Lead soaps formation and biodiversity in a XVIII Century wax seal coloured with minium.

A multidisciplinary approach was carried out in order to study the biodeterioration and the associated microbiome of a XVIII Century wax seal coloured with minium. A small wax seal fragment was observed by scanning electron microscopy combined with energy dispersive spectroscopy in non-destructive mode. The same object was analysed by Raman and Fourier-transform infrared spectroscopy. The identification of the microbiota growing on the seal was performed with both a culture-dependent strategy, combined with hydrolytic assays, and high-throughput sequencing using the MinION platform. The whole bacterial 16S rRNA gene and the fungal markers ITS and 28S rRNA were targeted. It was observed that the carnauba wax coloured with lead tetroxide (minium) was covered by a biofilm consisting of a network of filaments and other structures of microbial origin. The culture-dependent and culture-independent investigations showed the presence of a complex microbiota composed mainly by fungal members, which demonstrated interesting properties related to lipids and lead processing. The formation of lead soaps and secondary biogenic minerals was also described.

Newly Developed Nano-Calcium Carbonate and Nano-Calcium Propanoate for the Deacidification of Library and Archival Materials.

Paper-based cultural heritage objects are subject to natural deterioration due to internal and external factors, that is, the presence of heavy metals, incorrect conservation, humidity, exposure of the artifacts to pollutants, light, and high temperatures. To contrast the decay of the original objects, it is necessary to study and apply innovative specific techniques, set up novel preservation methodologies, and implement or synthesize new products. As the nanomaterial science field developed over the last decades, the usage of nanomaterials in cultural heritage gained a prominent role. Such an excitement for the novel materials opened the path for an uncontrolled transfer of nanoparticles developed for different applications to paper restoration, neglecting all their possible interactions with the support or the graphic media. The aim of this work was to synthesize new nanomaterials expressly conceived for the treatment of library materials. To evaluate their possible insertion in the official conservation treatments that are subjected to validation by Istituto Centrale Restauro e Conservazione Patrimonio Archivistico e Librario, the new nanomaterials were tested both on laboratory paper samples and on original documents. This work presents the results of these studies (some of which still preliminary) stressing the positive and extremely promising outcomes of this research.

Microbial Life and Death in a Foxing Stain: a Suggested Mechanism of Photographic Prints Defacement.

The gelatin-silver halide black and white prints represent an enormous photography heritage with a great value. Unaesthetic phenomena, the foxing stains that are caused by microbial growth on surface, have been described in stamps, drawings, books, and tissues but, until now, scarcely for photographic materials. In this study, a combination of various techniques, including culture-dependent and culture-independent approaches (RNA and DNA analysis), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and µ-Raman spectroscopy supported by X-ray fluorescence analysis (XRF), permitted to describe the microbial contamination dynamics of foxing stains present on the surface of two gelatin-silver halide photographs. The investigation provided also information on the effects of microbial activity on the materials' chemistry of the two prints. The action of microbial community resulted locally in either (a) formation of mixed aluminum-iron-potassium phosphate compounds that could be attributed to the hydrolytic activity of bacteria, (b) leaching of barite,

The purple Codex Rossanensis: spectroscopic characterisation and first evidence of the use of the elderberry lake in a sixth century manuscript.

This paper presents the results obtained during the measurements campaign started in June 2012 and ended in November 2013 on the invaluable purple Codex Rossanensis, sixth century, one of the oldest surviving illuminated manuscripts of the New Testament. The tasks of the chemistry laboratory were to answer a variety of questions posed both by historians and restorers, concerning the materials used in a previous restoration, the composition of the pictorial palette and the different inks and to determine which colouring material had been applied to dye the parchment support. It was also requested to determine the state of preservation of the manuscript, as a result of its interactions with the environment in which the manuscript had been stored and the vicissitudes experienced during its life (fire, previous restoration, exhibition). The spectroscopic analyses performed by micro-Raman, micro-Fourier transform infrared and X-ray fluorescence allowed to fill a gap in the knowledge of the pictorial materials used in the Early Middle Ages. The pictorial palette, the inks, the dye applied to obtain the purple parchments, the support and the materials used in the previous restoration treatment executed in 1917-19 were fully characterised. Moreover, to the author's knowledge, the article shows the first experimental evidence of the use of the elderberry lake in a sixth century-illuminated manuscript. The lake was characterised by Raman spectroscopy.

Non-destructive spectroscopic investigation on historic Yemenite scriptorial fragments: evidence of different degradation and recipes for iron tannic inks.

