The Use of UV-Visible Diffuse Reflectance Spectrophotometry for a Fast, Preliminary Authentication of Gemstones.

The identification of gemstones is an important topic in the field of cultural heritage, given their enormous value. Particularly, the most important precious stones, namely diamond, emerald, ruby and sapphire, are frequently subjected to counterfeit by substitution with objects of lesser value with similar appearance, colour or shape. While a gemmologist is able to recognise a counterfeit in most instances, more generally, it is not easy to do this without resorting to instrumental methods. In this work, the use of UV-visible diffuse reflectance spectrophotometry with optic fibres (FORS) is proposed as a fast and easy method for the preliminary identification of gemstones, alternative to the classical methods used by gemmologists or to Raman spectroscopy, which is by far the instrumental method with the best diagnostic potential, but it cannot be used in situations of problematic geometric hindrance. The possibilities and the limitations given by the FORS technique are critically discussed together with the spectral features of the most important gemstones. Finally, the application of chemometric pattern recognition methods is described for the treatment of large sets of spectral data deriving from gemstones identification.

On the Traceability of the Hazelnut Production Chain by Means of Trace Elements.

The production chain of hazelnuts has been studied by analyzing three sets of samples produced in purity from three different pools of hazelnuts of cultivar "Tonda Gentile Trilobata", "Tonda Gentile Romana" and "Mortarella", all cultivated in Italy. From each pool, five processed products were obtained: roasted hazelnuts, hazelnut paste, hazelnut cream, Gianduja paste and Gianduiotto paste. After pre-treatment by means of dry ashing, all samples from each cultivar, including raw hazelnuts, were then analyzed by means of Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES) and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). A good discrimination was obtained among the different chain stages according to the distribution of the trace elements, as expected. More interesting was the discrimination among the different cultivars: it was possible to distinguish the samples produced from the respective cultivar by means of specific chemical markers, particularly Mo and Ni.

New Hints on the Maya Blue Formation Process by PCA-Assisted In Situ XRPD/PDF and Optical Spectroscopy.

The exact recipe to prepare the ancient Maya Blue (MB), an incredibly resistant and brilliant pigment prepared from indigo (dye) and Palygorskite (clay), is lost to the ages. To unravel the key features of the MB formation process, several inorganic-dye couples were heated to 200 °C and cooled to RT, to investigate their reactivity and the diffusion and degree of sequestration of the dye into the inorganic host. In situ XRPD/PDF and fiber optic reflectance spectroscopy (FORS) data, along with TGA, provided a comprehensive overview on MB formation mechanism. XRPD/PDF gave information on long/short range behaviors of water desorption/adsorption and indigo sequestration, while TGA and in situ FORS gave information on mass and optical changes within temperature. Ex situ dye removal was used to understand the sample stability after the thermal treatment. A statistical approach based on principal component analysis was exploited to efficiently and jointly analyze the ≈3000 collected patterns. MB formation starts below 110 °C with disordered distribution of indigo within the channels, reaching maximum reaction speed and higher ordering at 150 °C. Above 175 °C, color changes and a stronger sequestration of indigo into framework channels are observed, whereas the affinity for water is dramatically reduced. The origin of different colors, hues, and stability in historical MB samples can then be explained in terms of different thermal histories of the starting mechanical indigo/palygorskite mixtures.

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.

It's Only a Part of the Story: Analytical Investigation of the Inks and Dyes Used in the Privilegium Maius.

The Privilegium maius is one of the most famous and spectacular forgeries in medieval Europe. It is a set of charters made in the 14th century upon commitment by Duke Rudolf IV, a member of the Habsburg family, to elevate the rank and the prestige of his family. These five charters, now kept at the Österreichisches Staatsarchiv in Vienna, have been subjected to a thorough interdisciplinary study in order to shed light on its controversial story. The charters are composed of pergamenaceous documents bound to wax seals with coloured textile threads. The present contribution concerns the characterisation of the inks used for writing and of the dyes used to colour to the threads: Are they compatible with the presumed age of the charters? Though showing only a part of the whole story of the charters, dyes analysis could contribute in assessing their complex history from manufacturing to nowadays. The dyes were characterised with non-invasive in situ measurements by means of fibre optic (FORS) and with micro-invasive measurements by means of Surface Enhanced Raman Spectroscopy (SERS) and High-Performance Liquid Chromatography with Mass Spectrometry (HPLC-MS) analysis. The results showed that the threads of four of the charters (three dyed with madder, one with orchil) were apparently coloured at different dyeing stages, then re-dyed in the 19-20th century.

