appendix 5 - universidade nova de lisboa

APPENDIX 5

Electronic Supplementary Material to the paper

“Investigation of crimson-dyed fibres for a new approach on the characterization of

cochineal and kermes dyes in historical textiles”

Published in the Analytica Chimica Acta, 2015, 2015 Oct 15, 897: 116-127,

doi: 10.1016/j.aca.2015.09.046

Ana Serrano a,b, Andre van den Doel a, c, Maarten van Bommel d, Jessica Hallett b, Ineke

Joosten a, Klaas J. van den Berg a

a Sector Research Movable Heritage, Cultural Heritage Agency of the Netherlands (RCE), P.O. Box 1600,

3800 BP, Amersfoort, The Netherlands.

b CHAM (Portuguese Centre for Global History), Faculdade de Ciências Sociais e Humanas, Universidade

Nova de Lisboa e Universidade dos Açores, Avenida de Berna, 1069 – 061 Lisboa, Portugal.

c Analytical Chemistry, IMM, Radboud University Nijmegen, Heyendaalseweg 135, 6525 AJ Nijmegen.

d Programme Conservation and Restoration of Cultural Heritage, University of Amsterdam, Johannes

Vermeerplein 1, 1071 DV, Amsterdam, The Netherlands.

ESM 1. Additional information about the materials used for dyeing experiments and the

samples provenance.

Materials for dyeing experiments. Lake water was collected in the shore of the Hemmeland

natural park facing the Gouwzee, North Netherlands. This and rain water were roughly cleared

using paper filter, before dyeing experiments. Bottled water was purchased in a local

supermarket, labelled with the following mineral concentrations per litre: Na 5 mg, K 3 mg,

HCO3 360 mg, Cl 8 mg, SO4 33 mg, NO3 < 0.5 mg and F 0.3 mg. Marseilles soap was purchased

in a local drugstore (Jacob Hooy & Co., Amsterdam, Netherlands). Copper sheets were

purchased in a local metal store (Amsterdam, Netherlands); energy dispersive X-ray

spectroscopy (EDX) revealed the presence of only copper in their matrix. Mediterranean sea

salt from Drogheria Alimentari (S. Piero a Sieve, Firenze) was purchased in a local supermarket.

Turmeric was part of the RCE’s reference collection and it was purchased in a drugstore

(Berlin, Germany). Ashes of a mixture of burnt oak wood types were provided by Annelies van

1

Hoesel (RCE, Amsterdam, Netherlands); XRF analysis principally detected the presence of

calcium, as well as potassium.

Insect samples [see also Appendix 4]. A total of 66 types of insect samples of kermes (Kermes

vermillio) and American (Dactylopius coccus), Armenian (Porphyrophora hamelii) and Polish

cochineal (Porphyrophora polonica) insect species were analysed with UHPLC-PDA (3 replicates

per type of insect sample) and, afterwards, modelled with multivariate statistical analyses.

These were obtained from the following sources: 4 types of D. coccus from Mexico and Peru,

given by Liberato Portillo (Botanical and Zoology Department, University of Guadalajara,

Mexico); 6 types of D. coccus from Mexico, Chile, Peru and Canary Islands, given by Mónica

González (Instituto Canario de Investigaciones Agrarias, Tenerife, Canary Islands); 2 types of D.

coccus from Canary Islands and Madeira, donated by Douglas Miller (Agricultural Research

Service, Systematic Entomology Laboratory, Maryland, U.S.A); 2 types of D. coccus, obtained

from Piero Tiano (ICVC-CNR, Florence); 2 types of D. coccus from Mexico, donated by Tatiana

Falcón Álvarez (Universidad Nacional Autónoma México, Mexico City, Mexico); 2 types of D.

coccus, purchased from Dott. Alessandro Bizarri (Florence, Italy) and Zecchi (Florence, Italy); 22

types of insects identified as D. coccus, from India, Peru, Ecuador, Indonesia, Honduras, Mexico

and Madeira, mainly collected during the 19th century, and supplied by Monique Simmonds

and Mark Nesbitt (Royal Botanic Gardens at Kew, London, England) [1]; 3 types of D. coccus, 1

type of P. hamelii and 1 type of Kermes vermillio donated by Dominique Cardon (CIHAM/UMR,

Lyon, France); 2 types of P. polonica given by Ewa Simon (Faculty of Biology and Environmental

Protection, University of Silesia, Katowice, Poland); 4 types of P. polonica (females and cysts)

donated by Łagowska Bożena and Katarzyna Golan (Department of Entomology, University of

Life Sciences, Lublin, Poland); 4 types of P. cynodontis (P. hamelii) from Iran, supplied by

Hassan-Ali Vahedi (College of Agriculture, Razi University, Kermanshah, Iran); 1 type of P.

hamelii provided by Cheryl Porter (Thesaurus Islamicus Foundation, Cairo, Egypt); 2 types of P.

hamelii provided by Jenny Balfour-Paul (Exeter University, Devon, England); 1 type of P.

hamelii obtained from Elizabeth Keheyan Yeghis (Sapienza University of Rome, Italy); 1 type of

P. hamelii, belonging to the reference collection of the RCE (Amsterdam, The Netherlands); 4

types of Kermes vermillio donated by Jo Kirby-Atkinson (independent researcher, London,

England); 1 type of Kermes vermillio obtained from Andre Verhecken (independent researcher,

Antwerp, Belgium) and 1 type of Kermes vermillio donated by Dimitrios Mantzouris and Yiannis

Karapanagiotis (University Ecclesiastical Academy of Thessaloniki, Greece). The insects

provided by Łagowska Bożena, Katarzyna Golan, Hassan-Ali Vahedi, Andre Verhecken,

Dimitrios Mantzouris and Yiannis Karapanagiotis were used to perform dyeing experiments.

