Monica Gulmini

Characterisation of colourants on illuminated manuscripts by portable fibre optic UV-visible-NIR reflectance spectrophotometry

The use of ultraviolet and visible diffuse reflectance spectrophotometry as a preliminary technique in the investigation of illuminated manuscripts is discussed. Because ancient manuscripts are amongst the most fragile and precious artworks, characterisation of the materials used in their decoration should be performed using non-invasive analytical methods. Ultraviolet and visible reflectance spectrophotometry with optical fibres (FORS) allows non-invasive identification of several colourants used by ancient illuminators, causing no damage or mechanical stress to the artworks subjected to analysis. Identification is usually based on the comparison of analytical data with a spectral database built from painted areas on parchment, created by preparing paints according to ancient recipes as described in medieval technical treatises. Such database and the spectral features of the colourants analysed are discussed, along with the benefits of extending the spectral range of analysis into the shortwave infrared (to 2500 nm). FORS can be best appreciated as a rapid preliminary tool that offers an overview on the main colourants employed and guides the selection of painted areas of manuscripts on which more selective techniques, such as X-ray fluorescence or Raman spectroscopy, can be employed for a more complete and accurate identification.

Silver colloidal pastes for dye analysis of reference and historical textile fibers using direct, extractionless, non-hydrolysis surface-enhanced Raman spectroscopy†

Surface-enhanced Raman spectroscopy (SERS) is an ideal tool for analyzing dyes on historical textiles because it requires very little sample compared to other available analytical methods and analysis can be done directly on the fiber. This paper reports on the first systematic study of the use of citrate-reduced silver colloidal pastes for the direct, extractionless, non-hydrolysis detection of dyes directly on wool, silk, cotton, and flax fibers. This type of study provides greater insight into the optimal conditions required for accurate analysis of dyes in historical samples. In this work, Ag colloidal pastes were characterized using localized surface plasmon resonance and scanning electron microscopy. The pastes were then employed for SERS analysis of twelve reference samples of different vegetal and animal fibers dyed with cochineal and eleven dyed with brazilwood. Furthermore, six historical textiles from an important collection of Mariano Fortuny (1871-1949) textiles at the Art Institute of Chicago were also examined, to test the efficacy of the paste on aged samples, and to shed light on Fortunys fascinating production techniques. A mixture of cochineal and brazilwood was detected in some of the historical samples demonstrating, for the first time, simultaneous identification of these colorants used in combination. In addition, the findings give substance to the claim that Fortuny kept using natural dyes at a time when many new and attractive synthetic products became available.

Comparison between microwave and conventional heating procedures in Tessier's extractions of calcium, copper, iron and manganese in a Lagoon sediment

The results of Tessiers extraction of calcium, copper, iron and manganese in sediments using conventional and microwave heating were compared. The metals were determined by atomic absorption spectrometry with flame and electrothermal atomization. Magnesium chloride (extractant of exchangeable fraction) was replaced with ammonium acetate. Sediments collected from the Venice lagoon were analysed. The results showed that microwave heating produces results comparable to those of conventional heating with a much shorter operating time.

Glass Fragments from the Crypta Balbi in Rome: the Composition of Eighth‐century Fragments

Eighth-century glass fragments from the Crypta Balbi in Rome were analysed by inductively coupled plasma emission spectroscopy. The samples included fragments of artefacts as well as ingots of raw glass and wasters. All the fragments proved to be soda-lime glasses. Manganese-to-iron atomic ratios are highly variable and determine the colour of a large number of samples. Fairly high copper contents, generally associated with relatively high amounts of antimony and lead, were detected in some green and blue-green samples: this suggests recycling of glass in the form of opaque mosaic tesserae. All three elements are higher in eighth-century than in previously analysed seventh-century fragments. This may indicate greater recourse to recycled glass, related to a reduction in trade exchanges in the Mediterranean.

Non-invasive investigation on a VI century purple codex from Brescia, Italy

Purple codices are among the most relevant and prestigious book productions of Late Antique and Medieval age. They usually contained texts from Holy Writings written with golden or silver inks on parchment dyed in a purple hue. According to the tradition, the colour of parchment was obtained by the well renowned Tyrian purple dye. From the material point of view, however, very little is known about the compounds actually used in the manufacture of these manuscripts. Presently, the information available is limited to the ancient art treatises, with very few diagnostic evidences supporting them and, moreover, none confirming the presence of Tyrian purple. It is more than apparent, then, the need to have at disposal larger and more complete information at the concern, in order to verify what came to us from the literary tradition only. In this study, preliminary results are presented from non-invasive investigation on a VI century purple codex, the so-called CodexBrixianus, held in the Biblioteca Civica Queriniana at Brescia (Italy). Analyses were carried out with XRF spectrometry, UV-visible diffuse reflectance spectrophotometry, molecular spectrofluorimetry and optical microscopy. The results suggest the hypothesis that Tyrian purple had been used as a minor component mixed with other less precious dyes such as folium or orchil.