Physiological Responses to Salt Stress at the Seedling Stage in Wild (Oryza rufipogon Griff.) and Cultivated (Oryza sativa L.) Rice.

Domesticated rice Oryza sativa L. is a major staple food worldwide, and the cereal most sensitive to salinity. It originated from the wild ancestor Oryza rufipogon Griff., which was reported to possess superior salinity tolerance. Here, we examined the morpho-physiological responses to salinity stress (80 mM NaCl for 7 days) in seedlings of an O. rufipogon accession and two Italian O. sativa genotypes, Baldo (mildly tolerant) and Vialone Nano (sensitive). Under salt treatment, O. rufipogon showed the highest percentage of plants with no to moderate stress symptoms, displaying an unchanged shoot/root biomass ratio, the highest Na+ accumulation in roots, the lowest root and leaf Na+/K+ ratio, and highest leaf relative water content, leading to a better preservation of the plant architecture, ion homeostasis, and water status. Moreover, O. rufipogon preserved the overall leaf carbon to nitrogen balance and photosynthetic apparatus integrity. Conversely, Vialone Nano showed the lowest percentage of plants surviving after treatment, and displayed a higher reduction in the growth of shoots rather than roots, with leaves compromised in water and ionic balance, negatively affecting the photosynthetic performance (lowest performance index by JIP-test) and apparatus integrity. Baldo showed intermediate salt tolerance. Being O. rufipogon interfertile with O. sativa, it resulted a good candidate for pre-breeding towards salt-tolerant lines.

On the Traceability of Honey by Means of Lanthanide Distribution.

Honey is a natural food appreciated all over the world since antiquity due to its well-recognised beneficial properties. However, it is also considered among the most counterfeited foods. Therefore, analytical methods are currently being developed to allow the verifying of its geographic provenance and its botanical origin. Trace- and ultra-trace elements are usually exploited as chemical descriptors in authentication studies, as they allow the properties declared in the label to be verified. A different matter is to trace a food by means of traceability, that is, to find the link between a food and the soil in which this food originates. For traceability, it has been demonstrated in several studies that the lanthanides are particularly useful to find this link. In the present study, the traceability of the honey chain has been studied by means of ICP-MS and ICP-OES analysis, by comparing the lanthanide distributions of 17 different monofloral honey chains, each one composed of honey, flowers and soil in which such flowers grew. The results show that, while the fingerprint of soil, described by the lanthanide distribution, is transmitted unaltered from soil to flowers, a slight fractionation on the heavier lanthanides (from Dy to Lu) occurs in the passage from flowers to honey.

The Vienna Genesis: An Example of Late Antique Purple Parchment.

The investigation and conservation of the Vienna Genesis, a Late Antique manuscript on purple parchment, included the study of parchment production and purple dyeing in the sixth century. The process of parchment making and of purple dyeing was recreated and compared with the Vienna Genesis and other manuscripts from the sixth and eighth centuries. Parchment made from the hides of young lambs and dyed with orchil resembled the folios of the Vienna Genesis. The results of material analysis and the study of parchment technology influenced decisions for the conservation and storage of the manuscript. Fragile areas of ink and parchment were stabilised with strips of adhesive coated Japanese tissue paper. The single folios are stored in folders of Japanese paper and museum matboard within a sink mat.

Screening for heavy metal accumulators amongst autochtonous plants in a polluted site in Italy.

The site around ACNA factory (Northern Italy) is characterized by multi-metal contamination, therefore it can be considered as a source of autochthonous plants able to tolerate or accumulate heavy metals (HMs). The hill A5, a waste dump of the chemical factory, was chosen as the study area, in order to assess the metal accumulation ability of the vegetation growing under HM stress. The plant species, biodiversity and health were related to the concentration of HMs in four areas of the hill A5, and to the metal accumulation in shoots and roots. Uptake of HMs occurred at different extent in the various plant species and differed according to the considered organ and metal. Polygonum aviculare hyperaccumulated Hg in the shoot suggesting its possible exploitation in phytoextraction. A number of species, that can be useful in phytoremediation plans, accumulated simultaneously more than two heavy metals both in the shoot and in the root.