2

Experimentally-dyed samples [see also Appendix 5]. A total of 141 experimentally-dyed

samples were submitted to UHPLC-PDA analyses. From these, 12 samples were previously

prepared by Harald Böhmer and donated by Regina Hoffman-de Keijzer (Universität für

angewandte Kunst, Wien, Austria) (3 samples), and by Jo Kirby-Atkinson (independent

researcher, London, England) (9 samples). Böhmer’s samples were prepared with alum, cream

of tartar, potash, kermes, American and Armenian cochineal on wool. Kirby-Atkinson’s samples

were mostly prepared with alum, kermes and American cochineal on silk and wool.

Historical samples [see also Appendix 7]. UHPLC-PDA and further multivariate statistical

analyses identified the presence of cochineal and/or kermes dyes on a total of 117 red samples

of silk and wool, belonging to 95 historical textiles. The majority of these samples had been

previously analysed in other works [2-5], although new samples were donated as well for this

study. Details on the textiles and permission to proceed with the UHPLC-PDA analyses on their

samples were kindly provided by the respective cultural heritage institutions: 2 textiles (2

samples) from Abegg-Stiftung (AS), Riggisberg, Switzerland [4] (contact with Bettina Niekamp

and Regula Schorta); 1 textile (1 sample) from Landesmuseum (LM), Zurich, Switzerland [4]

(contact with Erwin Hildbrand and Marie Wörle); 5 textiles (6 samples) from the Kungl.

Livrustkammaren (KLS), Stockholm, Sweden [4] (contact with Ann Grönhammar, Johanna

Nilsson and Lizette Gradén); 3 textiles (3 samples) from the Museu Nacional de Arte Antiga

(MNAA), Lisbon, Portugal [4] (contact with Ana Kol); 2 textiles (4 samples) from the Palácio de

Vila Viçosa (PVV), Portugal [4] (contact with Maria de Jesus Monge); 7 textiles (7 samples) from

the Deutsches Textilmuseum (DTM), Krefeld, Germany [4] (contact with Angelika Neuhausen);

1 textile (1 sample) from the Bernisches Historisches Museum (HMB), Bern, Switzerland [4]

(contact with Susan Marti); 2 textiles (3 samples) from the Metropolitan Museum of Art (MET),

New York, U.S.A. [4] (contact with Florica Zaharia, Janina Poskrobko and Sheila Canby); 3

textiles (6 samples) from the Musée des Tissus et musée des Arts décoratifs (MTMAD), Lyon,

France [4] (contact with Claire Berthommier); 6 textiles (7 samples) from the Rijksmuseum

(RMA), Amsterdam, The Netherlands [5] (contact with Suzan Meijer); 15 textiles (17 samples)

from the Schule für gestaltung auf der Lyss (SGL), Basel, Switzerland [4] (contact with Annette

Fluri); 1 [4] and 5 textiles (2 and 6 donated samples, respectively) from the Catharijneconvent

Museum (ABM), Utrecht, The Netherlands (contact with Micha Leeflang and Peter den Held);

11 textiles (12 samples) from the Calouste Gulbenkian Museum (CGM), Lisbon, Portugal [2, 3]

(contact with Clara Serra and Maria Fernanda Passos Leite); 5 [1] and 6 textiles (5 and 11

donated samples, respectively) from the Österreichisches Museum für Angewandte Kunst

(MAK), Wien, Austria (contact with Barbara Karl, Edith Oberhumer and Martina Dax); 6 textiles

3

(7 donated samples) from the Muzeum Narodowe w Warszawie (MNW), Warsaw, Poland

(contact with Ewa Orlińska-Mianowska and Monika Janisz); and 13 textiles (17 donated

samples) from the Victoria and Albert Museum (V&A), London, U.K. (contact with Susan North,

Joanne Hackett, Lucia Burgio and Rosemary Crill).

ESM 2. General procedure undertaken to obtain crimson shades on silk and wool fibres, based

on experimental results obtained in [6, 7] [see also Appendix 5].

Silk and wool fibres were washed in water with 50% Marseilles soap, kept at 80 ºC for 30 min –

percentage of ingredients in relation to the weight of fibres and volume of water in a

proportion of 1 to 500 to the weight of fibres. The fibres were thoroughly rinsed in water and

then immersed in a pre-mordant solution with 50% alum, 50% calcium nitrate and 25% cream

of tartar, at 80 ºC for 1h. Then, the solution was left to cool down to room temperature and pH

was brought to about 7 with potash or with oxalic acid - pH was controlled with a Horiba

compact pH meter B-212 twin pH waterproof. The fibres remained soaking in solution

overnight and, the next day, they were rinsed with water.

Meanwhile, circa 50% of grinded insects were extracted in water for 1h at 100 ºC – in this case,

the volume of water used had a proportion of 1 to 250 to the weight of fibres. In the case of

kermes and Armenian and Polish cochineal (100% of grinded insects), as soon as the solution

reached room temperature, the dye extract was separated from the insects’ fat with

chloroform in a separatory funnel, according to [8]. After that, 25% cream of tartar were added

into the solution and this was warmed up to 80 ºC. The mordanted fibres were immersed for

1h into this dye solution and kept at a constant temperature. Then, the solution with the dyed

fibres was left to cool down and pH was brought to 7. After that, the fibres were removed from

the dye bath and rinsed with water.

