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Article

Refining the Production Date of Historical Palestinian Garments Through Dye Identification

by
Diego Tamburini
1,*,
Ludovic Durand
2 and
Zeina Klink-Hoppe
3
1
Department of Scientific Research, The British Museum, London WC1B 3DG, UK
2
Department of Chemistry, Université Toulouse III Paul Sabatier, 31062 Toulouse, France
3
Department of the Middle East, The British Museum, London WC1B 3DG, UK
*
Author to whom correspondence should be addressed.
Heritage 2025, 8(1), 28; https://doi.org/10.3390/heritage8010028
Submission received: 19 December 2024 / Revised: 9 January 2025 / Accepted: 10 January 2025 / Published: 14 January 2025
(This article belongs to the Special Issue Dyes in History and Archaeology 43)
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Abstract

The dyes used to produce two Palestinian garments from the British Museum’s collection attributed to the late 19th–early 20th century were investigated by high pressure liquid chromatography coupled with diode array detector and tandem mass spectrometry (HPLC-DAD-MS/MS). Palestinian embroidery is a symbol of national identity and the topic of scholarly research. However, little attention has been given to the dyes and how these changed with the introduction of new synthetic formulations in the second half of the 19th century. The results revealed the use of natural indigoid blue and red madder (Rubia tinctorum), in combination with tannins. Yellow from buckthorn (probably Rhamnus saxatilis) and red from cochineal (probably Dactylopius coccus) were found mixed with synthetic dyes in green and dark red embroidery threads, respectively. Early synthetic dyes were identified in all the other colours. These include Rhodamine B (C.I. 45170), Orange II (C.I. 15510), Orange IV (C.I. 13080), Metanil Yellow (C.I. 13065), Chrysoidine R (C.I. 11320), Methyl Violet (C.I. 42535), Malachite Green (C.I. 42000), Fuchsin (C.I. 42510), Auramine O (C.I. 41000) and Methyl Blue (C.I. 42780). As the date of the first synthesis of these dyes is known, the production date of the garments was refined, suggesting that these were likely to be produced towards the end of the 1880s/beginning of the 1890s. The continuous use of historical local sources of natural dyes, alongside new synthetic dyes, is of particular interest, adding rightful nuances to the development of textile-making practices in this region.

1. Introduction

Natural dyes extracted from plants, fungi, lichens, insects and molluscs have been used for millennia to colour textiles and other objects [1]. In 1856, the accidental synthesis of the purple molecule mauveine, by Sir William Henry Perkin, marked the beginning of the synthetic dye revolution [2]. Fuelled by technological advancements, scientists found an exponentially increasing number of ways to reproduce the colours of nature by starting from simple molecules and, in a few decades, thousands of new formulations became available worldwide. Synthetic dye manufacture remained an exclusively European business until after World War I, but these materials started being exported globally very early and very rapidly after their invention [3].
The dynamics behind the introduction of synthetic dyes in textile-making practices outside Europe are complex and encompass components of social and cultural acceptance, as well as economic and colonial history. The phenomenon is often simplistically described as synthetic dyes wiping natural dyes away in a few years [4,5]. However, research has started revealing a more nuanced scenario [6], showing that certain natural dyes were never fully abandoned in some dyeing traditions, while mixtures of natural and synthetic dyes were often used intentionally to create specific colour shades [7,8,9,10,11,12,13,14,15,16,17,18,19,20]. Consequently, dye analysis emerges as an important research area to advance our knowledge of this phenomenon.
Various analytical techniques provide information on natural and synthetic dyes [2,21]. Non-invasive spectroscopic approaches, including UV–Vis-NIR reflectance and fluorescence spectroscopies, can be applied directly on the area of interest, for example via optical fibres; they can be used to differentiate between classes of dyes and identify some of them [22,23,24,25,26]. However, a combined spectrum is usually obtained, containing signals from the substrate, potential mixtures of dyes and possible degradation products. Therefore, although fibre optic reflectance spectroscopy (FORS) and spectrofluorimetry are valuable screening techniques, micro-invasive analysis is often needed for more accurate dye identification at a molecular level. Raman spectroscopy, especially in the surface-enhanced Raman spectroscopy (SERS) mode, can be used by depositing silver nanoparticles directly on the artwork, or on a micro-sample [27,28,29,30]. Common natural and synthetic dyes are generally identified by SERS, although the detection of minor components in dye mixtures, the identification of yellow natural dyes and molecular differentiation of isomers represent significant limitations of the technique. When sampling is allowed, high pressure liquid chromatography (HPLC) is the state-of-the-art technique for molecular identification of natural and synthetic dyes [31,32,33,34,35,36]. The technique requires minimal sampling (2–3 mm of a single thread) and provides insight into the molecular composition of dyes and dye mixtures, which is fundamental to achieve straightforward identifications. Synthetic dyes can be particularly challenging due to the high variety of dye formulations and the difficulties in building accurate reference databases [37,38]. Nevertheless, high-resolution mass spectrometry has proved particularly valuable to distinguish dyes with very similar molecular compositions [33,39,40,41,42,43].
Palestinian textiles and costumes are rich and varied and have a long history. They were made of various materials: wool, cotton, linen and silk, and were often embellished, particularly women’s garments, with a variety of embroidered stitches arranged in colourful patterns and harmonious combinations. Indeed, traditional Palestinian womenswear is famous for its rich embroidery (tatreez). Throughout historic Palestine, from Galilee in the north, to Hebron in the south, each region, city and village had its own distinctive style of dress, embroidery techniques and pattern arrangements. Embroidery skills were passed from one generation to the next, as women would gather whenever they had a moment to embroider. Embroidery also reflected a unique expression of a woman’s skill, creativity, wealth, individuality and identity. Palestinian embroidery continues to be a living practice today, but with the displacement of millions of Palestinians since 1948, it has evolved to represent the Palestinian national identity, ultimately leading to an intense commodification of embroidery with radical shifts in its use and meaning [44]. At the close of 2021, the art of embroidery in Palestine was inscribed to the UNESCO list of the Intangible Cultural Heritage of Humanity.
Some rare archaeological examples of nearly complete medieval embroidered garments from the Qadisha Valley, Lebanon, date to the 13th century [45]. However, museum textile collections, including the British Museum’s, tend to have examples from the 19th and 20th centuries, with their oldest textiles possibly dating back to the 1840s. Palestinian textiles, with their exquisite embroidery, are the ongoing subject of extensive research by Palestinian and Western scholars, with a focus on identifying regional styles, stitches, colour combinations, textiles used and new pattern introduction [46]. However, little attention has been given to the dyes and how these changed with the introduction of new synthetic formulations in the second half of the 19th century. Moreover, accurate dating of Palestinian garments and textiles in museum collections is rare due to the absence of dated contemporaneous materials. Many of the garments and textiles have date ranges based on the comparison of patterns and colour combinations, but these are often vague. Nevertheless, when precise dye identification is obtained, the dates of the first synthesis of synthetic dyes can be used to determine the terminus post quem production date of textiles [18]. In this framework, the dye analysis of two Palestinian garments from the British Museum collection was carried out using high pressure liquid chromatography coupled with diode array detector and electrospray ionisation, followed by quadrupole and time of flight detection (HPLC-DAD-ESI-Q-ToF), with the aim to refine their production date and better understand dyeing practices in the late 19th–early 20th centuries.

