Compositional and Micro-Morphological Characterisation of Red Colourants in Archaeological Textiles from Pharaonic Egypt.

When the imagination conjures up an image of an Egyptian mummy, it is normally one of a human body wrapped with undyed linen bandages. However, the reality was much more colourful, as shown by the set of red mummy shrouds and textile fragments from Pharaonic Egypt considered in this work. The textiles were subjected to scientific investigation with the main aim of shedding light on the sources of red colour and on the possible reasons for the different levels of colour fading. The red colourants were investigated using various non-invasive and micro-invasive approaches. The results pointed towards the presence of three sources of red colour, which, in increasing order of lightfastness, are safflower (Carthamus tinctorius), madder (Rubia spp.), and red ochre. Micro-morphological observations and elemental analyses also enabled some hypotheses to be formulated regarding the application of these colourants to the textiles. The results not only deepen our knowledge of dyeing technologies in ancient Egypt and shed new light on the function of red shrouds and textiles as part of the funerary practices of Pharaonic Egypt, but are also essential in planning the display and future preservation of these mummies and their associated textiles.

Tooth grooves, occlusal striations, dental calculus, and evidence for fiber processing in an Italian eneolithic/bronze age cemetery.

OBJECTIVES: We conducted a systematic macroscopic and microscopic examination of occlusal and para-occlusal wear in a large dental sample (n = 3,014) from 217 individuals dated to the Early Bronze age site of Gricignano d'Aversa, Italy. We used macroscopic and microscopic techniques to document nondietary occlusal and para-occlusal wear and to analyze calculus inclusions in some of the teeth. In combining an analysis of the wear with the calculus inclusions we linked the specific wear to the likely fiber that was involved in producing it. MATERIALS AND METHODS: Teeth and their high resolution epoxy casts were analyzed through SEM and reflected light microscopes. Nineteen individuals (fifteen with activity induced dental modifications and four as a control sample) were examined for the presence of calculus inclusions. RESULTS: Activity induced dental modifications (AIDMs), notches, grooves and micro-striations, were found in the 62.2% of the adult females, in 21.2% of the adults of unknown sex and in a single male. We found the full spectrum of dental manipulations from very minor nonocclusal wear in some young individuals to severe attrition at the other extreme. The width of the striations and grooves, mostly on the upper incisors, suggests a craft activity involving fibers and thread production and manipulation. From the dental calculus of two females with grooves and striations, we extracted three fragments of fibers, identified as hemp (Cannabis, sp.). Previously from Gricignano woven hemp fibers were found on both surfaces of a metal blade associated with a male burial. DISCUSSION: This study found the co-occurrence of tooth AIDMs and the actual fibers preserved in the dental calculus. As more work is done analyzing dental calculus in a variety of humans, it is apparent that this biological material holds rich resources documenting non-dietary habits.

Development of an enzyme-linked-immunosorbent-assay technique for accurate identification of poorly preserved silks unearthed in ancient tombs.

We report the preparation of a specific fibroin antibody and its use for the identification of unearthed ancient silk relics. Based on the 12-amino-acid repeat sequence "GAGAGSGAGAGS", which is found in fibroin of the silkworm Bombyx mori, a specific antibody against fibroin was prepared in rabbits through peptide synthesis and carrier-protein coupling. This antibody was highly specific for fibroin found in silk. Using this antibody we have successfully identified four silk samples from different time periods. Our results reveal, for the first time, a method capable of detecting silk from a few milligrams of archaeological fabric that has been buried for thousands of years, confirming that the ancient practice of wearing silk products while praying for rebirth dated back to at least 400 BCE. This method also complements current approaches in silk detection, especially for the characterization of poorly preserved silks, promoting the investigation of silk origins and of ancient clothing cultures.

Identification of unknown colorants in pre-Columbian textiles dyed with American cochineal (Dactylopius coccus Costa) using high-performance liquid chromatography and tandem mass spectrometry.