Selective recovery of uranium(VI) from aqueous acid solutions using micellar ultrafiltration

Preconcentration and removal of uranyl ions from aqueous solutions were achieved by using micellar-enhanced ultrafiltration with complexing micellar aggregates composed of Triton X-100 and different hydrophobic ligands. Derivatives of 4-aminosalicylic acid (PAS) and of 1-(2-pyridylazo)-2-naphthol (PAN) having tuned alkyl chains were used as suitable chelating agents. The selective recovery of uranyl from acid samples containing also SrII and CdII is possible using the multi-step ultrafiltration approach with the PAN derivatives, whereas effective uranyl retention can be obtained with salicylates only in neutral to basic media.

Acid-base properties of a river sediment: Applicability of potentiometric titrations

Abstract The application of potentiometric titrations to the study of the acid-base properties of a river sediment was investigated. A set of alkalimetric titrations were performed on suspensions containing different sediment-solution ratios and EMF measurements were elaborated by a suitable computer program. After the optimisation of the titration procedure, it was possible to refine conditional acid constants. For the considered sediment it was possible to calculate three protonation constants. Comparing calculated pKa with those reported in literature for the characterisation of humic and fulvic material of various origins and for inorganic hydrous oxides, it appears that calculated values are in the range indicated for the assignment of the constants to organic and inorganic titratable groups that can be present on the surface of a natural sediment.

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.

Spectroscopic Analysis to Characterize Finishing Treatments of Ancient Bowed String Instruments

Historical bowed string instruments exhibit acoustic features and aesthetic appeal that are still considered inimitable. These characteristics seem to be in large part determined by the materials used in the ground and varnishing treatments after the assembly of the instrument. These finishing processes were kept secret by the violinmakers and the traditional methods were handed down orally from master craftsmen to apprentices. Today, the methods of the past can represent a secret to be revealed through scientific investigations. The “Cremonese” methods used in the 17th and 18th centuries were lost as the last Great Masters from the Amati, Guarneri, and Stradivari families passed away. In this study, we had the chance of combining noninvasive and microinvasive techniques on six fragments of historical musical instruments. The fragments were detached from different instruments during extraordinary maintenance and restoration treatments, which involved the substitution of severely damaged structural parts like top plates, back plates, or ribs. Therefore, the fragments can offer to the scientists a valuable overview on the materials and techniques used by the violinmakers. The results obtained by portable X-ray fluorescence, optical microscopy, scanning electron microscopy coupled with energy dispersive X-ray spectrometry, and Fourier transform infrared microscopy allowed us to: (1) determine the stratigraphy of six instruments; (2) obtain new information about the materials involved in the finishing processes employed in Cremona; and (3) elucidate the technological relationship among the procedures adopted in the violin making workshops during the considered period.

Properties of a cobalt-reactivated form of yeast alcohol dehydrogenase

Abstract Yeast alcohol dehydrogenase (Y-ADH) is a widely studied metal-enzyme for its well-known biotechnological importance. Although its structure has been extensively investigated, some topics still remain controversial (zinc content and role), and various attempts aiming at modifying its structure to improve its catalytic properties have been made. In this paper, a metal-substituted Y-ADH has been prepared in vitro, in which one Zn atom per molecule (only one of those directly involved in catalysis) has been substituted by one Co atom. The substitution was obtained through zinc removal by a chelating treatment (with Chelex 100) followed by cobalt insertion. The zinc content in the native enzyme was preliminarily evaluated (taking care to avoid contamination) to be 4.1±0.1 g-at./molecule. After cobalt substitution, the ratio Zn:Co in the enzyme results to be 3:1. The active Co-Y-ADH has been compared with the native enzyme: it has lower specific activity (about 50%) and lower substrate affinity but greater thermo-resistance and a pH stability in a wider range than the native Y-ADH. A similar behavior, as far as cobalt content, thermo-resistance and pH stability are concerned, but greater specific activity and substrate affinity, were shown by an in vivo-substituted Co-Y-ADH obtained in a previous study.