2. Materials and Methods

2.1. Textiles and Samples

The British Museum has a large selection of Palestinian textiles, including garments, animal trappings, household textiles and amulets, mostly acquired between 1965 and 1967 when the Museum was approached by the Church Missionary Society who needed to move to new premises and were no longer in a position to store and care for the collections they had [44]. Missionary societies have been active in the Near East since the early part of the 19th century; they have amassed large collections, which were acquired by the missionaries, who purchased garments, jewellery, household goods and tools from local villagers and townspeople and who commissioned items from local craftsmen. The British Museum, with advice from colleagues and founders of the former Palestine Folk Museum (now known as the Dar al-Tifl Museum) in East Jerusalem, acquired from the Church Missionary Society 329 Palestinian garments, as well as 112 pieces of jewellery. Soon afterwards, the Museum was given a smaller collection of 21 Palestinian garments from Jerusalem and the East Mission. These additions to the Museum’s collection were all dated to the 19th and early 20th centuries [44]. Subsequently, the Museum continued to acquire Palestinian material through fieldwork, donation or purchase, both in the UK and in the Middle East, and its collection has grown to become one of the largest collections of Palestinian garments outside the Arab world. Several exhibitions have taken place at the British Museum on these materials, including “Costumes of Palestine” and “Spinning and weaving in Palestine” in the early 1970s, and the seminal exhibition “Palestinian Costume” between 1989 and 1991, when the British Museum’s ethnographic collections were housed in the Museum of Mankind. In 2023, as part of the regular gallery rotations in the Albukhary Foundation Gallery of the Islamic world, in a case focusing on the Arab world, a selection of Palestinian embroidered garments went on display. It was decided to examine the dyes used on two of these garments to gain a better understanding of their natural or synthetic nature. If synthetic, the data would be used to help date some of the garments more accurately.
Accession number As1967,02.15—A village woman’s special occasion coat/dress (jillayeh—Figure 1), made of blue-dyed handwoven linen, and heavily embroidered in cross-stitch on the bottom skirt, top sleeves and chest panel with red, light brown, green, cream, yellow, mauve and bright pink floss silk. The collar, cuffs, front opening and hem are reinforced with a cotton binding, and the neck has a glass button closure. This coat/dress would have been worn over an underdress, with a girdle around the waist. It was produced in Ramallah between the late 19th century and early 20th century. Eleven samples were collected, representative of most colours (Table 1).
Accession number As1967,02.21—A village woman’s coat (jillayeh—Figure 2) made of blue-dyed cotton and red-coloured linen for yoke facing and gussets, heavily embroidered on the back of the skirt with red, yellow, white, blue, turquoise, green and fuchsia floss silk thread. The front and sleeves are appliquéd with green, deep fuchsia and yellow silk patches, and decorated with a silk zig-zag trim. The edges of the coat are trimmed with a braided cotton cord, creating two button loops at the front for blue glass and brown wooden buttons. The attributed production date is the second half of the 19th century. Seven samples were collected, representative of most colours (Table 2).

2.2. Dye Analysis

The dye extraction was performed using a method published in [47], which briefly consists of a double mild extraction procedure using DMSO first, and secondly, a mixture of methanol/acetone/water/0.5 M oxalic acid in a 30:30:40:1 (v/v/v/v) ratio.
Analyses were carried out using a 1260 Infinity HPLC (Agilent Technologies), coupled to a 1100 DAD detector (Hewlett-Packard) and to a Quadrupole-Time of Flight tandem mass spectrometer 6530 Infinity Q-ToF detector (Agilent Technologies) by a Jet Stream ESI interface (Agilent Technologies). Separation was achieved using a Zorbax Extend-C18 column (Agilent Technologies, 2.1 mm × 50 mm, 1.8 μm particle size) with a 0.4 mL/min flow rate, 40 °C column temperature and a gradient of water with 0.1% formic acid (eluent A) and acetonitrile with 0.1% formic acid (eluent B). The elution gradient was programmed as follows: initial conditions 95% A, followed by a linear gradient to 100% B in 10 min, and held for 2 min. Re-equilibration time for each analysis was 10 min. An injection volume of 10 μL was adopted for MS experiments, and 20 μL was adopted for MS/MS experiments.
The DAD detector (cell volume 50 µL) scanned in the range of 20190–700 nm, with 2 nm resolution. The ESI operating conditions were as follows: drying gas (N2, purity > 98%) temperature 350 °C and 10 L/min flow; capillary voltage 4.0 kV; nebuliser gas pressure 40 psig; sheath gas (N2, purity > 98%) temperature 375 °C and flow 11 L/min. High-resolution MS and MS/MS spectra were acquired in both negative and positive mode in the range of 100–1700 m/z. The fragmentor was kept at 100 V, nozzle voltage 1000 V, skimmer 65 V and octapole RF 750 V. For the MS/MS experiments, different voltages (from 10 to 40 V) in the collision cell were tested for Collision Induced Dissociation (CID), in order to maximize the information obtained from the fragmentation of the single molecules. The collision gas was N2 (purity 99.999%). The data were collected by targeted MS/MS acquisition with an MS scan rate of 1.0 spectra/sec and an MS/MS scan rate of 1.0 spectra/sec. Auto-calibration was performed daily using Agilent tuning mix HP0321 (Agilent Technologies) prepared in 90% water/10% acetonitrile. MassHunter v.10 Workstation Software was used to carry out diode array detector and mass spectrometer control, data acquisition and data analysis. In particular, extract ion chromatograms were obtained using the software EIC function and selecting the mass range corresponding to the calculated mass ± 0.01 m/z. Molecular identifications were obtained by comparing with in-house databases [33,34,38].