The present study concerns the identification of nine thus-far unknown derivatives of carminic acid extracted from pre-Columbian Peruvian textiles dyed with American cochineal-these derivatives are not found in commercially available preparations of the dye. These compounds probably represent a unique fingerprint of dyed textiles from this region, as they have never been reported to occur in other fabrics of historical value. They were separated by reversed-phase high-performance liquid chromatography (phenyl column) and detected using a UV/vis spectrophotometer and two tandem mass spectrometers. Peaks observed in chromatograms registered at 450 and 500 nm were further identified by ESI QqQ MS (mainly in the negative ion mode), supported by high-resolution ESI QIT/ToF MS data. The characteristic fragmentation pathways of isolated carminic acid and its derivatives provided additional information concerning lost neutrals and thus the functional groups and substituents present in the parent molecules. This information mainly related to multiple cleavages of the hexoside moiety (initially cross-ring cleavage), which are characteristic of C-glucosides (loss of 90, 120, and 148 Da). This is accompanied by the elimination of H2O as well as the further loss of 60 Da from the hexoside moiety. Moreover, other losses from the carbonyl groups (44 Da from CO2 loss, 62 Da from ethylene glycol loss, 32 Da from O2 loss, 138 Da from hydroxybenzoic acid, and 120 Da from oxomethylene cyclohexadienone) provided more specific information about structures of the identified derivatives of carminic acid.

Identification of Natural Dyes in Ancient Textiles by Time-of-Flight Secondary Ion Mass Spectrometry and Surface-Enhanced Raman Spectroscopy.

The identification of dyes in archaeological remains is a long standing challenge. Major problems include contamination by environmental conditions over long periods of time, small amounts and limited availability of excavated samples, and low concentrations of dyestuff in the obtained samples. To address these issues, highly sensitive and non-destructive techniques are required. In response, in this work, two non-destructive analytical techniques, Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) and Surface-Enhanced Raman Spectroscopy (SERS), were used for dye detection and the analysis results are compared. TOF-SIMS provides high detection efficiency for the analysis of organic materials whereas SERS is a useful technique for the detection of dyes in ancient textiles. An Ag colloid was employed to surmount the limitations of normal Raman measurement such as background fluorescence and weak Raman signals in small amounts of components. To identify the dyes used in ancient textiles, standard samples prepared using various dyestuffs and historical samples were analyzed with TOF-SIMS and Raman techniques. From the TOF-SIMS and the SERS spectra, dyestuffs such as alizarin, berberine, an indigo were identified in ancient textiles. The results suggest that TOF-SIMS and SERS are efficient non-destructive techniques for the characterization of archaeological textiles.

Asbestos between science and myth. A 6,000-year story.

Asbestos was used in making pottery in Eastern Finland from around 4000 B.C. In the ancient era and in the Middle Ages, magic properties were frequently attributed to this mineral. In the first century A.D., the Latin encyclopaedist Pliny the Elder reported in his Historia Naturalis that asbestos protects against all poisonings, particularly that of magicians. Moreover, asbestos was often found in places of worship, in Rome as well as in Athens and in Jerusalem. In the Middle Ages asbestos was identified with some animals, such as the salamander and certain white rodents. With such appearance, the mineral  had a huge success in Western as well as in Eastern literature and the fine arts. Marco Polo (1254-1324) in the Milione tried to deny that asbestos was a salamander. Despite its noxious effects, asbestos continues to be used in much of the world. In the 21st century it seems to be maintaining its quality as a magic stone.

Electrospinning versus fibre production methods: from specifics to technological convergence.

Academic and industrial research on nanofibres is an area of increasing global interest, as seen in the continuously multiplying number of research papers and patents and the broadening range of chemical, medical, electrical and environmental applications. This in turn expands the size of the market opportunity and is reflected in the significant rise of entrepreneurial activities and investments in the field. Electrospinning is probably the most researched top-down method to form nanofibres from a remarkable range of organic and inorganic materials. It is well known and discussed in many comprehensive studies, so why this review? As we read about yet another "novel" method producing multifunctional nanomaterials in grams or milligrams in the laboratory, there is hardly any research addressing how these methods can be safely, consistently and cost-effectively up-scaled. Despite two decades of governmental and private investment, the productivity of nanofibre forming methods is still struggling to meet the increasing demand. This hinders the further integration of nanofibres into practical large-scale applications and limits current uses to niche-markets. Looking into history, this large gap between supply and demand of synthetic fibres was seen and addressed in conventional textile production a century ago. The remarkable achievement was accomplished via extensive collaborative research between academia and industry, applying ingenious solutions and technological convergence from polymer chemistry, physical chemistry, materials science and engineering disciplines. Looking into the present, current advances in electrospinning and nanofibre production are showing similar interdisciplinary technological convergence, and knowledge of industrial textile processing is being combined with new developments in nanofibre forming methods. Moreover, many important parameters in electrospinning and nanofibre spinning methods overlap parameters extensively studied in industrial fibre processing. Thus, this review combines interdisciplinary knowledge from the academia and industry to facilitate technological convergence and offers insight for upscaling electrospinning and nanofibre production. It will examine advances in electrospinning within a framework of large-scale fibre production as well as alternative nanofibre forming methods, providing a comprehensive comparison of conventional and contemporary fibre forming technologies. This study intends to stimulate interest in addressing the issue of scale-up alongside novel developments and applications in nanofibre research.

