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Polycaprolactone (PCL) bionanocomposites reinforced with microfibrillated cellulose (MFC), either plain or modified with 2 wt% of zinc oxide (ZnO) nanoparticles, were first time developed for possible application as multifunctional packing. The MFC was obtained by an alkali treatment, a steam explosion process, and ZnO modification applied to parchment (PAR), a husk waste from the coffee industry. X-ray diffraction (XDR), thermogravimetric analysis (TGA/DTG), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), tensile tests, and CO2 permeability characterized the MFCs and the bionanocomposites. As for the MCFs, the crystallinity index of 50.6% measured by XRD for the plain PAR fiber increases with the combined alkaline treatment and steam explosion (CFA/EXP) to 68.2%, and further with ZnO modification (ZnO-CFA/EXP) to 80.1%. TGA/DTG displays a rising onset of thermal degradation from 214 to 306 °C, as well as maximum degradation rate from 330 to 350 °C, for PAR and ZnO-CFA/EXP, respectively. Regarding the nanocomposites, the addition of 3 wt% of alkali/steam explosion and ZnO-modified CFA/EXP contributes to enhancing thermal stability. Tensile tests disclosed improved mechanical properties of the novel nanocomposites as compared to the PCL matrix. In particular, Young's modulus rose from 88.5 to 169.5 MPa for the plain PCL and PCL reinforced with 3(ZnO-CFA/EXP), respectively. SEM images evidenced the participation of cellulose micro and nanofibrils in the PCL matrix. Approximately 20% reduction in the CO2 permeability coefficient of both PCL and its 3CFA/EXP nanocomposite compared with 3(ZnO-CFA/EXP) proved that the ZnO nanoparticles provide a gas barrier to the nanocomposite, a convenient property for food packing.

This work presents the study of an XIII century French medieval Legendarium manuscript. The manuscript has a complex background of destruction and restoration attempts. Now the manuscript consists of 214 sheets encapsulated in polyethylene terephthalate conservation envelopes. The damaged manuscript sheets are in different states, some illustrations and text sections are in rather bad condition, some pages contain blurred traces of pigments and inks, which were used to write letters and make illustrations. Works carried out on this unique literary monument, included research using optical microscopy (OM), infrared reflectography (IRR), micro-Raman spectroscopy, and Scanning Electron Microscopy (SEM). The work was aimed at the estimation of the manuscript preservation and its current state. It has been demonstrated that even the study of micro-particles can be useful in the initial stages of the parchment manuscripts study that are in highly damaged condition. A wide variety of materials, which were used in different periods of time, have been found. Two types of red and four types of blue pigments were found in the studied particles from parchment. Locating the particles of iron-gall ink and pigments (for example, cinnabar and azurite) in the same region may indicate a possible use of this type of ink for both text and decoration. Pigments were revealed, the appearance of which date to a later time compared with the estimated date of Legendarium creations. These pigments include Prussian blue, pigments based on monoazo group and phthalocyanine blue. This contributes to the identification and localization of later interventions in the object under study, which were made both for the purpose of restoration and preservation.

Library material, and thus parchment, is frequently subjected to bio-deterioration processes caused by microorganisms. Fungi and bacteria cause alterations in the parchment inducing, in some cases, even the partial detachments of the surface layer and the loss of any text present on it. An important contribution to disinfection of the cultural heritage artefacts is given by the use of ionizing radiation. In this work, a preliminary study on the applicability of X-ray radiation as treatment for bio-deterioration removal is proposed. The results on the microbial growth after different irradiation treatments are shown in order to detect the dose protocol for the bio-degradation removal. Furthermore, the evaluation of the irradiation effects on the parchment microstructure is presented in order to define the applicability of the method on parchment artefacts.

© 2019 Elsevier B.V. The collagen denaturation process in several artificially aged modern parchment samples were studied by combining Adiabatic Scanning Calorimetry and Light Transmission Analysis investigations. It was found that the calorimetric evaluations enabled not only to confirm the previously reported specific heat results concerning the collagen denaturation peaks, but also to identify a novel broad feature most likely associated with additional transformations occurring once denaturation takes place. Moreover, the combination of the investigations by the two adopted techniques allowed to validate the Light Transmission Analysis as a novel simple method capable of recording the entire collagen denaturation temperature path of the analyzed samples. Finally, the polarization microscopy imaging, performed simultaneously with the optical transmission characterization, enabled to perform a direct correlation of the morphology changes of the parchment with the different stages of the collagen denaturation. ispartof: Thermochimica Acta vol:676 pages:263-270 status: published