3. Results

The results of the dye analysis are summarised in Table 1 and Table 2. Molecular identifications are reported in Table 3.
The blue fabrics in both garments were found to contain indigoid molecules, namely isatin, indigotin and indirubin, indicating that a natural source of indigo dye was used [48]. The exact source, i.e., woad from Isatis tinctoria, indigo from Indigofera tinctoria or other plants, cannot be inferred from chemical analysis.
The red fabric of As1967,02.15 shows some areas that are significantly faded, for example, the right sleeve in comparison with the left sleeve, as visible in Figure 1. It is reasonable to assume that these areas would have looked the same colour when the dress was produced, but that different dyes with different light sensitivity were used in these threads. Consequently, samples from both faded and non-faded areas were taken. The non-faded areas were found to be dyed with madder and tannins (Figure 3a). The molecular composition of the anthraquinones suggests the use of Rubia tinctorum, as relatively abundant alizarin and the presence of ruberythric acid are generally indicative of this plant [34,49]. The presence of ellagic acid and ellagic acid glucoside is not sufficient to ascertain the botanical source of tannins. Nevertheless, the combination of madder and tannins agrees with traditional dyeing practice in the Mediterranean and Middle Eastern area [50,51]. The faded red areas contain a mixture of early synthetic dyes of different colours, including Fuchsin (C.I. 42510; Basic Violet 14), Orange II (C.I. 15510; Acid Orange 7), Orange IV (C.I. 13080; Acid Orange 5), Auramine O (C.I. 41000; Basic Yellow 2) and Malachite Green (C.I. 42000; Basic Green 4) (Figure 3b). The lightfastness of some of these dyes is generally poor [52], as also confirmed by the detection of various degradation products of Malachite Green and Auramine O [33]. The presence of these dyes and degradation products explains the fading observed. However, this combination of dyes also provides us with information on how dyers attempted to recreate a red madder shade by using at least five different synthetic dyes, proving the experimental work needed for colour-matching in this early phase of synthetic dye introduction.
Interestingly, a similar mixture of dyes was used to obtain the dark red colour in the embroidered areas of As1967,02.15 (Figure 3c). In this case, the synthetic yellow dye Auramine O was replaced by the natural red dye extracted from the cochineal insect, probably American cochineal (Dactylopius coccus). These dark red areas have not faded in the same way as the lighter red areas. The use of a mordant is suspected in the dark red areas, as it would be needed to dye areas with cochineal, whereas mordanting is not necessarily needed for the synthetic dyes. Unfortunately, mordant analysis was not carried out in this instance. The fibres are also different in the two cases, with linen used for the lighter red and silk used for the darker red. Cellulosic fibres are notoriously more difficult to dye than proteinaceous ones [53]. This dye combination further highlights the complexities of mixing different dyes, including natural and synthetic ones, to obtain a particular shade of colour.
The red colour of the linen in As1967,02.21 was found to be obtained with a mixture of Fuchsin and Orange IV, whereas the magenta silk threads were dyed with Fuchsin and a small amount of Orange II. The choice of mixing Fuchsin and Orange IV to obtain a red colour is interesting. These orange azo dyes were first synthesised in 1877, almost at the same time as Scarlet Reds (e.g., C.I. 16150; Acid Red 26 and C.I. 16255; Acid Red 18) and Fast Reds (e.g., C.I. 15620; Acid Red 88), and after synthetic Alizarin Red (C.I. 58000; Mordant Red 11), which was first synthesised in 1869 [33,54]. Whether the use of these mixtures instead of purely red synthetic dyes is a result of local availability of certain dyes or a deliberate choice remains difficult to hypothesise and requires further investigation. Additionally, in all cases, the Fuchsin components exhibited a bell-shaped profile (Figure 3b,c). This is indicative of the early synthetic process of Fuchsin, in which a mixture of aniline and toluidine was oxidised, thus producing a mixture of rosanilines reflecting the ratios of the starting materials (Table 3) [33]. This process was exclusively used until 1889, when a different synthetic process for Fuchsin was introduced, targeting the synthesis of pure dimethylpararosaniline [33]. Thus, the result suggests that the dye used in these textiles was probably produced before 1889.
Orange threads in both garments were dyed with a mixture of Orange II and Orange IV (Figure 4). Notably, the correct identification of these molecules is not simple. For example, Orange II is an isomer of Orange I (C.I. 14600, Acid Orange 20) and Brilliant Orange G (C.I. 15970; Acid Orange 12), hence the accurate acquisition of retention times, UV-Vis absorption spectra and tandem mass spectra as well as comparison with data acquired from reference materials are fundamental for correct identifications [32,33,38].
Similarly, Orange IV has an isomer referred to as Metanil Yellow (C.I. 13065, Acid Yellow 36). These two molecules differ for the position of the sulphonate group, which results in a significant colour difference—orange for the former and yellow for the latter. This is only partially reflected in the UV-Vis absorption spectra, with Orange IV having λmax = 430 nm (Figure 4a) and Metanil Yellow having λmax = 425 nm (Figure 5a). The retention time of Metanil Yellow is slightly higher than Orange IV and the tandem mass spectra are slightly different (Figure 4d and Figure 5d). By taking into account these differences and comparing with reference samples [33,38], it was possible to ascertain that the bright yellow sample from As1967,02.15 contained a mixture of Orange II and Metanil Yellow (Figure 5). An additional molecule was detected and identified as related to Chrysoidine R (C.I. 11320, Basic Orange 1), which is the methylated form of Chrysoidine (C.I. 11270, Basic Orange 2), first synthesised in 1875 by coupling aniline to m-phenylenediamine [55]. Its chemical structure includes an amino group at the ortho position, with relation to the azo bond (Figure 6). This type of configuration has been shown to be susceptible to a particular type of degradation, probably occurring in the presence of formaldehyde, and referred to as chemical fading. The reaction results in the addition of a carbon atom and the formation of a five-atom ring [2,9,33,56], as shown in Figure 6. The resulting degradation product for Chrysoidine R was detected in this sample and the results agree with those obtained from a historic cotton sample dyed with Chrysoidine R from the book “A Manual of Dyeing”, published in 1893 [57]. Chrysoidine R is an orange dye, and the non-degraded molecule was not detected. By contrast, its degradation product has a pale-yellow colour, thus suggesting that this sample would have been significantly darker prior to fading.
Complex results were also obtained from the yellow sample from As1967,02.21 (Figure 7). Various flavonoids associated with glycosides of rhamnetin, rhamnazin and quercetin were detected, indicating the use of the natural yellow dye extracted from the buckthorn berries, also referred to as Persian berries [58,59]. These plants belong to the Rhamnus genus, which includes various species such as R. saxatilis, R. cathartica, R. alaternus, R. davurica, R. utilis, R. petiolaris, R. infectoria, R. amygdalin, R. oleodies and R. lycioides, etc. [1]. Small differences in the chemical composition of the dye extracted from various Rhamnus species have been investigated [59,60,61], showing, for example, that kaempferol glycosides are quite abundant in R. cathartica, R. alaternus and R. utilis, but not in R. saxatilis and R. petiolaris [34,59,61]. The molecular distribution observed in these samples represents a good match with R. saxatilis and R. petiolaris, the former being distributed in the whole Mediterranean area and the latter being found in Anatolia and Asia Minor [1]. Nevertheless, it is generally difficult to assign the exact buckthorn species, especially considering possible degradation reactions and dyeing recipes. However, the absence of aglycone molecules can be taken as indication for the good preservation of this natural yellow dye, which has been historically used in the Mediterranean area.
Interestingly, buckthorn was found to be mixed with Orange II, Orange IV and Malachite Green in the yellow sample from As1967,02.21, suggesting that a dark yellow colour was probably originally intended, and confirming the interesting practice of mixing and/or over-dyeing natural and synthetic dyes to obtain specific shades.
Different shades of green in As1967,02.15 were also obtained, combining the natural yellow dye from buckthorn with synthetic dyes, primarily Malachite Green, Orange II, Metanil Yellow and Methyl Violet (Figure 8); however, the green colour in As1967,02.21 was obtained by mixing buckthorn and Malachite Green. The practice of mixing Malachite Green with natural yellow dyes has been observed in other late-19th-century textiles from other regions, including Central Asian ikats [7,20] and Karen textiles from Myanmar [10], probably as an attempt of the dyers to counterbalance the bluish shade of this synthetic green colourant that was newly available to them.
Pure synthetic dyes were used in the purple and bright pink areas of As1967,02.15. These were identified as Methyl Violet and Rhodamine B (C.I. 45170, Basic Violet 10), respectively (Figure 9). While Methyl Violet is one of the first and most popular synthetic dyes produced as early as 1861, Rhodamine B was synthetised in 1887. It is important to distinguish it chromatographically from its isomer Rhodamine 6G (C.I. 45160, Basic Red 1), which was introduced in 1892 [33]. In fact, the two isomers have slightly different retention times and mass spectrometric fragmentation patterns, which require careful comparisons with reference samples to achieve an accurate differentiation [62,63].
As1967,02.21 exhibited some light blue areas obtained with the synthetic dye Methyl Blue (C.I. 42780; Acid Blue 93) (Figure 10). A small amount of Orange IV was also detected in this sample, but it is difficult to ascertain if this is a result of cross-sample contamination. Methyl blues are actually a category of dyes synthesised in 1862 by Nicholson and correspond to complex mixtures of molecules with different degrees of sulfonation, phenylation and methylation [33]. In this sample, di- and trisulphonated derivatives of triphenyl rosanilines were detected, as well as some oxidation products (Table 3).