Analysis of natural red dyes (cochineal) in textiles of historical importance using HPLC and multivariate data analysis.

A new analytical approach based on high-performance liquid chromatography with diode array detector (HPLC-DAD) and multivariate data analysis was applied and assessed for analyzing the red dye extracted from cochineal insects, used in precious historical textiles. The most widely used method of analysis involves quantification of specific minor compounds (markers), using HPLC-DAD. However, variation in the cochineal markers concentration, use of aggressive dye extraction methods and poor resolution of HPLC chromatograms can compromise the identification of the precise insect species used in the textiles. In this study, a soft extraction method combined with a new dye recovery treatment was developed, capable of yielding HPLC chromatograms with good resolution, for the first time, for historical cochineal-dyed textiles. After principal components analysis (PCA) and mass spectrometry (MS), it was possible to identify the cochineal species used in these textiles, in contrast to the accepted method of analysis. In order to compare both methodologies, 7 cochineal species and 63 historical cochineal insect specimens were analyzed using the two approaches, and then compared with the results for 15 historical textiles in order to assess their applicability to real complex samples. The methodology developed here was shown to provide more accurate and consistent information than the traditional method. Almost all of the historical textiles were dyed with Porphyrophora sp. insects. These results emphasize the importance of adopting the proposed methodology for future research on cochineal (and related red dyes). Mild extraction methods and HPLC-DAD/MS(n) analysis yield distinctive profiles, which, in combination with a PCA reference database, are a powerful tool for identifying red insect dyes.

Feet and fabrication: footbinding and early twentieth-century rural women's labor in Shaanxi.

The early twentieth-century transformations of rural Chinese women's work have received relatively little direct attention. By contrast, the former custom of footbinding continues to fascinate and is often used to illustrate or contest theories about Chinese women's status. Arguing that for rural women at least, footbinding needs to be understood in relation to rural economic conditions, the authors focus on changes in textile production and in footbinding in two counties in Shaanxi province. Drawing on historical sources and their own interview data from rural women who grew up in this period, the authors find evidence that transformations in textile production undercut the custom of footbinding and contributed to its rapid demise.

Lessons on textile history and fibre durability from a 4,000-year-old Egyptian flax yarn.

Flax has a long and fascinating history. This plant was domesticated around 8,000 BCE1 in the Fertile Crescent area2, first for its seeds and then for its fibres1,3. Although its uses existed long before domestication, residues of flax yarn dated 30,000 years ago have been found in the Caucasus area4. However, Ancient Egypt laid the foundations for the cultivation of flax as a textile fibre crop5. Today flax fibres are used in high-value textiles and in natural actuators6 or reinforcements in composite materials7. Flax is therefore a bridge between ages and civilizations. For several decades, the development of non- or micro-destructive analysis techniques has led to numerous works on the conservation of ancient textiles. Non-destructive methods, such as optical microscopy8 or vibrational techniques9,10, have been largely used to investigate archaeological textiles, principally to evaluate their degradation mechanisms and state of conservation. Vibrational spectroscopy studies can now benefit from synchrotron radiation11 and X-ray diffraction measurement in the archaeometric study of historical textiles12,13. Conservation of mechanical performance and the ultrastructural differences between ancient and modern flax varieties have not been examined thus far. Here we examine the morphological, ultrastructural and mechanical characteristics of a yarn from an Egyptian mortuary linen dating from the early Middle Kingdom (Eleventh Dynasty, ca. 2033-1963 BCE) and compare them with a modern flax yarn to assess the quality and durability of ancient flax fibres and relate these to their processing methods. Advanced microscopy techniques, such as nano-tomography, multiphoton excitation microscopy and atomic force microscopy were used. Our findings reveal the cultural know-how of this ancient civilization in producing high-fineness fibres, as well as the exceptional durability of flax, which is sometimes questioned, demonstrating their potential as reinforcements in high-technology composites.