The paper discusses the effects of a 4-year natural ageing on hydrothermal stability of new and previously accelerated aged parchments and leathers. It was observed that natural ageing generally lowers the denaturation temperature (measured using DSC), but in a different way for the two types of these collagen-based materials. Thus, for parchments the largest effect (up to 7 °C) was observed for the new samples, while for the strongly aged ones the temperature shift was negligible. For leathers, no relevant dependence of the denaturation temperature shift (3.0 ± 1.0 °C in average) with the previous accelerated ageing time was observed. For parchment, the enthalpy of denaturation decreases substantially following natural ageing, while for leathers no significant alteration was observed. It was also found that the 1-day accelerated ageing performed in 2013 had comparable effects on the denaturation temperature of these materials as the 4-year natural ageing, making the possibility of predicting the effects of natural ageing on patrimonial artifacts manufactured from parchment and leather.

A 14th Century illuminated codex underwent an extensive restoration in 1739. The intervention was necessary because the volume was “rotten”. Some purple stains are still visible and passed through multiple pages in the thickness of the volume, with a pattern that suggested a resurgence of the infection after the restoration of the manuscript. The unusual appearance of the halos and the light-pink colouring of some of the spots indicated that a topical treatment of some kind could have been carried out. The stains were analysed by non-invasive and micro-invasive methods in order to reveal the chemicals used to disinfect or bleach them and the structural effects of the treatment on the collagen fibres. The chemical compound used to treat the stains of the codex contained sulphur and potassium, it was strongly acidic and in a liquid form. Based on both the results and the knowledge of that time, we hypothesised that in 1739 the restorer was aware of “infectious” nature of the stains and tried to stop the action of microorganisms. The attempt to stop the process would be the testimony of a diffuse knowledge on biodeterioration phenomena, not yet consolidated, but already present.

In this work, we have explored the potentiality of energy dispersive X-ray fluorescence spectrometry (EDXRF), X-ray diffraction (XRD), the vibrational attenuated total reflection - Fourier transform infrared spectroscopy (ATR-FTIR), and scanning electron microscopy coupled to energy dispersive X-ray spectrometry (SEM-EDS) for the characterization of the natural degradation of old parchment. The samples used in this work comprise four Moroccan Jewish historical parchments belonging to private libraries. The results have been correlated with those obtained by a selected modern parchment. The results obtained allowed for the first time an accurate insight into the chemical composition of these parchments. EDXRF Analysis of the samples allowed us to study some of the undertaken process along the preparation of parchments, such as the liming treatment using CaCO3. XRD was used to elucidate the collagen main features, to identify the inorganic composition of the parchments, and to evaluate the crystallinity changes upon natural weathering. FTIR spectroscopy enabled us to determine the changes of collagen material in response to natural ageing, overall oxidation (detection of bands at 1716 cm−1) and collagen gelatinization. SEM-EDS results disclosed the morphological surface changes occurring at different levels in the fibrous network of collagen, and have proved a poor conservation state in some parchments.

It is well established that the ink pigment used for writing the Dead Sea Scrolls (DSS) is mainly composed of carbon soot. The ink's binder however has yet to be securely identified. By applying EVA (ethylene vinyl acetate containing strong anion and cation exchangers admixed with C8 and C18) diskettes on one fragment and analyzing the captured material, the following study was able to determine the composition of the binder. Proteins admixed of plant proteins (ribulose biphosphate carboxylase, rhamnogalacturonate lyase, α-galactosidase A, calmodulin, among those identified) as well as of a few glycoproteins with different combinations of pentosyl and hexosyl units with plant acids (stearic, palmitic, oleic, linoleic and linolenic acids) and terpenes (triacontanol, catechin, lupeol) are mixed attributes of acacia trees which suggests the use of gum Arabic as the ink's binder. SIGNIFICANCE: Whereas a huge body of reports has explored any possible aspect of the Dead Sea Scrolls, including the dating and the animal origin of the parchment, one aspect had not been investigated so far, namely which kind of ligand had been adopted to ensure a firm binding of the ink (in reality carbon soot) to the supporting parchment. In the present investigation it has been demonstrated that this "glue" is a mixture of plant proteins, as well as a few glycoproteins, together with plant acids and terpenes. These proteins and metabolites belong to two species of trees, Vachellia nilotica and Acacia Albida, widespread in this Middle East region. The EVA methodology here adopted has shown that it is possible to explore any item pertaining to the world Cultural Heritage in the absence of damage or contamination thus permititng to analyze any possible precious document stored in museum, public libraries and private collections.