4. Conclusions

The results obtained from the dye analysis of two Palestinian garments from the British Museum’s collection depicts complex dyeing practices employed in the second half of the 19th century, adding to a growing corpus of data that is highlighting the complexities of the introduction of early synthetic dyes in non-European textile-making traditions.
Both local and imported natural dyes, such as madder (R. tinctorum), buckthorn (R. saxatilis), cochineal (D. coccus) and woad/indigo, were used alongside various early synthetic dyes. In some cases, natural and synthetic dyes were found to be mixed to obtain specific colour shades. In other cases, various synthetic dyes were mixed to reproduce the colours of natural dyes, such as red from madder. Pure synthetic dyes were mostly used for secondary colours, such as pink, purple and orange, as well as in a sky-blue sample. These observations agree with the analysis from other 19th-century textiles, showing that red and yellow primary colours kept being obtained from natural dyes for longer than other mixed colours. Obtaining secondary colours with natural dyes can be complicated, hence, synthetic orange, purple, green and pink shades were more positively received by local dyers to simplify their work. Considerations on the fading of dyes could be drawn by detecting various molecular degradation products, thus highlighting that these textiles had even brighter colours at the time of their production. This information is particularly important to guide the conservation and future display of these precious traditional garments. The most recent dye identified in As1967,02.15 was Rhodamine B, synthesised in 1887, whereas the latest dyes detected in As1967,02.21 were synthesised in 1877, thus refining the terminus post quem production date of these textiles. Additionally, the detection of Fuchsin obtained from the early synthetic process in both garments, and the lack of detection of pure red synthetic dyes, further suggests that these garments were probably produced at the end of the 1880s/beginning of the 1890s, before the late synthetic process of Fuchsin and other red synthetic dyes became popular. However, the contextualisation of these results into the broader context of economic and fashion history, as well as trade of synthetic materials from Europe, requires further substantial investigations to refine the actual chronology of the introduction of synthetic colourants in Palestine and surrounding areas, as well as to unpack the complex dynamics behind this global phenomenon.

Author Contributions

Conceptualization, D.T. and Z.K.-H.; methodology, D.T. and L.D.; formal analysis, D.T. and L.D.; investigation, L.D. and D.T.; resources, Z.K.-H.; data curation, D.T. and L.D.; writing—original draft preparation, D.T.; writing—review and editing, D.T., L.D. and Z.K.-H.; visualization, D.T.; supervision, D.T. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Data Availability Statement

The raw data presented in this study are available on request from the corresponding author.

Conflicts of Interest

The authors declare no conflicts of interest.