Very close shades to those evidenced in historical fibres were obtained as well on silk fibres

dyed with American cochineal, when using rain water with additional (non-laboratory grade)

ingredients, namely sea salt (12.5%), wood ashes (10%), turmeric (5.5%) and gum Arabic (20%)

[9]. Experimental conditions followed the above mentioned procedure, with the exception that

pH was not altered.

Parameters displayed in Table 1 were tested to evaluate the quality of the dyed results, as well

as possible influences on the chromatographic ratio of compounds in the insects’ colorant.

4

Table 1. Parameters tested on the 129 experimentally-dyed samples of silk and wool.

Parameters that provided best results are underlined.

Type of water Materials Temperature Duration pH Soap bath

- distilled - tap - lake - rain - bottled

- Marseilles soap 80 30 min -

Mordant bath

- mordant – alum/ tin - additives – calcium nitrate, calcium carbonate, sodium nitrate, cream of tartar/ tannic acid/ oak galls, sea salt, copper sheets, wood ashes

40, 80, 80 + Troom, 100

1h, 1h + overnight

4, 7, 10

Dye extract

- American cochineal - Kermes - American cochineal + kermes - Armenian cochineal - Polish cochineal

40, 100, 100 + Troom

30 min, 1h, 1h + overnight

-

Dye bath

- cream of tartar/ tannic acid/ oak galls, copper sheets, turmeric, gum Arabic, starch (only for wool)

40, 80, 80 + Troom

30 min, 1h, 1h + overnight

4, 7, 10

5

ESM 3. Detailed information on multivariate statistical analyses carried out for the models

construction.

Multivariate statistical analyses were applied in this study, in order to (1) assess possible

differences between closely-related chromatographic profiles of cochineal insect species and

their respective dyed fibres, and (2) classify unknown cochineal-dyed historical fibres.

Partial-least squares discriminant analysis (PLS-DA) is a supervised classification method that

has previously demonstrated successful results for the classification of cochineal species [1].

Principal component analysis (PCA), a non-supervised method, has recently been applied as

well for the differentiation of cochineal species and their characterization in unknown

cochineal-dyed historical fibres [2]. While PCA has often been used for discrimination, this is

not a particularly reliable approach and more suitable methods exist, such as PLS-DA [10]. PLS-

DA is a classification method that performs discriminant analysis on scores on latent variables,

designed to capture information in the data that is most useful for predicting the class [11].

Thus separation between classes is improved, and the use of discriminant analysis allows for

estimation of the accuracy of the models. When using PLS-DA, a scoreplot can show similarities

and differences between samples, which can then be ascribed to specific regions in the

chromatograms, by investigating the loadings [12].

In this study, a total of 1242 chromatograms were submitted to PLS-DA analysis. From these,

1137 were used to develop the models and they are samples of known identity (i.e. known

insect species). They comprise insect dyes and artificially aged and non-aged silk and wool

fibres experimentally-dyed with them. Chromatographic profiles acquired for dyed wool and

silk fibres have shown to be quite dissimilar and, for this reason, the resulting models could be

compromised. Therefore, since the aim is to distinguish between insect species, separate

classification models were constructed for the two types of fibres (Table 2).

Data Preprocessing. This was applied in the same way to all samples, before selecting different

samples for each model. Every chromatogram was acquired from 0 to 30 min and sampled

every half second, resulting in a chromatogram that can be stored as a 1x3600 vector x. Each

element of this vector corresponds to the absorbance at 275 nm at a specific retention time.

All sample chromatograms were stored in a 1242x3600 matrix, with every row containing the

chromatogram of one sample.

The chromatograms were aligned using correlation optimized warping (COW) [13], with

segment length 16, slack 9 and a reference sample that includes all analysed peaks – a

chromatogram corresponding to a wool fibre dyed with a mixture of American cochineal and

6

kermes. A baseline correction was applied using asymmetric least squares with λ=107 and

p=0.005 [14]. Alignment and baseline correction were performed on the chromatographic

region ranging 13–24 min, and hereafter the region was narrowed further to 14.5–17.5 and

20.5–24 min, because this includes relevant dye compounds (dcIV, dcVII and/or fk and ka) and

excludes unnecessary noise and/or compounds. Regions including ca or dcII compounds were

not considered, because they substantially vary between samples of the same class. Selection

of a specific chromatographic region is especially important in historical samples, in which

other dyestuffs and contaminations might be present. Chromatograms were then subjected to

standard normal variate (SNV) scaling and mean-centering.

Modeling. Models were created using the PLS Toolbox 7.9.3 (Eigenvector Research, Manson,

WA, USA) in Matlab R2014a (Mathworks, Natick, MA, USA). For all models, samples were

grouped into classes of insect dye species (American cochineal, Armenian cochineal, Polish

cochineal and a mixture of American cochineal and kermes).

Cross-validation was performed using venetian blinds with 10 data splits and 1 sample per

blind. Before the model is made, every 10th sample is removed from the data and set aside to

make a set of test samples. These test samples are then used to estimate the performance of

the model. For each model, optimal parameters were selected based on the cross-validation,

Table 2. All figures of merit (number of LV’s, variance explained and confusion matrices)

reported here are based on cross-validated models. There are very few misclassifications in

these models, as depicted in Tables 3 to 6. For the models that were used for projection of

historical samples, outliers were removed based on the 95% confidence intervals of the

Hotelling T2 and the Q-statistic. It was found that 20 silk and 12 wool experimentally-dyed

samples are above both limits. These samples were reported to correspond to very

unsatisfactory dyeing conditions (use of tap or bottled water, for instance).

The classification of 105 (97 silk and 8 wool fibres) unknown cochineal-dyed historical samples

was performed by projecting the corresponding chromatograms onto PLS-DA models created

with known identity dyed-silk and wool samples (aged and non-aged). Because these models

do not include insect dyes, the number of LV’s required and the number of misclassifications

on the cross-validation test set is much lower (Table 2 and confusion matrices, Tables 5 and 6).