The Dead Sea scrolls (DSS) are the most important archaeological find in Israel. Relatively well preserved in caves for 2000 years, additional damage has occurred since their removal in the 1950s. Among other issues, thousands of fragments were stored between glass plates, and over the years white “halos” formed around some of these fragments. Different theories about these “halos” have been proposed: the first, most obvious, option being salt migration. Since the salt content everywhere in the Dead Sea area (including aerosols) is extremely high, all of the scroll fragments would have collected large amounts of salt. Another theory, that the halos could be gelatin recrystallizing after being squeezed out of the degraded parchment, was more worrisome. If gelatin was squeezed out of the parchment, it would result directly in significant changes to the scrolls’ physical properties. At the request of the Israel Antiquities Authority's (IAA) DSS conservation staff, we analyzed the powdery material with multiple methods: FTIR-ATR, Raman microscopy, XRD, ICP, and GC/MS. In addition to salt and minerals, our analysis found fatty acids (FA), but no gelatin, disproving that particular theory. By artificially aging modern parchment the phenomenon was recreated and the parchment samples were analyzed with destructive methods (electron microprobe, GC/MS) that could not be applied to the DSS in order to learn more about the process. The FAs are an important discovery not only for understanding the degradation process, but also as a source of information on the scrolls’ production and treatment history – a source that can be analyzed even more accurately through destructive methods, without needing to touch the scrolls themselves.

Raman spectroscopy has been utilized to study ancient documents conserved at the University Library of Cagliari (Italy) with the aim to give an exhaustive scenario about the employment of inks, pigments and supporting materials (papers and parchments) related to specific historical periods (XIV–XV centuries). The samples studied are selected between the most prestigious texts present in the collection: two accounting books of sixteenth and fifteenth centuries, a mathematical text of the sixteenth century, a navigation text of the same period, a copy of the most important Sardinian medieval constitutional text “Carta De Logu”, a medieval copy of the famous Italian poem: “La Divina Commedia”. Finally we characterized a declared false of the nineteenth century reproducing a famous document of the XIII century. The present study gives fundamental knowledge on the history of different inks used in the manuscripts and also on the conservation as well degradation of supporting materials. In addition we focused our characterization on different techniques and materials applied in previous restorations. Finally, we certified with modern techniques the presence of deliberate falsification processes of some specimens.

Two medieval illuminated parchment scrolls of the Museo Diocesano of Bari (Italy), i.e., the Exultet I and the Benedictio ignis et fontis, were examined. Micro-samples of parchment were analyzed by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) for the identification of collagen and its animal origin. Thanks to the overlapping folios, representing a unique situation for illuminated manuscripts, it was possible to sample tiny amounts of paint layers. A very small fraction was first investigated by pyrolysis-gas chromatography–mass spectrometry (Py-GC–MS), laying the way for an overview of all organic components. Detailed information on polysaccharides, and proteins and lipids were then attained by performing GC–MS and MALDI-MS analysis, respectively. Accordingly, the presence of paint binders based on egg white with the addition of some egg yolk was established in the Benedictio ignis et fontis, whereas in the Exultet I collagen and a fruit tree gum were identified, the latter probably due to a surface treatment of the entire scroll. The proposed multi-technique approach using easy sample pre-treatments on very small samples may shed a light on the medieval paint recipes and on the type of animal hides used for manufacturing this kind of precious parchment scrolls.

There exists recent formal theoretical evidence that, relative to true ages, Carbon-14 (¹⁴C) ages for fossils of living organisms (man or animals) are lacking in qualitative and quantitative robustness. This study examines the extent to which highlighted recent evidence extends to ¹⁴C ages for Paper, Ink that is derived from wood, Papyri, and Parchments. The formal axiomatic (mathematically theoretical) evidence establishes, relative to true ages for paper and ink, that ¹⁴C ages for either of paper or ink are qualitatively and quantitatively robust. While ¹⁴C ages for Papyri are not quite as robust as ¹⁴C ages for Paper, formal axioms establish that, asymptotically, and relative to true ages for Papyrus plants, ¹⁴C ages for Papyri are qualitatively and quantitatively robust. While ¹⁴C ages for Parchments originating within the same spatial location are shown to be (asymptotically) qualitatively and quantitatively robust, absent adjustments for spatial differences in rates of young carbon formation, the entire universe of ¹⁴C ages for Parchments is lacking in qualitative and quantitative robustness. The preliminary empirical evidence provides unequivocal support for study predictions. In aggregate, while there exist some concerns about robustness of ¹⁴C ages for Parchments, the evidence reveals boundedness of the concerns, with outcome it safely can be asserted that inferences derived from ¹⁴C ages for Paper, Ink that comes from wood, Papyri, and Parchments can be deemed to be robust.