References

  1. Cardon, D. Natural Dyes: Sources, Tradition, Technology and Science; Archetype Publications Ltd.: London, UK, 2007. [Google Scholar]
  2. Tamburini, D.; Sabatini, F.; Berbers, S.; van Bommel, M.R.; Degano, I. An Introduction and Recent Advances in the Analytical Study of Early Synthetic Dyes and Organic Pigments in Cultural Heritage. Heritage 2024, 7, 1969–2010. [Google Scholar] [CrossRef]
  3. Hagan, E.; Poulin, J. Statistics of the early synthetic dye industry. Herit. Sci. 2021, 9, 33. [Google Scholar] [CrossRef]
  4. Travis, A.S. The Rainbow Makers: The Origins of the Synthetic Dyestuffs Industry in Western Europe; Lehigh University Press: Bethlehem, PA, USA, 1993. [Google Scholar]
  5. Beer, J.J. The Emergence of the German Dye Industry; University of Illinois Press: Champaign, IL, USA, 1959. [Google Scholar]
  6. Simon, C. The transition from natural dyestuffs to synthetic dyestuffs: The case of Basel, 1850–1940. In Natural Dyestuffs and Industrial Culture in Europe, 1750–1880; Fox, R., Nieto-Galan, A., Eds.; Science History Publications: Canton, MA, USA, 1999; pp. 313–338. [Google Scholar]
  7. Tamburini, D.; Klink-Hoppe, Z.; McCarthy, B. New insights into the dyes of Central Asian ikat textiles. J. Cult. Herit. 2024, 66, 343–355. [Google Scholar] [CrossRef]
  8. Do, K.L.; Mushtaq, A.; Liu, J.; Zhao, F.; Su, M. Unveiling the Use of Natural and Early Synthetic Dyes in Indonesian Historical Silk Textiles. Fibers Polym. 2024, 6, 2233–2244. [Google Scholar] [CrossRef]
  9. Tamburini, D.; Kim-Marandet, M.; Kim, S.-A. Dye Identification in Mounting Textiles of Traditional Korean Paintings from the Late Joseon Dynasty. Heritage 2023, 6, 44–66. [Google Scholar] [CrossRef]
  10. Tamburini, D.; Dyer, J.; Cartwright, C.; Green, A. Changes in the production materials of Burmese textiles in the 19th century–dyes, mordants and fibres of Karen garments from the British Museum’s collection. Herit. Sci. 2023, 11, 150. [Google Scholar] [CrossRef]
  11. Tamburini, D.; Dyer, J.; Cartwright, C. First evidence and characterisation of rare chrome-based colourants used on 19th-century textiles from Myanmar. Dye. Pigment. 2023, 218, 111472. [Google Scholar] [CrossRef]
  12. Petroviciu, I.; Teodorescu, I.C.; Vasilca, S.; Albu, F. Transition from Natural to Early Synthetic Dyes in the Romanian Traditional Shirts Decoration. Heritage 2023, 6, 505–523. [Google Scholar] [CrossRef]
  13. Petroviciu, I.; Teodorescu, I.; Vasilca, S.; Albu, F.; Medvedovici, A. Liquid chromatography as analytical tool for the study of natural and early synthetic dyes in traditional Saxon textiles. Herit. Sci. 2023, 11, 164. [Google Scholar] [CrossRef]
  14. Longoni, M.; Gavazzi, M.; Monti, D.; Bruni, S. Early synthetic textile dyes of the late 19th century from the “Primo Levi” Chemistry Museum (Rome): A multi-technique analytical investigation. J. Cult. Herit. 2023, 59, 131–139. [Google Scholar] [CrossRef]
  15. Vermeulen, M.; Tamburini, D.; McGeachy, A.C.; Meyers, R.D.; Walton, M.S. Multiscale characterization of shellfish purple and other organic colorants in 20th-century traditional enredos from Oaxaca, Mexico. Dye. Pigment. 2022, 206, 110663. [Google Scholar] [CrossRef]
  16. Chen, V.J.; Smith, G.D.; Whitaker, M.R.; von Rabenau, B. Identification of Red Dyes in Selected Textiles from Chin and Karen Ethnic Groups of Myanmar by LC-DAD-ESI-MS. In Dyes in History and Archaeology 33/34; Kirby, J., Ed.; Archetype Publications: London, UK, 2021; pp. 92–101. [Google Scholar]
  17. Cesaratto, A.; Luo, Y.-B.; Smith, H.D.; Leona, M. A timeline for the introduction of synthetic dyestuffs in Japan during the late Edo and Meiji periods. Herit. Sci. 2018, 6, 22. [Google Scholar] [CrossRef]
  18. Tamburini, D.; Breitung, E.; Mori, C.; Kotajima, T.; Clarke, M.L.; McCarthy, B. Exploring the transition from natural to synthetic dyes in the production of 19th-century Central Asian ikat textiles. Herit. Sci. 2020, 8, 114. [Google Scholar] [CrossRef]
  19. Liu, J.; Zhou, Y.; Zhao, F.; Peng, Z.; Wang, S. Identification of early synthetic dyes in historical Chinese textiles of the late nineteenth century by high-performance liquid chromatography coupled with diode array detection and mass spectrometry. Color. Technol. 2016, 132, 177–185. [Google Scholar] [CrossRef]
  20. Chen, V.J.; Smith, G.D.; Holden, A.; Paydar, N.; Kiefer, K. Chemical analysis of dyes on an Uzbek ceremonial coat: Objective evidence for artifact dating and the chemistry of early synthetic dyes. Dye. Pigment. 2016, 131, 320–332. [Google Scholar] [CrossRef]
  21. Degano, I.; Ribechini, E.; Modugno, F.; Colombini, M.P. Analytical Methods for the Characterization of Organic Dyes in Artworks and in Historical Textiles. Appl. Spectrosc. Rev. 2009, 44, 363–410. [Google Scholar] [CrossRef]
  22. Grillini, F.; de Ferri, L.; Pantos, G.A.; George, S.; Veseth, M. Reflectance imaging spectroscopy for the study of archaeological pre-Columbian textiles. Microchem. J. 2024, 200, 110168. [Google Scholar] [CrossRef]
  23. Caggiani, M.C.; Forleo, T.; Pojana, G.; Lagioia, G.; Mangone, A.; Giannossa, L.C. Characterization of silk-cotton and wool-cotton blends pattern books by fibre optic reflectance spectroscopy. The booming market of first synthetic textile dyes in early 20th century. Microchem. J. 2022, 175, 107178. [Google Scholar] [CrossRef]
  24. Ding, L.; Gong, T.; Wang, B.; Yang, Q.; Liu, W.; Pemo, R.; Metok, T. Non-invasive study of natural dyes in textiles of the Qing Dynasty using fiber optic reflectance spectroscopy. J. Cult. Herit. 2021, 47, 69–78. [Google Scholar] [CrossRef]
  25. Tamburini, D.; Dyer, J. Fibre optic reflectance spectroscopy and multispectral imaging for the non-invasive investigation of Asian colourants in Chinese textiles from Dunhuang (7th-10th century AD). Dye. Pigment. 2019, 162, 494–511. [Google Scholar] [CrossRef]
  26. Selberg, S.; Vanker, E.; Peets, P.; Wright, K.; Tshepelevitsh, S.; Pagano, T.; Vahur, S.; Herodes, K.; Leito, I. Non-invasive analysis of natural textile dyes using fluorescence excitation-emission matrices. Talanta 2023, 252, 123805. [Google Scholar] [CrossRef] [PubMed]
  27. Ciccola, A.; McClure, K.R.; Serafini, I.; Vincenti, F.; Montesano, C.; Gentili, A.; Curini, R.; Favero, G.; Postorino, P. The 20th century and its new colours: Investigating the molecular structures of historical synthetic dyes using Raman spectroscopy. J. Raman Spectrosc. 2024, 55, 324–335. [Google Scholar] [CrossRef]
  28. Haddad, A.; Nakie-Miller, T.; Jenks, J.B.; Kowach, G. Andy Warhol and His Amazing Technicolor Shoes: Characterizing the Synthetic Dyes Found in Dr. Ph. Martin’s Synchromatic Transparent Watercolors and Used in À la Recherche du Shoe Perdu. Colorants 2023, 2, 1–21. [Google Scholar] [CrossRef]
  29. Sessa, C.; Steuer, C.; Quintero Balbas, D.; Sciutto, G.; Prati, S.; Stege, H. Analytical studies on commercial artists’ colour charts from Das Deutsche Farbenbuch (1925)—Identification of synthetic and natural organic colourants by Raman microscopy, surface-enhanced Raman spectroscopy and metal underlayer ATR-FTIR spectroscopy. Herit. Sci. 2022, 10, 109. [Google Scholar] [CrossRef]
  30. Quintero Balbas, D.; Lanterna, G.; Cirrincione, C.; Ricci, M.; Becucci, M.; Fontana, R.; Striova, J. Non-invasive identification of turmeric and saffron dyes in proteinaceous textile fibres using Raman spectroscopy and multivariate analysis. J. Raman Spectrosc. 2022, 53, 593. [Google Scholar] [CrossRef]