Direct evidence of Neanderthal fibre technology and its cognitive and behavioral implications.

Neanderthals are often considered as less technologically advanced than modern humans. However, we typically only find faunal remains or stone tools at Paleolithic sites. Perishable materials, comprising the vast majority of material culture items, are typically missing. Individual twisted fibres on stone tools from the Abri du Maras led to the hypothesis of Neanderthal string production in the past, but conclusive evidence was lacking. Here we show direct evidence of fibre technology in the form of a 3-ply cord fragment made from inner bark fibres on a stone tool recovered in situ from the same site. Twisted fibres provide the basis for clothing, rope, bags, nets, mats, boats, etc. which, once discovered, would have become an indispensable part of daily life. Understanding and use of twisted fibres implies the use of complex multi-component technology as well as a mathematical understanding of pairs, sets, and numbers. Added to recent evidence of birch bark tar, art, and shell beads, the idea that Neanderthals were cognitively inferior to modern humans is becoming increasingly untenable.

Phytochemical analysis of young fustic (Cotinus coggygria heartwood) and identification of isolated colourants in historical textiles.

Young fustic (Cotinus coggygria Scop.; Anacardiaceae) has been used as a dyestuff since antiquity. Phytochemical investigation of the methanol extract of the heartwood has led to the isolation and structure elucidation by nuclear magnetic resonance and mass spectrometry (MS) of 3',4',6-trihydroxyaurone (sulfuretin) and 3',4',7-trihydroxyflavonol (fisetin) as well as 3',4',7-trihydroxyflavanol (fustin), 3',4',5,7-tetrahydroxyflavonol (quercetin), 3',4',5,7-tetrahydroxyflavanol (taxifolin), 4',7-dihydroxyflavanol, 3',4',7-trihydroxyflavanone (butin), 4',7-dihydroxyflavanone (liquiritigenin), trans-2',3,4,4'-tetrahydroxychalcone (butein), 4',5,7-trihydroxyflavanone and trans-2',4,4'-trihydroxychalcone (isoliquiritigenin). The isolated compounds were used as reference materials for the development of a high-performance liquid chromatography-diode array detector-MS method, which was then applied to analyse (1) fresh silk samples dyed with young fustic, (2) dyed silk subjected to artificially accelerated light ageing and (3) historical silk micro-samples, extracted from ecclesiastical post-Byzantine garments (fifteenth to eighteenth century), which belong to monasteries of Mount Athos. Sulfuretin and fisetin, which are usually used as markers for the identification of the yellow dye and, for the first time, some of the aforementioned flavonoid components of young fustic were identified in the historical extracts. Furthermore, preliminary experiments suggested that although the amounts of the dye components decrease with light ageing, the relative ratio of fisetin and sulfuretin, after a first step of ageing, seems to be almost unaffected by such degradation processes raised by light. The effect of the latter on the morphology of the dyed silk fibres is briefly investigated by scanning electron microscopy.

A new multi analytical approach for the identification of synthetic and natural dyes mixtures. The case of orcein-mauveine mixture in a historical dress of a Sicilian noblewoman of nineteenth century.

In this paper, the application of a multi-analytical approach for the characterisation of synthetic and natural dyes in a historical textile is presented. The work is focused on a historical dress of a Sicilian noblewoman, dating from about 1865-1870. Firstly, SERS on fibre was performed, in order to individuate the classes of dyes employed. The SERS spectra suggested the presence of two main dyes: mauveine and orcein. In order to confirm these preliminary results, two different extraction protocols were applied. The extracts obtained were analysed by ESI-MS, MALDI-ToF and UHPCL-MS analyses, confirming the SERS results. In particular, the application of the ammonia mild extraction technique allowed to selectively extract the phenoxazonic dyes, separating them already in the extraction step from the synthetic ones. Thanks to this multi-analytical approach, this dress could be considered as one of the first examples of employment of synthetic dyes in association with natural ones.

Liquid chromatography determination of natural dyes in extracts from historical Scottish textiles excavated from peat bogs.