Combined use of FORS, XRF and Raman spectroscopy in the study of mural paintings in the Aosta Valley (Italy).

Mural paintings which decorate the external façade and the internal apsidal wall of a chapel dedicated to St. Maxime and located at Challand St. Victor in the Aosta Valley (Italy) have been analysed with a combined approach involving high-resolution fibre-optic reflectance spectroscopy (FORS), X-ray fluorescence (XRF) spectrometry and Raman spectroscopy. The paintings are attributed to Giacomino from Ivrea, a painter active around the mid-fifteenth century. In order to characterise the palette used by the painter and to yield information useful to restorers, the cited techniques were used either in situ with portable instruments and in laboratory, working on micro samples withdrawn from paintings. The global analytical approach, though not entirely non-invasive, can indeed be considered non-destructive as multiple analyses, including SEM-EDX, could be carried out on the micro samples, exploiting the features of each technique. On the basis of the information obtained, the palette was found to be composed of typical fresco pigments such as calcite, azurite, malachite, vermilion, red and yellow ochres. A particular situation was noted for black pigments since the presence of graphite, rather than wood or lamp carbon, was found, possibly related to the presence of graphite deposits in the Aosta Valley. Furthermore, the presence of smalt superimposed to azurite in areas showing evidence of repainting was detected, suggesting that paintings were subjected to retouching at a relatively early stage after the original execution. Finally, the presence of tin foils, used to decorate haloes of Evangelists, was ascertained.

A preliminary study on the authentication and traceability of extra virgin olive oil made from Taggiasca olives by means of trace and ultra-trace elements distribution.

Extra virgin olive oil (EVO) is among the most counterfeit foodstuffs in the present market. The Italian production is with no doubt one of the most valuable and therefore mostly counterfeit, due to the difficulty in checking the geographic provenance of olives. In order to provide a way for verifying the provenance of EVO, the role of microelements and, in particular, of lanthanides in the oil production chain has been studied. The distribution of lanthanides as determined by means of ICP-MS analysis appeared to provide a good tool for tracing the EVO production chain. Lanthanides and other microelements were then used for distinguishing a particularly prised EVO production from Liguria (northwestern Italy) made from Taggiasca olive variety, verifying that this production can be easily authenticated on the base of these chemical descriptors.

Analytical methods for determination of anthraquinone dyes in historical textiles: A review.

Historical and archaeological textiles are among the most crucial and vulnerable records of our social and cultural history. Analysis of organic colorants found in these materials is unquestionably one of the most powerful tools to understand historical developments, cultural exchanges, and progress in science and technology. Natural anthraquinones represent the most commonly used natural colorants for textile dyeing until the late 19th century. The identification of anthraquinones in cultural heritage objects is a challenging task due to the small size of historical samples, diversity of potential dye sources, variable extraction procedures and dyeing methods, complex chemical constitution, structurally analogous chromophores, and possible presence of degradation products and contaminants. Developments in dye analysis of historical interest have originated and expanded along with the general advances in analytical science. In the last few decades, a close cooperation between science and cultural heritage disciplines contributed enormously to this field. The topic of historical dyes and their analysis in textiles, artworks, archaeological objects and cultural heritage materials has been reviewed several times in the last fifteen years. However, no review has been published to-date exclusively on the analysis of anthraquinone colorants in historical and archaeological textiles. Overall, liquid chromatography (LC)-based techniques have been the most widely used method for anthraquinone dye analysis. Owing to increasing demand of minimally invasive/non-invasive techniques, recent developments of novel techniques have resulted in the availability of many alternative/complementary methods to LC-based analysis. This review begins with a short overview of sources, chemistry and importance of natural anthraquinone dyes found in historical textiles before turning to a detailed discussion on developments involving established and emerging analytical techniques of anthraquinone dye analysis for textile cultural heritage materials. To illustrate the state-of-the-art, representative examples of analytical techniques highlighting their advantages, limitations and applicability are also presented.