  31. Pirok, B.W.J.; den Uijl, M.J.; Moro, G.; Berbers, S.V.J.; Croes, C.J.M.; van Bommel, M.R.; Schoenmakers, P.J. Characterization of Dye Extracts from Historical Cultural-Heritage Objects using State-of-the-Art Comprehensive Two-Dimensional Liquid Chromatography and Mass Spectrometry with Active Modulation and Optimized Shifting Gradients. Anal. Chem. 2019, 91, 3062–3069. [Google Scholar] [CrossRef]
  32. Souto, C. Analysis of Early Synthetic Dyes with HPLC-DAD-MS-An Important Database for Analysis of Colorants Used in Cultural Heritage. Master’s Thesis, Univerisy of Lisbon, Lisbon, Portugal, 2010. [Google Scholar]
  33. Tamburini, D. On the reliability of historic books as sources of reference samples of early synthetic dyes–The case of “The Coal Tar Colours of the Farbwerke vorm. Meister, Lucius & Brüning, Höchst on the Main, Germany–A General Part” (1896). Dye. Pigment. 2024, 221, 111796. [Google Scholar] [CrossRef]
  34. Tamburini, D. Investigating Asian colourants in Chinese textiles from Dunhuang (7th–10th century AD) by high performance liquid chromatography tandem mass spectrometry–Towards the creation of a mass spectra database. Dye. Pigment. 2019, 163, 454–474. [Google Scholar] [CrossRef]
  35. Degano, I. Liquid chromatography: Current applications in Heritage Science and recent developments. Phys. Sci. Rev. 2019, 4, 20180009. [Google Scholar] [CrossRef]
  36. Vasileiadou, A.; Karapanagiotis, I.; Zotou, A. Determination of Tyrian purple by high performance liquid chromatography with diode array detection. J. Chromatogr. A 2016, 1448, 67–72. [Google Scholar] [CrossRef]
  37. Lech, K.; Wilicka, E.; Witowska-Jarosz, J.; Jarosz, M. Early synthetic dyes–a challenge for tandem mass spectrometry. J. Mass Spectrom. 2013, 48, 141–147. [Google Scholar] [CrossRef] [PubMed]
  38. Tamburini, D.; Shimada, C.M.; McCarthy, B. The molecular characterization of early synthetic dyes in E. Knecht et al’s textile sample book “A Manual of Dyeing” (1893) by high performance liquid chromatography-Diode array detector-Mass spectrometry (HPLC-DAD-MS). Dye. Pigment. 2021, 190, 109286. [Google Scholar] [CrossRef]
  39. Berbers, S.V.J.; Gaibor, A.N.P.; Ligterink, F.; Neevel, J.G.; Reissland, B.; van der Werf, I.D. Shades of violet: Study of the compositional variability of historical Methyl violet dyes. J. Cult. Herit. 2024, 66, 464–475. [Google Scholar] [CrossRef]
  40. Sabatini, F.; Degano, I.; van Bommel, M. Investigating the in-solution photodegradation pathway of Diamond Green G by chromatography and mass spectrometry. Color. Technol. 2021, 137, 456–467. [Google Scholar] [CrossRef]
  41. Lech, K.; Nawała, J.; Popiel, S. Mass Spectrometry for Investigation of Natural Dyes in Historical Textiles: Unveiling the Mystery behind Safflower-Dyed Fibers. J. Am. Soc. Mass Spectrom. 2021, 32, 2552–2566. [Google Scholar] [CrossRef]
  42. Álvarez-Martín, A.; Newsome, G.A.; Janssens, K. High-Resolution Mass Spectrometry and Nontraditional Mass Defect Analysis of Brominated Historical Pigments. Anal. Chem. 2021, 93, 14851–14858. [Google Scholar] [CrossRef]
  43. Degano, I.; Sabatini, F.; Braccini, C.; Colombini, M.P. Triarylmethine dyes: Characterization of isomers using integrated mass spectrometry. Dye. Pigment. 2019, 160, 587–596. [Google Scholar] [CrossRef]
  44. Weir, S. Palestinian Costume; British Museum Publications: London, UK, 1989. [Google Scholar]
  45. Ghnaim, W. Tatreez in Time-The Memory, Meaning, and Makers of Palestinian Embroidery; The Metropolitan Museum of Art: New York, NY, USA, 2024. [Google Scholar]
  46. Skinner, M. Palestinian Embroidery Motifs: A Treasury of Stitches 1850–1950; Melisende Publishing and Rimal Publications: Woodbridge, CT, USA, 2007. [Google Scholar]
  47. Tamburini, D.; Cartwright, C.R.; Pullan, M.; Vickers, H. An investigation of the dye palette in Chinese silk embroidery from Dunhuang (Tang dynasty). Archaeol. Anthropol. Sci. 2019, 11, 1221–1239. [Google Scholar] [CrossRef]
  48. Frignani, E.; D’Eusanio, V.; Grandi, M.; Pigani, L.; Roncaglia, F. A Continuous Extraction Protocol for the Characterisation of a Sustainably Produced Natural Indigo Pigment. Life 2024, 14, 59. [Google Scholar] [CrossRef]
  49. Mouri, C.; Laursen, R. Identification of anthraquinone markers for distinguishing Rubia species in madder-dyed textiles by HPLC. Microchim. Acta 2012, 179, 105–113. [Google Scholar] [CrossRef]
  50. Torgan Güzel, E. Ottoman palace weavings between different periods: Material characterization, comparison and suggestions for conservation. Herit. Sci. 2023, 11, 179. [Google Scholar] [CrossRef]
  51. Shahid, M.; Wertz, J.; Degano, I.; Aceto, M.; Khan, M.I.; Quye, A. Analytical methods for determination of anthraquinone dyes in historical textiles: A review. Anal. Chim. Acta 2019, 1083, 58–87. [Google Scholar] [CrossRef] [PubMed]
  52. Hagan, E.; Castro-Soto, I.; Breault, M.; Poulin, J. The lightfastness of early synthetic organic dyes. Herit. Sci. 2022, 10, 50. [Google Scholar] [CrossRef]
  53. Knecht, E.; Rawson, C.; Loewenthal, R. A Manual of Dyeing: For the Use of Practical Dyers, Manufacturers, Students, and All Interested in the Art of Dyeing (Volume I); Charles Griffin and Company: London, UK, 1893; Volume 1. [Google Scholar]
  54. Welham, R.D. The Early History of the Synthetic Dye Industry. J. Soc. Dye. Colour. 1963, 79, 146–152. [Google Scholar] [CrossRef]
  55. Knecht, E.; Rawson, C.; Loewenthal, R. A Manual of Dyeing: For the Use of Practical Dyers, Manufacturers, Students, and All Interested in the Art of Dyeing (Volume II); Charles Griffin and Company: London, UK, 1893; Volume 2. [Google Scholar]
  56. Chen, V.; Minto, R.; Manicke, N.; Smith, G. Structural elucidation of two Congo red derivatives on dyed historical objects indicative of formaldehyde exposure and the potential for chemical fading. Dye. Pigment. 2022, 201, 110173. [Google Scholar] [CrossRef]
  57. Knecht, E.; Rawson, C.; Loewenthal, R. A Manual of Dyeing: For the Use of Practical Dyers, Manufacturers, Students, and All Interested in the Art of Dyeing (Specimen of Dyed Fabrics); Charles Griffin and Company: London, UK, 1893. [Google Scholar]
  58. Mouri, C.; Mozaffarian, V.; Zhang, X.; Laursen, R. Characterization of flavonols in plants used for textile dyeing and the significance of flavonol conjugates. Dye. Pigment. 2014, 100, 135–141. [Google Scholar] [CrossRef]
  59. Liu, J.; Ji, L.; Chen, L.; Pei, K.; Zhao, P.; Zhou, Y.; Zhao, F. Identification of yellow dyes in two wall coverings from the Palace Museum: Evidence for reconstitution of artifacts. Dye. Pigment. 2018, 153, 137–143. [Google Scholar] [CrossRef]
  60. Chen, G.; Li, X.; Saleri, F.; Guo, M. Analysis of Flavonoids in Rhamnus davurica and Its Antiproliferative Activities. Molecules 2016, 21, 1275. [Google Scholar] [CrossRef]
  61. Cuoco, G.; Mathe, C.; Vieillescazes, C. Liquid chromatographic analysis of flavonol compounds in green fruits of three Rhamnus species used in Stil de grain. Microchem. J. 2014, 115, 130–137. [Google Scholar] [CrossRef]
  62. Sabatini, F.; La Nasa, J.; Degano, I.; Campanella, B.; Legnaioli, S.; Saccani, I.; Modugno, F. Fluorescent Paints in Contemporary Murals: A Case Study. Heritage 2023, 6, 5689–5699. [Google Scholar] [CrossRef]