Textiles excavated from Scottish sites belonging now to the collections of the National Museums of Scotland, including seventeenth century textiles from peat bogs in the Scottish Highlands and Islands, were selected for analysis by high performance liquid chromatography with photodiode array detection (PDA HPLC) to detect whether any dyes remained and, if so, to identify their biological sources. Dye components were identified in 36 of the 81 samples analysed. Although it was not possible to identify the exact sources of the dyestuffs because of the wide-spread occurrence of these natural dyes components, the study has shown that textiles previously not thought to have been coloured had detectable traces of dye. Before the historical textiles were analyzed, an improved extraction procedure that combined the routine acid hydrolysis method with one using dimethylformamide (DMF) was applied. The DMF method enabled increased recovery of major flavonoid and anthraquinoid compounds, and very high efficiency of recovery of indigotin even in textiles with no colour visible, thereby complementing the acid hydrolysis method already in use. Extracts from historical thread samples were analysed by PDA HPLC using a reversed-phase gradient system comprising of a C18 column (150 mm x 4.6 mm i.d., 25 +/- 1 degrees C) with water, methanol and o-phosphoric acid at an eluent flow rate of 1.2 ml/min. A preliminary investigation to improve the detection limits further for a selection of natural dyes was made by comparing results from the 4.6mm internal diameter (i.d.) column with a narrow bore C18 column (2.1 mm i.d.). An increase in the detector response was observed for narrow-bore column proving its possibility of enhancement of sensitivity.

Biomolecular Evidence of Silk from 8,500 Years Ago.

Pottery, bone implements, and stone tools are routinely found at Neolithic sites. However, the integrity of textiles or silk is susceptible to degradation, and it is therefore very difficult for such materials to be preserved for 8,000 years. Although previous studies have provided important evidence of the emergence of weaving skills and tools, such as figuline spinning wheels and osseous lamellas with traces of filament winding, there is a lack of direct evidence proving the existence of silk. In this paper, we explored evidence of prehistoric silk fibroin through the analysis of soil samples collected from three tombs at the Neolithic site of Jiahu. Mass spectrometry was employed and integrated with proteomics to characterize the key peptides of silk fibroin. The direct biomolecular evidence reported here showed the existence of prehistoric silk fibroin, which was found in 8,500-year-old tombs. Rough weaving tools and bone needles were also excavated, indicating the possibility that the Jiahu residents may possess the basic weaving and sewing skills in making textile. This finding may advance the study of the history of silk, and the civilization of the Neolithic Age.

Early pre-Hispanic use of indigo blue in Peru.

Archaeological research has identified the use of cultivated cotton (Gossypium barbadense) in the ancient Andes dating back to at least 7800 years ago. Because of unusual circumstances of preservation, 6000-year-old cotton fabrics from the Preceramic site of Huaca Prieta on the north coast of Peru retained traces of a blue pigment that was analyzed and positively identified as an indigoid dye (indigotin), making it the earliest known use of indigo in the world, derived most likely from Indigofera spp. native to South America. This predates by ~1500 years the earliest reported use of indigo in the Old World, from Fifth Dynasty Egypt [ca. 4400 BP (before present)]. Indigo is one of the most valued and most globally widespread dyes of antiquity and of the present era (it being the blue of blue jeans).

Provenancing Archaeological Wool Textiles from Medieval Northern Europe by Light Stable Isotope Analysis (δ13C, δ15N, δ2H).

We investigate the origin of archaeological wool textiles preserved by anoxic waterlogging from seven medieval archaeological deposits in north-western Europe (c. 700-1600 AD), using geospatial patterning in carbon (δ13C), nitrogen (δ15N) and non-exchangeable hydrogen (δ2H) composition of modern and ancient sheep proteins. δ13C, δ15N and δ2H values from archaeological wool keratin (n = 83) and bone collagen (n = 59) from four sites were interpreted with reference to the composition of modern sheep wool from the same regions. The isotopic composition of wool and bone collagen samples clustered strongly by settlement; inter-regional relationships were largely parallel in modern and ancient samples, though landscape change was also significant. Degradation in archaeological wool samples, examined by elemental and amino acid composition, was greater in samples from Iceland (Reykholt) than in samples from north-east England (York, Newcastle) or northern Germany (Hessens). A nominal assignment approach was used to classify textiles into local/non-local at each site, based on maximal estimates of isotopic variability in modern sheep wool. Light element stable isotope analysis provided new insights into the origins of wool textiles, and demonstrates that isotopic provenancing of keratin preserved in anoxic waterlogged contexts is feasible. We also demonstrate the utility of δ2H analysis to understand the location of origin of archaeological protein samples.