Six fragments of different Yemenite manuscripts (three on parchment and three on paper) were analyzed by means of attenuated total reflectance Fourier transform infrared, micro-Raman and X-ray fluorescence spectroscopies. The combination of molecular and elemental techniques allowed the characterization of the conservation state of all the fragments, the identification of sizing agents and salts on the supports and the identification of the composition all red and black writing media. In particular, analysis of black inks provided interesting insights: independent of the substrate, all inks seemed to have identical composition, corresponding to rather well preserved high-quality iron tannic inks to which carbon black had not been added. However, in some samples, the most intense Raman peak of the ink was clearly shifted with respect to the typical bands of iron gall ink. Starting from the hypothesis that the shift could have been produced by the use of sources of tannin other than gallnuts, research was undertaken by preparing and characterizing seven different tannic inks. The experimental results confirmed the hypothesis of different tannin sources.

Biodegradation of ivory (natural apatite): possible involvement of fungal activity in biodeterioration of the Lewis Chessmen.

Fungal biodeterioration of ivory was investigated with in vitro inoculation of samples obtained from boar and walrus tusks with the fungi Aspergillus niger and Serpula himantioides, species of known geoactive abilities. A combination of light and scanning electron microscopy together with associated analytical techniques was used to characterize fungal interactions with the ivory, including changes in ivory composition, dissolution and tunnelling, and the formation of new biominerals. The research was aimed at providing further understanding of the potential roles of fungi in the colonization and deterioration of ivory in terrestrial environments, but also contributes to our knowledge regarding the possible origins of the surface damage observed on early medieval sculptures made largely from walrus tusks, referred to as 'the Lewis hoard of gaming pieces', that were presumably produced for playing chess. The experiments have shown that the possibility of damage to ivory being caused by fungi is realistic. Scanning electron microscopy revealed penetration of fungal hyphae within cracks in the walrus tusk that showed also widespread tunnelling by fungal hyphae as well as 'fungal footprints' where the surface was etched as a consequence of mycelial colonization. Similar phenomena were observed with boar tusk ivory, while production of metabolites could lead to complete dissolution of the sample. Colonization of ivory and/or exposure to fungal activity lead to extensive secondary biomineral formation, and this was identified as calcium oxalate, mainly as the monohydrate, whewellite.

The Indian drawings of the poet Cesare Pascarella: non-destructive analyses and conservation treatments.

The Italian dialect poet Cesare Pascarella travelled all around the world, noting down in notebooks his keen and caustic observations, and drawing sketches that are a visual reportage of his journeys. The sketches were mounted as a random collage over acidic cardboards that were exposed to direct sunlight in his studio. Their poor state of conservation is related to the use of modern paper: chemical instability of raw materials caused acidification and strong oxidation of the support, with intense yellowing of the surfaces and brittleness of the paper. To ensure future preservation of the drawings, chemical stabilisation with simultaneous alcoholic treatment by deacidification (calcium propionate) and reduction (borane tert-butylamine complex) appeared necessary. To verify its applicability, it was indispensible to characterise the support and identify the nature of all the graphic media. The use of Raman, Infrared, X-ray fluorescence spectroscopies and scanning electron microscopy coupled with X-ray microanalysis allowed us to clear the problems related to the different penetration depth of each analytical technique and the different responses of pigments/dyes to each spectroscopy. The palette, how it varied along the journeys, the different supports used and preparations were completely identified showing a choice of colours compatible with the reduction treatment.

Modifications of the mesoscopic structure of cellulose in paper degradation.

Paper is the main component of a huge quantity of cultural heritage. It is primarily composed of cellulose that undergoes significant degradation with the passage of time. By using small angle neutron scattering (SANS), we investigated cellulose's supramolecular structure, which allows access to degradation agents, in ancient and modern samples. For the first time, SANS data were interpreted in terms of water-filled pores, with their sizes increasing from 1.61 nm up to 1.97 nm in natural and artificially aged papers. The protective effect of gelatine sizing was also observed.

The Assisi Chartula by the hand of Saint Francis: non-destructive characterization by spectroscopic spectrometric and optical methods.

Just two examples of writings by the hand of S. Francesco are known to exist: a letter to Brother Leone, kept in the archives of Spoleto cathedral and the Chartula, displayed in the Hall of Reliquaries at Assisi's Sacro Convento. For the first time in its history the Chartula has undergone a series of non-destructive analyses, with the object of establishing its current state of conservation and the types of inks used in its making. A new display case has been designed and built for the improved conservation of this precious document. The new housing substitutes an ancient case, which was located inside the original reliquary.