e-PS, 2012, 9, 90-96 ISSN: 1581-9280 web edition e-PRESERVATIONScience ISSN: 1854-3928 print edition www.Morana-rtd.com published by MORANARTD d.o.o. © by M O R A N A RTD d.o.o. A DISCUSSION ON THE RED ANTHRAQUINONE DYES DETECTED IN HISTORIC TEXTILES SCIENTIFIC PAPER FROM ROMANIAN COLLECTIONS Irina Petroviciu1,5, Ileana Creƫu2, Ina Vanden Berghe3, Jan Wouters4, Andrei Medvedovici5, Florin Albu6, Doina Creanga7 This paper is based on a presentation at Biological sources containing anthraquinone dyes of vege- the 2nd International Conference “Matter tal and animal origin have been used for dyeing textiles and Materials in/for Cultural Heritage” from ancient times. Initially available only locally, later (MATCONS 2011) in Craiova, Romania, object of trade, different species were used in various 24-28 August 2011. areas of the world, in different historic periods. Moreover, the preference for certain biological sources also depend- Guest editor: ed on the value, destination and manufacturing technique Prof. Dr. Elena Badea of the objects to be created. A large number of textiles from Romanian museum collections have been studied 1. National Museum of Romanian History, since 1997, in order to identify the natural dyes and their Centre of Research and Scientific biological sources. Analysis were first performed by Liquid Investigation, Bucharest, Romania Chromatography with Diode Array Detection (LC-DAD) and 2. National Museum of Art of Romania, more recently by Liquid Chromatography with Mass Bucharest, Romania Spectrometric detection (LC-MS). Anthraquinones of vege- 3. Royal Institute for Cultural Heritage tal origin, such as Rubia tinctorum L. (madder), as well as (KIK/IRPA), Brussels, Belgium from scale insects: Kerria lacca Kerr (lac dye), Dactylopis 4. Conservation scientist – Consultant, coccus Costa (Mexican cochineal), Porphyrophora hamelii Zwijndreecht, Belgium Brandt (Armenian carmine dyeing scale insect), 5. University of Bucharest, Faculty of Porphyrophora polonica L. (Polish carmine dyeing scale Chemistry, Department of Analytical insect), Kermes vermilio Planchon (kermes) were identified Chemistry, Bucharest, Romania in various textiles dating from the 15th-20th century and in 6. Bioanalytical Laboratory, S.C. seal bound fibres, in 15th-16th century documents. This LaborMed Pharma S.A., Bucharest, paper presents the procedures used in the identification of Romania the above-mentioned biological sources, based on the use 7. Bucovina Museum, Suceava, Romania of an ion trap mass spectrometer as the LC detector. The preferences for certain biological sources are discussed, corresponding authors: according to the textile manufacturing technique, period [email protected] and provenance. [email protected] 1 Introduction Anthraquionone-based dyes are among the oldest biological sources used for textile dyeing. Rubia tinctorum L. (madder) was used in ancient Egypt (not prior to 1350 BC), Mesopotamia, in the Greek and Roman times, India and surrounding countries, as well as in Middle East and Europe.1 Other Rubiaceae, such as Rubia peregrina L. (wild madder), Rubia cordifolia L. (Indian madder or munjeet), Galium verum L. (lady’s received: 29.02.2012 bedstraw), Relbunium hypocarpium L. (relbún) were used in various parts accepted: 02.11.2012 of the world.1,2 The use of these plants in textile dyeing was also con- firmed in scientific studies.2-8 The widespread use of Rubiaceae plants key words: may be explained by the variety of hues they may produce - from orange- natural dyes, historic textiles, liquid chro- red to pink, violet and brown - due to the high number of dye components matography, mass spectrometry, identifi- contained in the same plant and the dye’s ability to combine with several cation 90 © by M O R A N A RTD d.o.o. metallic mordants.1 Moreover, many of these plants was identified in various textiles in European collec- are widely distributed around the world and were tions, starting with the third quarter of the 16th accessible as local, valuable dye sources to different c.1,2,14,18-20 civilizations.1 From the analytical point of view, useful analyses of Although of less importance as compared to anthraquinone containing dyes started with the appli- Rubiaceae, other anthraquinone based plants such cation of thin-layer chromatograpy in the late 1960s. as Rheum, Rumex and Rhamnus species have been A systematic approach to the analysis of also used in textile dyeing.1,2 anthraquinone containing dyes and based on high- performance liquid chromatography and UV-VIS Insect dyes have also played a prominent role in tex- spectrometric detection and identification was pub- tile dyeing. Original to the Mediterranean basin where lished by Wouters in 1985.21 Since then, the identifi- it may be found as a