  63. Ferreira, B.R.V.; Correa, D.N.; Eberlin, M.N.; Vendramini, P.H. Fragmentation Reactions of Rhodamine B and 6G as Revealed by High Accuracy Orbitrap Tandem Mass Spectrometry. J. Braz. Chem. Soc. 2017, 28, 136–142. [Google Scholar] [CrossRef]
Heritage 08 00028 g001
Figure 1. Front, back and details of the embroidery of As1967,02.15 (length: 129 cm; width: 103 cm). Light blue rectangles indicate the discoloured red areas. ©The Trustees of the British Museum.
Figure 1. Front, back and details of the embroidery of As1967,02.15 (length: 129 cm; width: 103 cm). Light blue rectangles indicate the discoloured red areas. ©The Trustees of the British Museum.
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Figure 2. Front, back and details of the embroidery and appliqués of As1967,02.21 (length: 132 cm; width: 94 cm). ©The Trustees of the British Museum.
Figure 2. Front, back and details of the embroidery and appliqués of As1967,02.21 (length: 132 cm; width: 94 cm). ©The Trustees of the British Museum.
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Figure 3. Extracted ion chromatograms obtained by HPLC-MS analysis of (a) non-faded red, (b) faded red and (c) dark red samples from As1967,02.15. For peak labels and molecular details, see Table 3. ©The Trustees of the British Museum.
Figure 3. Extracted ion chromatograms obtained by HPLC-MS analysis of (a) non-faded red, (b) faded red and (c) dark red samples from As1967,02.15. For peak labels and molecular details, see Table 3. ©The Trustees of the British Museum.
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Figure 4. Results obtained for the orange sample from As1967,02.15: (a) UV-Vis chromatogram extracted at 450 nm and absorption spectra (insets) of the two molecules; (b) extracted ion chromatograms of ions [M-H]− = 327.045 m/z and 352.076 m/z; (c,d) corresponding tandem mass spectra (CID = 30 eV). For peak labels and molecular details, see Table 3. ©The Trustees of the British Museum.
Figure 4. Results obtained for the orange sample from As1967,02.15: (a) UV-Vis chromatogram extracted at 450 nm and absorption spectra (insets) of the two molecules; (b) extracted ion chromatograms of ions [M-H]− = 327.045 m/z and 352.076 m/z; (c,d) corresponding tandem mass spectra (CID = 30 eV). For peak labels and molecular details, see Table 3. ©The Trustees of the British Museum.
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Figure 5. Results obtained for the yellow sample from As1967,02.15: (a) UV-Vis chromatogram extracted at 450 nm and absorption spectrum (insets) of Metanil Yellow; (b) extracted ion chromatograms of ions [M-H]− = 327.045 m/z and 352.076 m/z and ion [M]+ = 237.114 m/z; (c,d) tandem mass spectra (CID = 30 eV) of Metanil Yellow and Chrysoidine R degradation product. For peak labels and molecular details, see Table 3. ©The Trustees of the British Museum.
Figure 5. Results obtained for the yellow sample from As1967,02.15: (a) UV-Vis chromatogram extracted at 450 nm and absorption spectrum (insets) of Metanil Yellow; (b) extracted ion chromatograms of ions [M-H]− = 327.045 m/z and 352.076 m/z and ion [M]+ = 237.114 m/z; (c,d) tandem mass spectra (CID = 30 eV) of Metanil Yellow and Chrysoidine R degradation product. For peak labels and molecular details, see Table 3. ©The Trustees of the British Museum.
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Figure 6. Conversion of Chrysoidine R into its degradation product.
Figure 6. Conversion of Chrysoidine R into its degradation product.
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Figure 7. Results obtained for the yellow sample from As1967,02.21: (a) UV-Vis chromatograms extracted at 350, 450 and 600 nm; (b) extracted ion chromatograms of ions corresponding to the flavonoid components of Rhamnus sp. and molecular structure of rhamnazin-3-O-rhamninoside. For peak labels and molecular details, see Table 3. ©The Trustees of the British Museum.
Figure 7. Results obtained for the yellow sample from As1967,02.21: (a) UV-Vis chromatograms extracted at 350, 450 and 600 nm; (b) extracted ion chromatograms of ions corresponding to the flavonoid components of Rhamnus sp. and molecular structure of rhamnazin-3-O-rhamninoside. For peak labels and molecular details, see Table 3. ©The Trustees of the British Museum.
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Figure 8. Extracted ion chromatograms in (a) negative and (b) positive ionisation modes, obtained by HPLC-MS analysis of the green sample from As1967,02.15. For peak labels and molecular details, see Table 3. ©The Trustees of the British Museum.
Figure 8. Extracted ion chromatograms in (a) negative and (b) positive ionisation modes, obtained by HPLC-MS analysis of the green sample from As1967,02.15. For peak labels and molecular details, see Table 3. ©The Trustees of the British Museum.
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Figure 9. Extracted ion chromatograms obtained by HPLC-MS analysis of (a) purple and (b) bright pink samples from As1967,02.15. For peak labels and molecular details, see Table 3. ©The Trustees of the British Museum.
Figure 9. Extracted ion chromatograms obtained by HPLC-MS analysis of (a) purple and (b) bright pink samples from As1967,02.15. For peak labels and molecular details, see Table 3. ©The Trustees of the British Museum.
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Figure 10. Results obtained for the light blue sample from As1967,02.21: (a) UV-Vis chromatogram extracted at 600 nm; (b) extracted ion chromatograms of ions corresponding to the molecular components of Methyl Blue. For peak labels and molecular details, see Table 3. ©The Trustees of the British Museum.
Figure 10. Results obtained for the light blue sample from As1967,02.21: (a) UV-Vis chromatogram extracted at 600 nm; (b) extracted ion chromatograms of ions corresponding to the molecular components of Methyl Blue. For peak labels and molecular details, see Table 3. ©The Trustees of the British Museum.
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Table 1. Summary of the results obtained by HPLC-DAD-ESI-Q-ToF analysis of the samples taken from As1967,02.15.
Table 1. Summary of the results obtained by HPLC-DAD-ESI-Q-ToF analysis of the samples taken from As1967,02.15.
ColourDye IdentifiedDate of First Synthesis
Heritage 08 00028 i001BlueIndigo/woad (natural)-
Heritage 08 00028 i002Red from bottom panelTannins-
Madder (Rubia tinctorum) -
Heritage 08 00028 i003Red from central chest panelTannins
Madder (Rubia tinctorum)
Heritage 08 00028 i004Faded red from right sleeveFuchsin (C.I. 42510)1859
Auramine O (C.I. 41000)1883
Orange II (C.I. 15510)1877
Orange IV (C.I. 13080)1877
Malachite green (C.I. 42000)1877
Heritage 08 00028 i005Dark redCochineal (probably Dactylopius coccus)-
Fuchsin (C.I. 42510)1859
Orange II (C.I. 15510)1877
Orange IV (C.I. 13080)1877
Malachite Green (C.I. 42000)1877
Heritage 08 00028 i006OrangeOrange II (C.I. 15510)1877
Orange IV (C.I. 13080)1877
Heritage 08 00028 i007YellowMetanil Yellow (C.I. 13065)1879
Orange II (C.I. 15510)1877
Chrysoidine R (C.I. 11320)1877
Heritage 08 00028 i008PinkRhodamine B (C.I. 45170)1887
Heritage 08 00028 i009PurpleMethyl violet (C.I. 42535)1861
Heritage 08 00028 i010GreenBuckthorn (Rhamnus sp.)-
Malachite green (C.I. 42000)1877
Methyl violet (C.I. 42535)1861