Mythic dyes or mythic colour? New insight into the use of purple dyes on codices.

The traditional knowledge concerning the use of Tyrian purple in Late Antique and Medieval purple codices - those precious biblical texts written with noble metal inks on parchment dyed or painted with purple colourants - is here updated in view of new analytical evidence. Recent literature reports the analysis carried out on some purple codices, suggesting that Tyrian purple has not, if ever, been used in their making. A large number of purple codices has been considered in this work to elucidate the nature of the purple colour. Results have been discussed within the frame of previous information, thus covering a vast majority of the purple codices presently identified. In most of the instances the use of less expensive dyes such as folium or orchil is suggested. Moreover, analytical results from a non-invasive spectroscopic approach have been definitely confirmed by micro-invasive surface-enhanced Raman analysis performed on micro samples of purple parchment taken from two 6th century codices.

Analytical evidences of the use of iron-gall ink as a pigment on miniature paintings.

Iron-gall ink (IGI) has been used by scribes for writing since at least the 4th century CE. Another typical use of this ink was for drawing: many Old Masters created beautiful sketches in brown-black hues. Despite its widespread use to draw lines, it seems like IGI was hardly used for painting as well. In fact, the number of identification on manuscripts is very low at present. This could be partially due to a lack of reliable diagnostic information. In this work we tried to better define the possibility of identifying IGI as a pigment on illuminate manuscripts, evaluating the pros and cons of three different techniques: UV-visible diffuse reflectance spectrophotometry with optic fibres (FORS), Raman spectroscopy and XRF spectrometry. With concern to in situ non-invasive analysis, Raman spectroscopy has the best diagnostic power but FORS seems to provide the better compromise between selectivity and ease of application. Moreover, new analytical evidences was given on the particular use of IGI by ancient illuminators: a non-invasive and micro-invasive diagnostic survey on Western manuscripts datable in the range 6-16th centuries was carried out showing that, apart from its widespread use as an ink for writing and drawing, IGI was largely used as a pigment too. The large number of identification obtained allows us to hypothesise that this pigment was used all through medieval Europe up to at least the Renaissance, where its use is already documented in drawing. The occurrence of IGI in miniature paintings older than 6th century or more recent than 16th century cannot be excluded, as is its use beyond Europe; further measurements could instead widen the time range and the geographic area. Nevertheless, the present study allows shedding a new light on the use of this colourant all along the period of medieval and Renaissance miniature painting art.

Non-invasive characterization of colorants by portable diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and chemometrics.

During the last years the need for non-invasive and non-destructive analytical methods brought to the development and application of new instrumentation and analytical methods for the in-situ analysis of cultural heritage objects. In this work we present the application of a portable diffuse reflectance infrared Fourier transform (DRIFT) method for the non-invasive characterization of colorants prepared according to ancient recipes and using egg white and Gum Arabic as binders. Approximately 50 colorants were analyzed with the DRIFT spectroscopy: we were able to identify and discriminate the most used yellow (i.e. yellow ochres, Lead-tin Yellow, Orpiment, etc.), red (i.e. red ochres, Hematite) and blue (i.e. Lapis Lazuli, Azurite, indigo) colorants, creating a complete DRIFT spectral library. The Principal Component Analysis-Discriminant Analysis (PCA-DA) was then employed for the colorants classification according to the chemical/mineralogical composition. The DRIFT analysis was also performed on a gouache painting of the artist Sutherland" and the colorants used by the painter were identified directly in-situ and in a non-invasive manner.

Role of Lanthanides in the Traceability of the Milk Production Chain.

The traceability and authentication of milk were studied using trace and ultratrace elements as chemical markers. Among these variables, the group of lanthanides resulted in being particularly useful for this purpose as a result of their homogeneous distribution inside milk, which showed on the contrary to be intrinsically inhomogeneous from the elemental point of view. Using in this pilot study milk samples from a factory in Piedmont (Italy), we demonstrated that the distribution of lanthanides can be used as a fingerprint to put into relation the soil of the pasture land on which cows graze and the bottled milk produced in the factory. In fact, the distribution is maintained nearly unaltered along the production chain of milk, apart from the passage into the stomachs of the cows. Using the same variables, it was possible to discriminate between milk produced in the factory and milk samples taken from the large-scale retail trade.

