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20 páginas.- 10 figuras.- 2 tablas.- 59 referencias.- Supplementary Information The online version contains supplementary material available at https://doi.org/10.1007/s10570-022-04573-y, Papyrus, produced from the white pith of Cyperus papyrus L., has been used for millennia as the major writing support by ancient cultures, but there was no continuous papyrus production until modern times. Therefore, papyrus production had to be rediscovered. Modern Egyptian papyrus producers claim that their sheets possess 'the same physical and chemical properties as ancient papyri'. To study if this is accurate, commercially available papyrus sheets were compared to ancient papyri and papyri produced according to Pliny's historic description. Material characterization was performed with a focus on the potentially color-bearing lignin. Two-dimensional nuclear magnetic resonance spectroscopy, derivatization followed by reductive cleavage, and pyrolysis-gas chromatography/mass spectrometry were complemented with microscopy and tests for surface pH and sodium content. The lignin data in the native pith and commercial sheets were compared to 10 ancient samples from the Papyrus Museum Vienna. The analytical data clearly show the involvement of a strong alkaline treatment followed by chlorine bleaching for commercial papyri, as expressed by higher pH values, altered lignin structures, and chlorinated lignin compounds. The inclusion of an alkaline step in ancient papyrus manufacture is discussed but dismissed, since the alkali-treatment causes a huge decrease in lignin content, that was not found for the analysed ancient specimen. We assume that this additional treatment was introduced to obtain yellowish papyrus sheets meeting optical expectations of modern spectators. Linguistic and art historic evidence indicates that such a step would not have made sense in antiquity, since it was desired to produce white papyri., Open access funding provided by University of Natural Resources and Life Sciences Vienna (BOKU). The authors acknowledge the financial support from the Austrian Biorefinery Centre Tulln (ABCT), the County of Lower Austria, the Spanish State Research Agency, the European Regional Development Fund (project AGL2017-83036-R) and the Junta de Andalucia (project P20-00017).

We report a non-invasive and multi-analytical physico-chemical method for the characterization of paper artworks, able to identify sizing, inks, and glues and to quantify oxidative degradation by-products. The proposed methodology is mostly carried out in situ by using easy-to-use and cheap portable instrumentation for the acquisition of multispectral images, punctual ultraviolet-visible-near infrared fiber-optics reflectance spectroscopy (FORS) and punctual fiber optics fluorescence spectroscopy. Further analytical information is provided by non-invasive in-situ sampling of paper surface by using soft latex sponges, making possible laboratory chromatographic and infrared spectroscopic analyses on the aqueous sponge extracts. The proposed diagnostics method was applied to two 17th century letters written by St Francis of Sales (1567-1622), collected at the Chigi Palace in the town of Ariccia (Italy). Results show an intense oxidative degradation of the letters, also localized in water spots, and the presence of carboxylic acids by-products. Analysis of FORS spectra provided the concentration of chromophores in the paper substrate. The diagnostic method allowed the identification of gelatin sizing, the presence of starch glue in specific areas of the letters and the type of ink used in the text. Our diagnostic approach aims to offer to conservator-restorer a characterization of a paper artwork, that can be applied to other, for a correct planning of conservation interventions.

An innovative method to quantitatively assess the state of degradation of paper in a non-destructive way has been developed by using THz time-domain spectroscopy (THz-TDS). The method relies on the observation that the hydrolytic and oxidative degradation of cellulose in paper is accompanied with rearrangement of the hydrogen bonds (H-bond) network of cellulose polymers. This gives clear fingerprints in the THz spectral profiles. THz-TDS is a suitable approach to study low-energy vibrational properties of biological materials in a non-destructive way. The THz photon energy range (about 1-40 meV) is particularly suitable to probe the H-bonds between molecules. However, the quantitative assessment of the state of preservation of artworks poses significant challenges, in particular when measurements on low refractive index and thin samples, such as ancient documents and drawings, must be carried out [1]. In the present study, we have successfully solved this problem obtaining a precise determination of the absorption by cellulose fibers in the 0.2-3.5 THz (7-117cm-1) range in single freely standing paper sheets. This has been achieved by developing a new procedure to remove from the experimental signals the spurious interference effects generated by the Fabry-Pérot resonances in the sheet. By using this approach, the THz absorption coefficient of cellulose fibers in ancient and modern samples artificially aged has been obtained. The THz absorption spectra are explained in terms of absorption peaks of the cellulose crystalline phase superimposed to a background contribution due to a disordered H-bonds network [2]. The complex evolution of the spectra as a function of natural and artificial aging is explained with a reduction up to 30% of the H-bond density in the cellulose polymer networks and a parallel increasing of the sample crystallinity evident in the peaks at about 2.1 and 3.1 THz. The comparison with density functional theory ab-initio calculations suggests that the observed THz spectral changes could be related not only to the recrystallization of amorphous regions, but also to the progressive degradation of the external surfaces of crystalline domains. These results demonstrate a significant potential in the non-destructive analysis of the structural modifications of cellulose and paper artifacts by aging, resulting, at a macroscopic scale, in a progressive weakening of the mechanical properties of paper [3]. [1] T. Trafela, M. Mizuno, K. Fukunaga, and M. Strlic, Appl. Phys. A, 111, 2013, 83-90. [2] E. Scarpellini, M. Ortolani, A. Nucara, L. Baldassarre, M. Missori, R. Fastampa, and R. Caminiti, J. Phys. Chem. C 120, 2016, 24088-24097. [3] L. Teodonio, M. Missori, D. Pawcenisc, J. ?ojewskac, F. Valle, Micron 91, 2016, 75-81.