Orange II (C.I. 15510)1877
Metanil Yellow (C.I. 13065)1879
Heritage 08 00028 i011Lime greenBuckthorn (Rhamnus sp.)-
Malachite green (C.I. 42000)1877
Methyl violet (C.I. 42535)1861
Orange II (C.I. 15510)1877
Metanil Yellow (C.I. 13065)1879
Table 2. Summary of the results obtained by HPLC-DAD-ESI-Q-ToF analysis of the samples taken from As1967,02.21.
Table 2. Summary of the results obtained by HPLC-DAD-ESI-Q-ToF analysis of the samples taken from As1967,02.21.
ColourDye IdentifiedDate of First Synthesis
Heritage 08 00028 i012BlueIndigo/woad (natural)-
Heritage 08 00028 i013RedFuchsin (C.I. 42510)1859
Orange IV (C.I. 13080)1877
Heritage 08 00028 i014MagentaFuchsin (C.I. 42510)1859
Orange II (C.I. 15510)1877
Heritage 08 00028 i015OrangeOrange II (C.I. 15510)1877
Orange IV (C.I. 13080)1877
Heritage 08 00028 i016YellowBuckthorn (Rhamnus sp.)-
Orange II (C.I. 15510)1877
Orange IV (C.I. 13080)1877
Malachite green (C.I. 42000)1877
Heritage 08 00028 i017GreenBuckthorn (Rhamnus sp.)-
Malachite green (C.I. 42000)1877
Heritage 08 00028 i018Light BlueMethyl blue (C.I. 42780)1862
Orange IV (C.I. 13080)1877
Table 3. Molecular and mass spectrometric details and the identified compounds.
Table 3. Molecular and mass spectrometric details and the identified compounds.
DyeMoleculeFormula[M-H]− (m/z)[M]+/[M+H]+ (m/z)
Buckthorn (probably Rhamnus saxatilis)Quercetin-3-O-rhamnosideC21H20O11447.093449.108
Rhamnetin-3-O-rhamnosideC22H22O11461.109463.124
Quercetin-3-O-robinoside *C27H30O16609.146611.161
Rhamnetin-3-O-robinoside *C28H32O16623.162625.176
Rhamnazin-3-O-robinoside *C29H34O16637.177639.192
Rhamnocitrin-3-O-rhamninoside **C34H42O19753.225755.239
Quercetin-3-O-rhamninoside **C33H40O20755.204757.219
Rhamnetin-3-O-rhamninoside **C34H42O20769.220771.234
Rhamnazin-3-O-rhamninoside **C35H44O20783.235785.250
Rhamnetin-3-O-rhamninoside sulphate **C34H42O23S849.177851.191
Cochineal (probably Dactylopius coccus)dcII (C-glucopyranoside of flavokermesic acid)C22H20O12475.088477.103
Carminic acid (C-glucopyranoside of kermesic acid)C22H20O13491.083493.098
dcIV (C-glucofuranoside of kermesic acid)C22H20O13491.083493.098
dcVII (C-glucofuranoside of kermesic acid)C22H20O13491.083493.098
Madder
(Rubia tinctorum)		AlizarinC14H8O4239.035241.049
RubiadinC15H10O4253.051255.065
PurpurinC14H8O5255.031257.044
AnthragallolC14H8O5255.031257.044
NordamnacanthalC15H8O5267.030269.045
MunjistinC15H8O6283.025285.039
PseudopurpurinC15H8O7299.020301.034
Ruberythric acidC25H26O13533.130535.145
TanninsEllagic acidC14H6O8300.999303.014
Ellagic acid glucosideC20H16O13463.052465.067
IndigoIsatinC8H5NO2146.025148.039
IndigotinC16H10N2O2261.067263.082
IndirubinC16H10N2O2261.067263.082
Fuchsin (C.I. 42510; Basic Violet 14)Pararosaniline (Fuchsin − CH2)C19H18N3+ 288.150
Methylpararosaniline (Fuchsin)C20H20N3+ 302.166
Dimethylpararosaniline (Fuchsin + CH2)C21H22N3+ 316.181
Trimethylpararosaniline (Fuchsin + 2CH2)C22H24N3+ 330.196
Methyl Violet (C.I. 42535; Basic Violet 1)PararosanilineC19H18N3+ 288.150
N-methylpararosaniline (Methyl Violet − 5CH2)C20H20N3+ 302.166
N,N′-dimethylpararosaniline (Methyl Violet − 4CH2)C21H22N3+ 316.181
N,N,N′-trimethylpararosaniline (Methyl Violet − 3CH2)C22H24N3+ 330.196
N,N,N′,N′-tetramethylpararosaniline (Methyl Violet − 2CH2)C23H26N3+ 344.212
N,N,N′,N’,N″-pentamethylpararosaniline (Methyl Violet − CH2)C24H28N3+ 358.228
N,N,N′,N′,N″,N″-hexamethylpararosaniline (Methyl Violet)C25H30N3+ 372.243
Malachite green (C.I. 42000; Basic Green 4)N-methyl-4,4′-(phenylmethylene)dianiline (Malachite Green − 3CH2)C20H19N2+ 287.154
N,N-dimethyl-4,4′-(phenylmethylene)dianiline (Malachite Green − 2CH2)C21H21N2+ 301.170
N,N,N’-trimethyl-4,4′-(phenylmethylene)dianiline (Malachite Green − CH2)C22H23N2+ 315.186
N,N,N’,N’-tetramethyl-4,4′-(phenylmethylene)dianiline (Malachite Green)C23H25N2+ 329.201
Degradation products of Malachite Green4-(aminophenyl)phenyl-methanone (Malachite Green DP − 2CH2)C13H12NO+ 198.091
[4-N-methyl(aminophenyl)]phenyl-methanone (Malachite Green DP − CH2)C14H14NO+ 212.107
[4-N,N-dimethyl-(aminophenyl)phenyl]-methanone/[4-N-ethyl-(aminophenyl)phenyl]-methanone (Malachite Green DP)C15H16NO+ 226.123
Rhodamine B (C.I. 45170; Basic Violet 10)Bisdeethylated Rhodamine B (Rhodamine B − 2C2H4)C24H23N2O3+ 387.170
Deethylated Rhodamine B (Rhodamine B − C2H4)C26H27N2O3+ 415.202
Rhodamine BC28H31N2O3+ 443.232
Auramine O (C.I. 41000; Basic Yellow 2)Bisdemethylated Auramine O (Auramine − 2CH2)C15H18N3+ 240.150
Demethylated Auramine O (Auramine − CH2) C16H20N3+ 254.165
4,4′-Carbonimidoylbis(N,N-dimethylaniline) (Auramine)C17H22N3+ 268.181
Degradation products of Auramine OBisdemethylated Michler’s ketone (Michler’s ketone - 2CH2)C15H17N2O+ 241.134
Demethylated Michler’s ketone (Michler’s ketone − CH2)C16H19N2O+ 255.149
Bis [4-(dimethylamino)phenyl]methanone (Michler’s ketone)C17H21N2O+ 269.165
Methyl Blue (C.I. 42780; Acid Blue 93)Disulphonated N,N,N-triphenyl-pararosaniline (Di-SO3)-(Tri-Ph)C37H29N3O6S2674.143676.157
Disulphonated N,N,N-triphenyl-N-methyl-pararosaniline (Di-SO3)-(Tri-Ph)-(Me)C38H31N3O6S2688.158690.173
Disulphonated N,N,N-triphenyl-N,N-dimethyl-pararosaniline (Di-SO3)-(Tri-Ph)-(Di-Me)C39H33N3O6S2702.174704.188
Trisulphonated N,N,N-triphenyl-pararosaniline (Tri-SO3)-(Tri-Ph)C37H29N3O9S3754.099/376.546 [M-2H]2−756.114
Trisulphonated N,N,N-triphenyl-N-methyl-pararosaniline (Tri-SO3)-(Tri-Ph)-(Me)C38H31N3O9S3768.115/383.225 [M-2H]2−770.130
Trisulphonated N,N,N-triphenyl-N,N-dimethyl-pararosaniline (Tri-SO3)-(Tri-Ph)-(Di-Me)C39H33N3O9S3782.131/390.562 [M-2H]2−784.145
Degradation products of Methyl BlueHeritage 08 00028 i019
Methyl Blue DP		C25H20N2O4S443.107445.1217
Methyl Blue DP + CH2C26H22N2O4S457.123459.1373
Methyl Blue DP + 2CH2C27H24N2O4S471.138473.153
Orange II (C.I. 15510; Acid Orange 7)4-(2-Hydroxy-1-naphthylazo)benzenesulfonic acid (Orange II)C16H12N2O4S327.045329.059
Orange IV (C.I. 13080; Acid Orange 5)4-[(4-Anilinophenyl)azo]benzenesulfonic acid (Orange IV)C18H15N3O3S352.076354.091
Metanil Yellow (C.I. 13065, Acid Yellow 36)3-[(4-Anilinophenyl)diazenyl]benzenesulfonic acid (Metanil Yellow)C18H15N3O3S352.076354.091
Chrysoidine R (C.I. 11320, Basic Orange 1)Heritage 08 00028 i020
Chrysoidine R degradation product		C14H13N4+ 237.114
* Robinoside = α-L-rhamnopyranosyl-(1→6)-O-β-D-galactopyranoside. ** Rhamninoside = α-L-rhamnopyranosyl-(1→3)-O-α-L-rhamnopyranosyl-(1→6)-O-β-D-galactopyranoside.
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Tamburini, D.; Durand, L.; Klink-Hoppe, Z. Refining the Production Date of Historical Palestinian Garments Through Dye Identification. Heritage 2025, 8, 28. https://doi.org/10.3390/heritage8010028

AMA Style

Tamburini D, Durand L, Klink-Hoppe Z. Refining the Production Date of Historical Palestinian Garments Through Dye Identification. Heritage. 2025; 8(1):28. https://doi.org/10.3390/heritage8010028

Chicago/Turabian Style

Tamburini, Diego, Ludovic Durand, and Zeina Klink-Hoppe. 2025. "Refining the Production Date of Historical Palestinian Garments Through Dye Identification" Heritage 8, no. 1: 28. https://doi.org/10.3390/heritage8010028

APA Style

Tamburini, D., Durand, L., & Klink-Hoppe, Z. (2025). Refining the Production Date of Historical Palestinian Garments Through Dye Identification. Heritage, 8(1), 28. https://doi.org/10.3390/heritage8010028

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