On the identification of folium and orchil on illuminated manuscripts.

The identification of the two purple dyes folium and orchil has rarely been reported in the analysis of painted artworks, especially when analysing illuminated manuscripts. This is not consistent with the fact that ancient literary sources suggested their use as substitutes for the more expensive Tyrian purple dye. By employing non-invasive spectroscopic techniques, the present work demonstrates that these dyes were actually widely used in the production of ancient manuscripts. By employing UV-visible diffuse reflectance spectrophotometry with optic fibres (FORS) and spectrofluorimetry, the abundant identification of both dyes on medieval manuscripts was performed by comparing the spectra recorded on ancient codices with those obtained on accurate replicas of dyed or painted parchment. Moreover, examples are also reported whereby the considered purple dyes were used in mixtures with other colourants. The overall information obtained here allowed us to define new boundaries for the time range in which orchil and folium dyes were used which is wider than previously thought, and to focus on their particular uses in the decoration of books.

Analytical investigations on the Coronation Gospels manuscript.

The Coronation Gospels or Krönungsevangeliar is a manuscript kept in Vienna at the Kunsthistorisches Museum Wien, datable to the end of VIII century A.D. and produced at Charlemagne court. It is an example of a purple codex, i.e. its parchment is coloured in purple. It has to be considered as one of the most important medieval codices, according to its use to take oath in the coronation ceremony of kings and emperors of the Holy Roman Empire up to 1792. In order to gather information of the manufacture of the manuscript and its present conservation state, a diagnostic investigation campaign has been carried out in situ with totally non-invasive techniques. X-ray Fluorescence Spectrometry (XRF), UV-visible diffuse reflectance spectrophotometry with optical fibres (FORS), spectrofluorimetry, optical microscopy and multispectral analysis have been applied in order to identify the colourants used in the decoration of the manuscript, with the main concern to the dye used to impart the purple hue to the parchment. The information collected was useful in order to address some of the questions raised by art historians concerning its history.

A diagnostic study on folium and orchil dyes with non-invasive and micro-destructive methods.

Folium and orchil are dyes of vegetal origin. Folium is obtained from Chrozophora tinctoria (L.) A. Juss., whereas orchil is obtained from Roccella and other genera of lichens. These dyes were used in the past to impart purple hue to paintings and textiles as substitutes for the more prised Tyrian purple dye, obtained from shellfish. Despite several citations in ancient technical treatises dating back at least to the Greek-Roman age, the identification of these dyes in artworks is rare. In the case of folium, an additional drawback is that its composition is presently unknown. In this work different non-invasive (FT-IR, FT-Raman, fibre optic reflectance spectrophotometry, spectrofluorimetry, X-ray fluorescence spectrometry) and micro-invasive (surface enhanced Raman spectroscopy, matrix assisted laser desorption ionisation-time of flight-mass spectrometry, inductively coupled plasma-mass spectrometry) techniques were used in order to increase the diagnostic information available on these dyes. Measurements were carried out on the dyes extracted from raw materials and on painted or dyed parchments. The possibility to distinguish between folium and orchil by chemical analysis is discussed.

Classification of Nebbiolo-based wines from Piedmont (Italy) by means of solid-phase microextraction-gas chromatography-mass spectrometry of volatile compounds.

Sixty-eight samples of wines from Piedmont (Italy) were analysed to determine their content of volatile compounds, using the solid-phase microextraction (SPME) technique coupled with gas chromatography-mass spectrometry (GC-MS). Samples were from five groups of wines: Barolo, Barbaresco, Nebbiolo d'Alba, Roero and Langhe Nebbiolo, all produced from the Nebbiolo grape in the Langhe and Roero areas (province of Cuneo, Piedmont) but differing in vintage (respectively, 3 years, 2 years, 1 year, 8 months and few months) and production zone. Thirty-five analytes were identified; peak area data, corrected for internal standard, were used for pattern recognition treatments. Principal components analysis, hierarchical cluster analysis, Kohonen self organising map, stepwise linear discriminant analysis and soft independent modelling of class analogy were applied to the data, revealing a good separation between the five groups. A main factor, strictly connected to wine vintage, was identified and found to be related to some analytes.