During the centuries paper has been the most widely used writing support and therefore paper degradation is a major issue for cultural heritage conservation. The main component of paper is cellulose, one of the most abundant biomaterials on Earth. Cellulose oxidation is mainly responsible for the yellowing of the ancient samples, through the formation of optically active oxidized functional groups (chromophores). This results in severe chromatic deterioration of works of art on paper. In order to investigate the issue we applied several spectroscopic techniques (UV/Vis-IR-THz) interpreted by ab-initio theoretical computational simulations based on Density Functional theory (DFT) and Time-Dependent DFT (TDDFT) methods [1-4]. In this talk, we illustrate the experimental and theoretical methods and show their application to ancient work of art on paper. In particular, we show how to transform UV/Vis reflectance spectra of ancient samples into absorption spectra of cellulose fibers by using an improved version of the Kubelka-Munk theory suitable for strongly absorbing media. The procedure based on experimental and theoretical UV/Vis spectroscopy is particularly promising since it uses non-invasive and non-destructive measurements, which can be performed in-situ, allowing diagnostic analysis of delicate paper artifacts and the monitoring of their restoration interventions. We also present results on the state of degradation of the Leonardo Da Vinci's drawings including the famous self-portrait as well as other famous works of art on paper. [1] A Mosca Conte, O Pulci, MC Misiti, J ?ojewska, L Teodonio, C Violante and M Missori "Visual degradation in Leonardo da Vinci's iconic self-portrait: A nanoscale study" Appl. Phys. Lett.104, 224101-4 (2014). [2] M Peccianti, R Fastampa, AM Conte, O Pulci, C Violante, J ?ojewska, M Clerici, R Morandotti, M Missori "Terahertz absorption by cellulose: Application to ancient paper artifacts" Physical Review Applied 7 (6), 064019 (2017). [3] L Micheli, C Mazzuca, M Missori, L Teodonio, A Mosca Conte, O Pulci, L Arcadipane, S Dominijanni, A Palleschi, G Palleschi, S Iannuccelli, S Sotgiu, "Interdisciplinary approach to develop a disposable real time monitoring tool for the cleaning of graphic artworks. Application on "le Nozze di Psiche", Microchemical Journal 138, 369-378 (2018). [4] M Missori, D Pawcenis, J Bagniuk, A Mosca Conte, C Violante, MS Maggio, M Peccianti, O Pulci, J Lojewska, "Quantitative diagnostics of ancient paper using THz time-domain spectroscopy", Microchemical Journal 142, 54-61 (2018).

In the past, the animal glues were used in paper manufacturing and in restoration of artworks preserved in museums, libraries and archives. By ageing they went through deterioration creating distortions, tensions, cockling and discolouration in paper materials. Consequently, the removal of glue residues becomes an essential step in the restoration of ancient and artwork paper material. Current mechanical and chemical methods display serious drawbacks mainly related to aggressiveness towards material or toxicity for restorers. Bio-based methods for paper cleaning rely on the use of enzymes that require skilled operators, optimal application conditions and high costs, creating difficulties in mastering enzyme use so far. This paper describes a first attempt of biocleaning ancient paper from organic deposits using living bacteria. The non-pathogenic, non-spore-forming and non-cellulolytic original strain Ochrobactrum sp. TNS15 E was successfully applied -immobilised in an agar gel-on original paper specimens dating back to the 17th. After 4 h of contact with the bacterial pack, the cellulose fibres underlying glue were disclosed, highlighting the bacterial capacity of removing the glue layer without damaging the paper or leaving undesirable residues. Both colorimetry and SEM analyses proved the results. The procedure is simple, low-cost and safe for the artefact, the restorers and the environment.

