Identification of natural dyes in historical textiles from Romanian collections by LC-DAD and LC-MS (single stage and tandem MS)

In this study, the dyes present in five 17th- to 18th-century textiles from the National Museum of Art of Romania, three religious embroideries and two brocaded velvets, are characterized and discussed, together with earlier results on textiles from Romanian collections obtained by the same research group. Dye analyses were performed using two methods: the well-established liquid chromatography-diode array detection (LC–DAD) and a recently developed liquid chromatography-mass spectrometry (LC–MS) analytical protocol. The examination of very small historical samples by both techniques allows a better insight in the advantages and limitations of the two approaches to real analyses to be obtained. LC–MS data interpretation is based entirely on the results accumulated for dye standards. Electrospray ionization (ESI) was used in the negative ion mode and an ion trap served as mass analyzer. Both single stage (MS) and tandem (MS/MS) mass spectrometric approaches were considered. The dyes and natural sources identified by both analytical techniques are discussed in the historical context of the textiles, with respect to earlier results collected for similar Romanian objects. The study showed that the dye sources found in the 17th- and 18th-century Romanian velvets and embroideries were produced using a wide variety of dye sources, suggesting influences from Europe as well as from Asia Minor. Dye sources imported from New World have been also detected. The range of biological sources is in very good correspondence with earlier results obtained from textiles in the Romanian Collections. LC-MS (single stage and tandem MS) approaches have been demonstrated to be valuable tools for dye identification in small-scaled samples from historical textile objects only if sufficient knowledge on the dyes and their biological sources is first accumulated within experiments performed on standard dyes and standard dyed fibers.