parasite on the kermes oak cation of such dyes in historic textiles based on a (Quercus coccifera L.), Kermes vermilio Planchon. variety of liquid chromatographic separation methods (kermes) has been used by cultures on the shores of kept attracting the attention of scientists in many lab- the Mediterranean Sea since prehistoric times. Later, oratories and results obtained have been the subject it became an object of commerce, exchanged with of several publications.14-16,18,19,22-31 Nowadays, liq- various parts of the world.1 Its appreciation as an uid chromatographic separation is ideally combined expensive and precious dye culminated in 1464, with photodiode-array (PDA; or diode array detection, when Pope Paul II decided that the cardinals’ robes DAD) and mass spectrometric (MS) detectors in a must be dyed with kermes. It declined rapidly in the hyphenated configuration.22-32 second half of the 16th c., when cochineal became available from the New World. Since 1997, a collaborative project entitled “Dyes in textiles from Romanian collections” has been devel- Kerria lacca Kerr. (lac dye) has been known and used oped, between Romanian institutions and KIK/IRPA in India and China, mostly for dyeing silk, wool and Brussels. The project aims to enrich the existing cashmere.1 Lac dye was identified in textiles from information on textiles in local collections, based on Palmyra9 as well as in various textiles from Asia dye analysis. Several categories of textiles have been Minor.10,11 It is rarely identified in European medieval studied until now: religious embroideries (from the silks, probably due to regulations restricting its use.1 National Museum of Art of Romania, Putna and Sucevita Monasteries), brocaded velvets, knotted There are two genuses of carminic acid containing carpets, kilims and sumak from Minor Asia (National insects, both living as parasites on plants in different Museum of Art of Romania), Romanian ethnographi- parts of the world: Porhyrophora species, that may be cal textiles (from “Bucovina” Museum, Suceava and found in Europe and Asia and Dactylopius, in the the National Village Museum “Dimitrie Gusti”, Americas. Porhyrophora polonica L. (Polish Bucharest), knotted carpets from the Black Church, cochineal, preferably called Polish carmine dyeing Brasov. The categories of textiles should be consid- scale insect) and Porhyrophora hamelii Brandt ered as representative for the Romanian textile her- (Armenian cochineal, preferably called Armenian car- itage. However, within each group of textiles studied, mine dyeing scale insect) are mostly discussed in objects selection and sampling was made based on relation to historic textiles. According to the current several criteria such as accessibility to collections, knowledge, other Porhyrophora species have also possibilities of sampling (in most cases sample with- been known and used, sold as substitutes for the drawal was possible for objects undergoing conser- above and even mixed with them.1 Identification of vation interventions) and specific research interest Polish and Armenian carmine dyeing scale insect (studies on dated objects to be used as references, dyes, and their distinction from Mexican cochineal objects of particular interest to art historians etc.) and (Dactylopius coccus Costa) in textiles of historic inter- did not follow any statistical sample selection. est, became possible with the method developed by Wouters and Vercheken.12,13 Based on this method, a This article is an overview of anthraquinone-based mixture of Polish carmine dyeing scale insect with biological sources identified in textiles from kermes could be identified in three Florentine borders Romanian collections, based on LC-PDA and LC-MS dated 14th-15th c.14 Polish carmine dyeing scale analysis,33-37 with special emphasis on the progres- insect was also identified by thin layer chromatogra- sive use of an ion-trap mass spectrometer as detec- phy in various textiles from Western European collec- tor.38 Rather than reporting the results themselves, tions (1450-1600) as well as in a Hungarian embroi- the article intends to underline the variety of sources dery from the 17th-18th c.8,15 Porhyrophora hamelii identified in textiles from local collections and the Brandt (Armenian carmine dyeing scale insect) was contribution this knowledge is bringing to better identified in Coptic textiles (3rd-10th c.), in a cashmere understanding the historic context in which the cloth used in a Sassanid kaftan (6th-7th c.) as well as respective textiles have been created. in Ottoman fabrics, such as velvets and lampas (15th- 17th c).16-18 Dactylopius coccus Costa (Mexican cochineal), the main relevant representative of the 2 Experimental Dactylopius genus, was known and used by Pre-