This paper aims to identify causes and processes of an undesired age-related optical phenomenon in which two kinds of paper – a white paper and a green one – and an iron-gall ink are involved together with unavoidable environmental agents. Documents under examination are dated 1893 and come from the Trieste cadastral system archive (Ufficio del catasto tavolare di Trieste). The green paper, with a high content of lignin and kaolin is a pre-printed payment order used in accounting operations and it is adjacent to a white lignin-free paper. Diffused brown stains appear on the white paper mainly from being in prolonged contact with the green one which was handwritten using iron-gall ink. The green page induces a strong browning effect on the contact side of the white one, except for inked areas. The manuscript black lines of the lignin-containing page seem to protect the adjacent surface, where a mirror image appears. A particular type of mirror effect, which we propose to call negative mirror effect, is clearly evidenced. Micro-XRF (micro-X-ray fluorescence spectroscopy) and FT-IR ATR (attenuated total reflectance Fourier transform infrared spectroscopy) techniques were used to achieve information on both diagnostic inorganic and organic components. By way of our chemical model we can hypothesise the migration of oxidised brown low molecular weight extra-cellulose compounds (from lignin and/or hemicelluloses) from green recto to white verso pages. The browning process is only hindered in sharp correspondence with the areas of the green recto folio written with the iron-gall ink: this ink acts as a physical barrier to the migration or, as a second hypothesis, it is able to withhold the mobile organic compounds by way of a specific but still unknown interaction. In the field of scientific research on metal-gall ink corrosion this is a novel, interesting and surprising case of the reverse, in which the ink itself is not the cause of the corrosion, but the unforeseen preventive agent.

The degradation process of cellulose-made materials was investigated by means of nuclear magnetic resonance (NMR) spectroscopy, with particular emphasis on the role of water and on the hydration mechanism of cellulose fibrils. To accomplish this, the structure and dynamics of water within ancient and modern samples with different aging histories were investigated. The results mainly indicated that hydrolytic and oxidative reactions provoked the formation of acidic by-products. Furthermore, degradation processes were enhanced by higher amounts of water because of the progressive consumption of the amorphous regions of the cellulose. We propose NMR experiments as a benchmark for characterization of the degradation state of paper, as well as for investigating the effectiveness of restoration treatments.

The action of water within biological systems is strictly linked either with their physical chemical properties and with their functions. Cellulose is one of the most studied biopolymers due to its biological importance and its wide use in manufactured products. Among them, paper is mainly constituted by an almost equimolar ratio of cellulose and water. Therefore the study of the behavior of water within pristine and aged paper samples can help to shed light on the degradation mechanisms that irremediably act over time and spoil paper. In this work we present Nuclear Magnetic Resonance (NMR) experiments on modern paper samples made of pure cellulose not aged and artificially aged as well as on ancient paper samples made in 1413 in Perpignan (France). The line shape parameters of the proton NMR spectra were studied as a function of the hydration content. Results indicate that water in aged samples is progressively involved in the hydration of the byproducts of cellulose degradation. This enhances the degradation process itself through the progressive consumption of the cellulose amorphous regions.

The surface composition of 18th century papers was investigated by means of ToF-SIMS and XPS. The aim of the present study was to explore the possibility of using these surface sensitive methods to obtain information which can help to determine the manufacturing process, provenance and state of conservation of ancient papers. The ToF-SIMS results indicate that the analyzed papers were sized by gelatin and that alum was added as hardening agent. The paper sheets produced in near geographical areas but in different paper mills exhibit a similar surface composition and morphology of the fibers as shown by the ToF-SIMS measurements. The ToF-SIMS and the XPS results indicate that a significant fraction of the cellulose fibers is not covered by the gelatin layer. This was observed for the ancient papers and for a modern handmade paper manufactured according to the old recipes.

Ancient paper yellowing, inducing major esthetic damage, is mainly due to cellulose oxidation. The complexity of cellulose is an obstacle to the interpretation of optical spectra for the characterization and quantification of chemical damage induced by ageing in ancient paper. Here we report optical absorption measurements of paper samples obtained in a temperature range from 14 to 300 K. Their interpretation by abinitio theoretical computational simulations revealed a dominant role of static disorder on oxidized cellulose optical response, compared to temperature effect. Our findings are of crucial importance to understand ancient paper degradation processes and to conceive new diagnostic methods.

The role of gelatine sizing in ancient paper discoloration is still subject to debate. In this report we have addressed this issue by comparing the optical reflectance of sized and non-sized artificially aged modern papers with reflectance data obtained from a set of ancient specimens. We have used different ageing procedures and prepared the gelatine following methods set down in ancient recipes. Gelatinesized aged papers showed an optical response comparable with that of ancient paper specimens, while very small reflectance modifications were observed in pure cellulose unsized samples under the same ageing conditions. In addition, measurements carried out on pure gelatine films confirmed that gelatine plays a major role in paper discoloration. Some differences in discoloration effects induced by arti- ficial and natural ageing on sized paper are discussed and a possible explanation is proposed.

Our purpose is to study the effect of degradation processes on the optical response of ancient paper specimens. The paper samples under study originate from several European countries, date back to the XV and XVI centuries and show different states of degradation. Paper optical response is checked by reflectance spectroscopy in the wavelength range of 250–1100 nm. Similar spectral forms are shown by paper specimens displaying a broad range of widespread discoloration, of different manufacture, geographical origins and ages. A similar form is also observed by measuring foxing spots of several intensities on a single foxed sheet. Moreover, the entire spectra set shows a clear connection between the paper’s state of degradation and a monotonic transformation of the spectral curves, suggesting the existence of uniform degradation effects implied in the optical response of both foxed as well widespread discoloured papers. These results suggest for usage of optical reflectance as a general and non-destructive method for degradation calibration.