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Table 2. Summary of the PLS-DA models developed in this study.

Model Number

of samples

Sample description LV1 and LV2 Full model

% of total variance

Number of LV’s

% of total variance

Figure 3 670 All cochineal insect dyes and all experimentally-dyed silks 37.18 5 61.04

Figure 4 442 All cochineal insect dyes and all experimentally-dyed wools 50.48 9 82.89

Figure 6 609 All artificially aged and non-aged experimentally-dyed silk fibres

and all historical silks 39.95 3 45.06

Figure 7 289 All artificially aged and non-aged experimentally-dyed wool fibres

and all historical wools 66,77 3 71.03

Table 3. Confusion table for the model of Figure 3.

Insect dyes and experimentally-dyed silk samples American Armenian Polish American + kermes

Pred

ictio

n (5

LV’

s)

American 567 3 0 0 Armenian 7 48 1 0 Polish 9 0 20 12 American + kermes 0 0 3 0


Insect dyes and experimentally-dyed wool samples American Armenian Polish American + kermes

Pred

ictio

n (9

LV’

s)



Experimentally-dyed and artificially-aged silk samples American Armenian Polish American + kermes

Pred

ictio

n (3

LV’

s)



Experimentally-dyed and artificially-aged silk samples American Armenian Polish American + kermes

Pred

ictio

n (3

LV’

s)


8

ESM 4. Cochineal compounds detected with UHPLC-PDA and UHPLC-MS [15, 16].

Compounds Characteristics UV spectra

dcII (2-C-glucopyranoside of flavokermesic acid)

[M-H]- – 475 (m/z) tR – 11.2 min.

carminic acid (ca) (2-C-glucopyranoside of kermesic acid)

[M-H]- – 491 (m/z) tR – 11.8 min.

DCOFK (3-O-glucoside of flavokermesic acid)

[M-H]- – 475 (m/z) tR – 14.8 min.

dcIV (2-C-α-glucofuranoside of kermesic acid)

[M-H]- – 491 (m/z) tR – 16.4 min.

dcVII (2-C-β-glucofuranoside of kermesic acid)

[M-H]- – 491 (m/z) tR – 17.0 min.

283

442

494

274

494

277

494

422

276

283

9

Compounds Characteristics UV spectra flavokermesic acid (fk)

[M-H]- – 313 (m/z) tR – 22.4 min.

kermesic acid (ka)

[M-H]- – 329 (m/z) tR – 22.6 min.

285

432

274

490

10

ESM 5. Photo-degradation compounds detected with UHPLC-PDA and UHPLC-MS.

Compounds Characteristics UV spectra

Photo-degradation compound 1

[M-H]- – 475 (m/z) tR – 7.6 min.

Photo-degradation compound 2

[M-H]- – n.a. tR – 7.7 min.

Photo-degradation compound 3 (unknown anthraquinone) Only in aged and historical fibres.

[M-H]- – n.a. tR – 8.9 min.

Photo-degradation compound 4 (isomer of dcII) Only in aged insect extracts.

[M-H]- – 475 (m/z) tR – 11.2 min.

255

277

340 498

285

340

280

11

ESM 6. Characterization of cochineal and kermes species in historical textiles, through the qualitative (visual examination) and quantitative evaluation (relative percentage of dcII and fk+ka markers – Figure 5) of the UHPLC-PDA chromatograms; the PLS-DA models using 2 LV’s (Figures 6 and 7) and 3LV’s (strict and/or most probable predictions); and the textiles date and the provenance [see also Appendix 7].

Classification [a] Provenance Date Type of sample Previous dyestuff attribution

Compounds detected with UHPLC-PDA

Qualitative/quantitative attribution PLS-DA classification

AS 416 Peru 17th cent Wool Cochineal [4] ca + dcIV + dcVII (dcII, fk and ka not detected)

American cochineal [c] (probably a wild species)

American cochineal (probably a wild species)

AS 4921 Southwest China mid-8th to mid-9th cents. Silk

Cochineal, brazilwood type, lac dye, madder (possibly chayroot) and indigo [4]

Ca + dcIV + dcVII + ka (eq.), type C comp. + laccaic acids C, E, B and A + alizarin + indigotin (dcII, fk and ka not detected)

“Root” cochineal [c] [d], brazilwood type, lac dye, madder (possibly chayroot) and indigo/woad (possibly a cross-contamination)

-

ABM st00910b Italy mid-16th cent.

Silk, warp Cochineal [4] ca + dcIV + dcVII + indigotin (dcII and fk not detected)

American/Armenian cochineal and cross-contamination of woad/indigo from the weft

American cochineal

Silk, weft Cochineal [4] American/Armenian cochineal and woad/indigo (blue fibres part of the weft)

American cochineal [e]

ABM st00882a Italy 2nd half 15th cent. (?) Silk - ga + dcII + ca + ea +dcIV + dcVII + fk + ka

American/Armenian cochineal and tannins American cochineal [f]

ABM st00887b Italy 15th/16th cents. Silk - ca + ea + dcIV + dcVII + ka (dcII and fk not detected)

Armenian/Polish cochineal and tannins Armenian cochineal [e]

ABM st00976 Italy beginning 15th cent. (?)

