1 shows the identification

of RW(1) and RW(2) in sample 6.1, along with the

identification of carminic acid (CA), luteolin (LU),

apigenin (AP) and genistein (GE). The comparison of

the spectra of Fig. 1 with other relative reports, leads

to the conclusion that RW(1) corresponds to type B

(brazilein derivative) and RW(2) to type C spectrum

[5]. Both spectra have been recorded in hydrolysed

extracts of redwoods [5].

Finally, the presence of traces of ellagic acid

(tannin source) in samples 2.1, 3.2, 4.3 and 5.1 is not

indicative of a particular natural dyestuff source. This

compound can be synthesized by several plants or it

can be produced by the decomposition of vegetal frag-

ments present in the environment [2, 13]. Tannins can

contribute to degradation mechanisms, developed on

historical textiles [23].

Conclusion

A chromatographic method for the identification of

several ingredients of natural organic dyes, found in

objects of the cultural heritage has been developed.

The limits of detection were calculated for alizarin,

purpurin, carminic acid, laccaic acid A, luteolin, api-

genin, genistein, fisetin, sulfuretin, ellagic acid, in-

digotin and indirubin and were found to range from

0.002 to 0.029 mg mL�1. All compounds mentioned

above were detected in microsamples extracted from

ecclesiastical garments (15th–19th century) from the

Holy Mountain of Athos. Their identification led to

the conclusion that the following organic dyes have

been used for the decoration of the tested art objects:

dyer’s broom (Genista tinctoria L.), young fustic

(Cotinus coggygria Scop.), an indigoid dye source

either indigo (Indigofera species) or woad (Isatis

tinctoria L.), madder-type dyestuff, cochineal and lac

dye (Kerria lacca Kerr). Furthermore, two more un-

known compounds, which are components of soluble

redwoods (Caesalpinia trees) were found to be pres-

ent in few samples.

Acknowledgements. This work has been supported by the European

Commission through the European project INCO CT 2005 015406

MED-COLOUR-TECH (www.medcolourtech.org) and also by the

General Secretariat for Research and Technology (GSRT) of Greece

through the PENED 2003 Grant (Code no. 03E�697). The authors

would like to thank C. Karydis for providing the historical sam-

ples and for valuable discussions. Also, the authors would like to

acknowledge R. Karadag, I. Petroviciu, I. V. Berghe and J. Kirby for

providing some reference samples.

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