Silk, pile - ca + ea +dcIV + dcVII + fk + ka (dcII not detected)

American/Armenian cochineal and tannins

American cochineal [f] Silk, weft - ca + ea + dcIV + dcVII + ka

(dcII and fk not detected) American/Armenian cochineal and tannins

ABM t02191a North Netherlands, Utrecht end 15th cent. (?) Silk - ca +dcIV + dcVII + ka (dcII and fk not detected)


ABM t02013 The Netherlands 2nd half 15th cent. Silk - ca + ea +dcIV + dcVII + ka + fk eq. (dcII not detected) Polish cochineal and tannins Polish cochineal

CGM 1501B Italy, Genoa (?) 16th/17th cents. Silk, pile Porphyrophora spp. + tannins [2, 3] [b]

dcII + ca + ea + dcIV + dcVII + fk + ka

American/Armenian cochineal and tannins American cochineal

CGM 246 Italy, Genoa (?) 16th cent. Silk, pile Porphyrophora spp. + tannins [2, 3] [b]

dcII + ca + ea + dcIV + dcVII + fk + ka


CGM 188B Turkey, Scutari 17th cent. Silk, pile Porphyrophora spp. + tannins [2, 3] [b]

dcII + ca + ea + dcIV + dcVII + orcein + indigotin + ka (fk not detected)

American/Armenian cochineal, tannins, lichen and indigo (possibly a cross-contaminat.)

American cochineal

CGM 1431B Turkey, Scutari 17th cent. Silk, pile Porphyrophora spp. + tannins [2, 3] [b]

ca + dcIV + dcVII + ka (dcII and fk not detected) American/Armenian cochineal American cochineal

12




CGM 245 Turkey 16th cent. Silk, pile Porphyrophora spp. + tannins [2, 3] [b]

dcII + ca + dcIV + dcVII + fk + ka American/Armenian cochineal American cochineal

CGM 1388A Turkey 16th/17th cents. Silk, pile Porphyrophora spp. + tannins [2, 3] [b]

ca + dcIV + dcVII (dcII, fk and ka not detected) American/Armenian cochineal [c] American cochineal

CGM 1449 India 17th cent. Silk, pile American cochineal + tannins [2, 3] [b]

Ga + dcII + ca + ea + dcIV + dcVII + indigotin + fk + ka

American/Armenian cochineal, tannins and indigo (possibly a cross-contamination)

American cochineal

CGM 1422 India 17th cent. Silk Porphyrophora spp. + tannins[2, 3] [b]

Ca + dcIV + dcVII + indigotin + ka (dcII, fk and ka not detected)

American/Armenian cochineal [c]

and indigo (possibly a cross-contamination)

American cochineal

CGM T100 Iran 16th cent. Silk, pile

Porphyrophora spp. + tannins [2, 3] [b]

ca + ea + dcIV + dcVII (dcII, fk and ka not detected)


and tannins American cochineal

Silk, pile Porphyrophora spp. + tannins [2, 3] [b]

ca + dcIV + dcVII (dcII, fk and ka not detected) American/Armenian cochineal [c] American cochineal

CGM 1446 Iran, Yazd (?) 17th cent. Silk, pile Porphyrophora spp. + tannins [2, 3] [b]

ca + dcIV + dcVII + indigotin (dcII, fk and ka not detected)


and indigo/woad (possibly a cross-contamination)

American cochineal

CGM 1513 Iran 16th cent. Silk, pile Porphyrophora spp. + tannins [2, 3] [b]

Ga + dcII + ca + ea + dcIV + dcVII + indigotin + ka (fk not detected)

American/Armenian cochineal, tannins and indigo/woad (possibly a cross-contamination)

American cochineal

DTM00185 Italy 15th cent. Silk Kermes [4] Fk + ka + ka eq. Kermes - DTM01270 Spain, Granada about 1500 Silk Kermes [4] Fk + ka + ka eq. Kermes -

DTM00059 Italy 15th cent. Silk Kermes [4] Type C component + fk +ka Kermes and possibly a cross-contamination of brazilwood type

-

DTM01982 Italy 16th cent. Silk Cochineal [4]

dcII + ca + luteolin-7-O-ß-D-glycoside + apigenin-7-glycoside + type C component + dcIV + dcVII + luteolin (fk and ka not detected)

American/Armenian cochineal and cross-contamination of weld and brazilwood type

American cochineal

DTM01156 Italy 2nd half 15th cent. Silk Kermes [4] Fk + ka + ka eq. Kermes - DTM01151 Italy mid-15th cent. Silk Kermes [4] Fk + ka + ka eq. Kermes -

DTM01310 Italy or Spain c. 1600 Silk Cochineal [4] Ga + ca + ea + cIV +dcVII + indigotin + fk + ka (dcII not detected)

American/Armenian cochineal, tannins and possibly a cross-contamination of indigo/woad

American cochineal

HMB25 Italy 2nd half 15th cent. Silk Kermes [4] ea + fk + indigotin + ka Kermes, tannins and, possibly, a cross-contamination of indigo/woad

-

13




KLS 9735 Italy, Milan 1548 Silk, pile Polish cochineal [4] ga +dcII + ca +ea +dcIV +

dcVII + indigotin + fk + ka

American/Armenian cochineal, tannins and, possibly, a cross-contamination of woad/indigo

American cochineal

Silk, fringe Polish cochineal and kermes [4]

ga +dcII + ca + ea + dcIV + dcVII + fk + ka


American cochineal

KLS 9358 Italy, Milan late 16th cent. Silk, pile Polish cochineal [4] ga + dcII + ca + ea + dcIV + dcVII + fk + ka


American cochineal

KLS 31450 Sweden, Stockholm c. 1561 Silk, weft Polish cochineal [4] ga +dcII + ca +ea +dcIV + dcVII + fk + ka


American cochineal

KLS 755 Poland c. 1605 Silk Polish cochineal [4] ga + dcII + ca +ea + dcIV + dcVII + indigotin + fk + ka


KLS 26090 Belgium, Antwerp 1560-62 Silk, pile Polish cochineal [4] ga +dcII + ca + ea + dcIV + dcVII + indigotin + fk + ka


LM 6096 Switzerland, Kanton Luzern 1552 Wool Polish cochineal [4] ca + dcVII + alizarin (dcII, dcIV, fk and ka not detected)


and, possibly, a cross-contamination of madder


MAKT4128 Spain mid-16th cent. Silk Cochineal [4] ca + ea + dcIV +dcVII + indigotin + ka (dcII and fk not detected)

American cochineal, tannins and, possibly, a cross-contamination of indigo/woad

American cochineal

MAKT5597 Italy beginning 16th cent. Silk Cochineal [4] ca + ea + dcIV +dcVII + fk + indigotin + ka + fk eq. (dcII not detected)

Polish cochineal, tannins and, possibly, a cross-contamination of indigo/woad

Polish cochineal [e]

MAKT922 Italy mid-15th cent. Silk Polish cochineal [4] ca + ea + dcIV +dcVII + fk + ka +fk eq. + ka eq. (dcII not detected)

Polish cochineal and tannins Polish cochineal [e]

MAKT9236 Italy 2nd half 15th cent. (?) Silk Cochineal [4] ga + dcII + ca + ea + dcIV +dcVII + fk + ka


MAKT2320 Italy or Spain 2nd half 16th cent. Silk Cochineal [4] ca + ea + dcIV + dcVII + ka (dcII and fk not detected)


MAKT8473a Italy c. 1500 Silk, pile - ca + ea + dcIV +dcVII + fk + ka + fk eq. + ka eq. (dcII not detected)


MAKT8473e Austria 18th cent. Silk, pile - dcII + ca + ea + type c component + dcIV +dcVII (fk and ka not detected)

American/Armenian cochineal, tannins and brazilwood type (cross-contamination from the warp/weft)


MAKT918 Italy, Florence around 1500 Silk, pile - Fk + ka + ka eq. + kermes unknown compounds Kermes -

MAK T 9208 Italy 15th/16th centuries Silk, pile - Fk + ka Kermes -

14




MAKT8978 Italy 2nd half 16th cent. Silk - ca + dcIV +dcVII + indigotin (dcII, fk and ka not detected)

American/Armenian cochineal [c] and indigo/woad

American cochineal

MAKF221a France End 16th cent.

Silk, weft - ga + dcII + ca + ea + type C comp. + dcIV +dcVII (fk and ka not detected)

American/Armenian cochineal, tannins and cross-contamin. of brazilwood type


Silk, weft - dcII + ca + type C comp. +dcVII (dcIV, fk and ka not detected)

American/Armenian cochineal and cross-contamination of brazilwood type


Silk, warp - ga + ca + ea + type C comp. + dcIV +dcVII (dcII, fk and ka not detected)

American/Armenian cochineal [c], tannins and cross-contamin. of brazilwood type


Silk, warp - ga + ca + ea + type C comp. + dcIV +dcVII (dcII, fk and ka not detected)


American cochineal

Silk, weft - ga + dcII + ca + ea + type C comp. + dcIV +dcVII (fk and ka not detected)

American/Armenian cochineal, tannins and cross-contamin. of brazilwood type


Silk - ga + ca + ea + type C comp. + dcIV +dcVII (dcII, fk and ka not detected)


American cochineal

MET46156140 Italy 15th/16th cent. Silk, pile Polish cochineal [4] ca + ea + dcIV + dcVII + fk +

ka (dcII not detected) American/Armenian cochineal and tannins American cochineal

Silk, weft Polish cochineal [4] ca + ea + dcIV + dcVII + fk + ka (dcII not detected)

Polish/Armenian cochineal and tannins Polish cochineal [e]

MET522011 Iran mid-16th century Silk Polish cochineal [4] dcII + ca + dcIV + dcVII + fk + ka American/Armenian cochineal American cochineal

MT30935 Italy 2nd half 15th cent.

Silk, pile Polish cochineal [4]

Ca + ea + type c component + dcIV + dcVII + fk + ka + fk eq. + ka eq. (dcII not detected)

Polish cochineal, tannins and cross-contamination of brazilwood type

Polish cochineal

Silk, weft Polish cochineal [4]

Ca + ea + type c component + dcIV + dcVII + fk + ka + fk eq. + ka eq. (dcII not detected)

Polish cochineal, tannins and cross-contamination of brazilwood type

Polish cochineal

MT33357 Italy 2nd half 15th cent. Silk, pile Polish cochineal [4]

Ca + ea + dcIV + dcVII + fk + ka + fk eq. + ka eq. (dcII not detected) + unknown compounds from kermes

Mixture of Polish cochineal and kermes, tannins and cross-contamination of brazilwood type

Polish cochineal

Silk, weft Polish cochineal [4] Ca + ea + fk + ka + fk eq. + ka eq. (dcII not detected)

Kermes, tannins and cross-contamination of cochineal -

15




MT22864 Italy End 15th cent. Silk, pile Polish cochineal [4] Ca + dcVII + ka + ka eq. (dcII,

dcIV and fk not detected) Kermes and cochineal (very small amount) -

Silk, weft Polish cochineal [4] Ca + dcVII + ka + ka eq. (dcII, dcIV and fk not detected)

Kermes and cochineal (very small amount) -

MNAA 2136 tec India 17th cent. Silk Cochineal [4] ga + ca + ea +dcIV +dcVII + fk + ka (dcII not detected)


MNAA 1925 tec Italy, Florence 15th / 18th cents. Silk, pile Polish cochineal [4] ca + ea + dcIV +dcVII + fk + ka + fk eq. + ka eq. (dcII not detected)

Polish cochineal and tannins Polish cochineal

MNAA 1616 tec Italy, probably Florence 15th century Silk, pile

Polish cochineal [4] / Porphyrophora spp. or mixture with kermes [2, 3] [b]

ca + ea + dcIV +dcVII + ka (dcII and fk not detected)

Polish/Armenian cochineal and tannins Polish cochineal [e]

PVV 3102a Unknown After 16th century Silk, warp Cochineal [4] Ga + dcII + ca + ea +dcIV

+dcVII +fk (ka not detected) American/Armenian cochineal and tannins American cochineal

Silk, weft Cochineal [4] Ga + dcII + ca + ea +dcIV +dcVII +fk + ka


PVV 3102b Italy 15th cent.

Silk, pile Polish cochineal [4] Ga + ca + ea +dcIV +dcVII +fk + ka + fk eq. + ka eq. (dcII not detected)


Silk, weft Polish cochineal [4] Ga + ca + ea +dcIV +dcVII +fk + ka + fk eq. + ka eq. (dcII not detected)


RMA38A North Netherlands mid-17th century Wool Cochineal [5] dcII + ca + dcIV + dcVII + ka (fk not detected) American/Armenian cochineal American cochineal

RMANM1999L North Netherlands 1st half 17th cent. Wool Cochineal and madder [5]

dcII + ca + dcIV + dcVII+ alizarin + fk + purpurin (ka not detected)

American/Armenian cochineal and cross-contamination of madder

American cochineal

RMA58D North Netherlands mid-17th century Wool Cochineal [5] dcII + ca + dcIV + dcVII+ indigotin + ka (fk not detected)

American/Armenian cochineal and possibly a cross-contamination of indigo/woad

American cochineal

RMA2271K

North Netherlands mid-17th century

Wool Cochineal [5] dcII + ca + dcIV + dcVII+ fk + indigotin + ka

American/Armenian cochineal and and possibly a cross-contamination of indigo/woad

American cochineal

RMA2271L Wool Cochineal and madder [5]

dcII + ca + ruberythric acid + lucidin-3-O-primeveroside + dcIV + dcVII + alizarin + fk + Xantho-purpurin + purpurin + nordamnacanthal + rubiadin (ka not detected)

American/Armenian cochineal and madder American cochineal [e]

16




RMA49K Brussels mid-17th century Silk Cochineal [5] Ga + dcII + ca + ea + dcIV + dcVII+ fk co-eluting w/ indigotin + ka


American cochineal

RMA16495A North Netherlands mid-17th century Wool Cochineal [5] dcII + ca + dcIV + dcVII+ fk + ka American/Armenian cochineal American cochineal

SGL1907/114 Italy (?) c. 1600 Silk, pile Kermes [4] Ga + dcII + ca + ea + dcIV + dcVII (fk and ka not detected)

American cochineal and tannins American cochineal [e]

SGL1907/230 unknown provenance 16th/17th cent. Silk, pile Polish cochineal + kermes? [4]

Ga + dcII + ca + ea + dcIV + dcVII (fk and ka not detected)

American cochineal and tannins American cochineal

SGL1907/208 Italy 15th cent. Silk, pile Polish cochineal + kermes? [4]

ca + ea + dcIV + dcVII + fk + ka (dcII not detected) Polish cochineal and tannins Polish cochineal [e]

SGL1907/106

Italy 2nd half of the 16th cent.

Silk, warp Cochineal [4]



Silk, weft Cochineal [4]



American cochineal

SGL1929/28

Italy late 16th cent.

Silk, warp Cochineal [4] ca + ea + dcIV + dcVII (dcII, fk

and ka not detected) American/Armenian cochineal [c]


Silk, weft Cochineal [4] ca + ea + dcIV + dcVII (dcII, fk



SGL1966/33a-c Italy c. 1500

Silk, pile Kermes [4]

ca + ea + dcIV + dcVII + ka + fk eq. + ka eq. (dcII not detected)


SGL1966/7

Italy 16th cent.

Silk, warp

Polish cochineal [4]

ca + luteolin-7-O-ß-D-glyc. + ea + apigenin-7-glyc. + dcIV + dcVII + ka (dcII and ka not detected)

American/Armenian cochineal and tannins; cross-contamination of weld

American cochineal

SGL1926/26 Presumably Italy 16th/17th cent.

Silk, pile Polish cochineal + kermes? [4]

ca + ea + dcIV + dcVII (dcII, fk and ka not detected)



SGL1966/32 b Italy 1460 (?) Silk Cochineal + kermes [4] dcII + ca + ea + dcIV + dcVII (fk and ka not detect.)


SGL1923/8 Italy 3rd quarter 16th cent.

Silk Polish cochineal [4]



SGL1967/st.41 Italy late 16th cent.

Silk Cochineal [4]

ca + ea + dcIV + dcVII + indigotin (dcII, fk and ka not detected)


and tannins and possibly a cross-contamination of indigo/woad

American cochineal

17




SGL1967/st.33 Italy 16th cent.

Silk Polish cochineal [4] ca + ea + dcIV + dcVII (dcII, fk



SGL1967/54 Italy 14th cent. Silk Kermes [4] Ea + fk + ka + fk eq. + ka eq. Kermes and tannins - SGL1967/51

Italy or France 16th cent. Silk

Cochineal [4] Ga + ca + ea + dcIV + dcVII (dcII, fk and ka not detected)



SGL1907/105 Switzerland c. 1600 Silk Cochineal [4]



SZT 1502 Italy 15th cent.

Silk, pile -

Ca + ea + dcIV + dcVII + ka + fk eq. (dcII and fk not detected)

Polish/Armenian cochineal Armenian cochineal [e]

Silk, weft - Ca + dcIV + dcVII + ka (dcII and fk not detected) Polish/Armenian cochineal Armenian cochineal [e]

SZT 1330 Italy 15th/16th cents. Silk, weft

- Ca + dcVII + indigotin + fk + ka (dcII and dcIV not detected)

Polish cochineal and possibly a cross-contamination of indigo/woad

Armenian cochineal

SZT 268 Italy 16th cent. Silk, weft - Ca + dcIV + dcVII + ka + fk eq. (dcII and fk not detected) Polish/Armenian cochineal Polish cochineal [e]

SZT 316 Italy 17th cent. Silk, warp - Ga + dcII + ca + ea + dcIV + dcVII + fk (ka not detected)


SZT 292 Italy or Turkey 15th cent. Silk, pile - ca + dcIV + dcVII + ka (dcII and fk not detected) Polish/Armenian cochineal Armenian cochineal

SZT 291 Turkey 16th cent. Silk, pile - ca + dcIV + dcVII (dcII, fk and ka not detected)

American/Armenian cochineal [c] and tannins American cochineal

V&A28-1889 Iran c. 1700

Silk, embroidery - dcII + ca + ea + dcIV + dcVII + fk co-eluted w/ indigotin + ka

American/Armenian cochineal, tannins and possibly a cross-contamin. of indigo/woad

American cochineal

Silk, embroidery - dcII + ca + dcIV + dcVII + fk co-eluted w/ indigotin (ka not detected)

American cochineal and possibly a cross-contamin. of indigo/woad American cochineal

Silk, pile - dcII + ca + dcIV + dcVII + fk (ka not detected) American/Armenian cochineal American cochineal

V&A34-1903 Iran 16th century Silk, warp - ca + ea + dcIV + dcVII + ka (dcII and fk not detected)


V&A1752A-1892 Iran 17th century Silk, warp - Ga + dcII + ca + ea + dcIV + dcVII + indigotin + (fk and ka not detected)

American/Armenian cochineal, tannins and cross-contamination of indigo/woad

American cochineal

V&A832A-1898 Iran 16th century Silk, warp - Ca + type C component + dcIV + dcVII + ka (dcII and fk not detected)

American/Armenian cochineal and cross-contamination of brazilwood type

American cochineal

18




V&A750-1884 Turkey, Istanbul or Bursa 16th/17th centuries Silk, warp - dcII + ca + ea + dcIV + dcVII + ka (fk not detected)


V&A94-1878 Turkey 1st half 17th cent. Silk, pile - dcII + ca + ea + dcIV + dcVII + fk + ka


V&A101-1878 Turkey 16th/17th centuries Silk, pile - dcII + ca + ea + dcIV + dcVII + fk + ka


V&A964-1898 Turkey 16th/17th centuries Silk, warp - dcII + ca + dcIV + dcVII + fk +

ka American/Armenian cochineal American cochineal

Silk, weft - dcII + ca + ea + dcIV + dcVII + fk + ka


V&A624-1892 Turkey 16th century Silk, warp - dcII + ca + dcIV + dcVII + fk + ka American/Armenian cochineal American cochineal

V&A758-1884 Turkey 1500-1600 Silk, weft - dcII + ca + ea + dcIV + dcVII + ka (fk not detected)


V&A145-1891 Turkey 1550-1599 Silk, warp - ca + ea + dcIV + dcVII (dcII, fk and ka not detected)


and tannins Armenian cochineal

V&A1028-1900 Italy 1450-1475 Silk, pile ca + ea + dcIV + dcVII + ka eq. (dcII and fk not detected)

Armenian/Polish cochineal and tannins Armenian cochineal

V&A1016-1888 Italy 1550-1599

Silk, warp - Ga + dcII + ca + ea + dcIV + dcVII (fk and ka not detected)

American/Armenian and tannins American cochineal

Silk, weft - Ga + dcII + ca + ea + dcIV + dcVII (fk and ka not detected)

American/Armenian and tannins American cochineal

[a] Inventory numbers attributed to the historical textiles by the respective institutions (ESM 1); [b] Tannin compounds (ellagic acid, ea, or gallic acid, ga) were not always found in these samples, although they were previously reported [2, 3]. The absence of these compounds might be related to the type of extraction method applied in this study. [c] Attribution was based on the qualitative evaluation of the results. Quantitative results were not available because minor compounds dcII, fk and ka were not detected. [d] “Root” cochineal [17] has been designated as a form of referring to any Porphyrophora species that is probably present in European and Asian historical textiles dated before the 16th century, and which species cannot be accurately characterized. In this case, the term is used to classify a result that comprises a complex mixture of dyestuffs much different than the cochineal-dyed references and, for this reason, PLSDA models/predictions are not able to provide a correct classification. [e] When strict predictions (a sample being classified in precisely one class) were not available, attribution was based on: the most probable predictions (% of highest probability for one class of species, based on 3 LV’s model); the evaluation of the plots in Figures 6 and 7 (2 LV’s); the qualitative and quantitative interpretation of the chromatographic results; and the textiles date and provenance. [f] Cochineal species are strictly predicted, but results do not match with the date of the textiles. This date should be probably reconsidered.

19

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[16] K. Lech, K. Witkoś, B. Wileńska, M. Jarosz, Identification of unknown colorants in

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[17] R.H. Keijzer, M.R. van Bommel, M. de Keijzer, Coptic textiles: dyes, dyeing

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appendix 5 - universidade nova de lisboa

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