The data library collected investigating reconstructed red paints was successfully applied for the characterization for the first time of historical illuminated and rubricated manuscripts printed in the territory of the Grand Duchy of Lithuania. Two different red pigments (cinnabar and red lead) and three different binding media (fish glue, parchment glue, and gum Arabic) were identified in the manuscripts using SEM/EDX, FTIR, XRD and TG/DTG analysis methods. It is interesting to note, that according to the SEM/EDX results the red paints determined in the manuscripts were sufficiently pure without a large amount of impurities. The binding media in the original samples were easily identified using developed FTIR spectra of red paint with different binding media. The TG analysis showed that all TG curves of original samples were shifted toward the lower temperatures range. Finally, this work once again demonstrated the importance of using several analysis methods for the characterization of cultural heritage materials.

Green chemistry is considered a suitable approach for the sustainable preparation of nanoparticles (NPs) attributable to it is safe and clean technique. In the present work, tea tree leaves extract were used for preparing silver nanoparticles (Ag-NPs). Ecofriendly fashioned Ag-NPs was evaluated by transmission electron microscopy (TEM), X-ray diffraction pattern (XRD), ultraviolet–visible (Uv–Vis) spectroscopy, and dynamic light scattering (DLS). The obtained results confirmed the capability of tea tree leaves extract to produce spherical Ag-NPs with an average size of 40 nm at wavelength 468 nm. Furthermore, the XRD analysis affirmed the crystallographic structure of the synthesized Ag-NPs. DLS displayed that the particle size of Ag-NPs with an average diameter of about 40 nm. This study aimed to examine the influence of green synthesis Ag-NPs disinfection process on the reduction of the number of microorganisms: Aspergillus fumigatus EGY-N1, Byssochlamys spectabilis EGY-N2, Cladosporium xanthochromaticum N3-EGYand Streptomyces albidoflavus SP11 previously isolated from historical parchment manuscript. Correspondingly, the chemical, mechanical, and morphological characteristic changes of disinfected parchment arising through disinfection and after the accelerated aging process were assessed. The obtained data revealed that Ag-NPs are microbiostatic against tested microbes at a concentration of 0.005%. The microbicidal effect was achieved at a concentration of 0.025%. Moreover, the established sensitivity of microorganisms was in the following order (Streptomyces albidoflavus > Cladosporium xanthochromaticum > Byssochlamys spectabilis > Aspergillus fumigatus). Finally, chemical as well as mechanical characteristics of disinfected parchment did not significantly influence during the accelerated thermal aging at 80 °C for three weeks. Thus, Ag-NPs could be a good candidate for sustainable maintenance of historical parchment against microbial biodegradation.

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.

Laccases are enzymes belonging to the group of oxidases. Laccases catalyze the oxidation of a variety of phenolic compounds, diamines and aromatic amines. Twenty-four fungal isolates were isolated from biodeteriorated ancient paper and parchment. These isolates were identified and found to belong to six genera: Alternaria, Aspergillus, Cladosporium, Penicillium, Rhizopus and Trichoderma, and were tested for producing laccase enzyme. Trichoderma harzianum have the ability of secreted laccase enzyme. The maximum production of laccase enzyme by T. harzianum was observed at 35 ○C and pH 5 after 6 days. The highest activity of laccase achieved at 35 ○C and pH 5 during the reaction. FTIR analysis revealed that the structure of extracted fungal pigments has aromatic ring and phenols group. Crude laccase was capable to decolorize different pigment structures. The enzyme showed great decolorization efficiency toward the extracted yellow pigment produced from Asp. terrus and Asp. ochareceous treated by 200 μl of partially purified enzyme. Laccase enzyme was used to decolorization pigment secreted from deteriorated pigmented fungi on paper and parchment during 30 days by using a pieces of paper and parchment inoculated by spore suspension. The results indicated that a high removal effect of fungal pigment on paper (71.21%) was recorded comparing to parchment samples (32.39%).

The Dead Sea Scrolls are often described as the most important archaeological find of the 20th century. These 2000 years old manuscripts have great religious, historical and linguistic importance. The fact that large parts of these texts are obscured by the darkening of the parchment is extremely unfortunate. In our previous research we explored the possible causes of parchment browning or darkening using artificial aging, which allowed both destructive and non-destructive testing. Our results could be summarized as two main theories, one related to parchment fibers flattening and changing the way light is reflected, the second related to the formation of strong brown pigments, likely from the melanoidin family. Here we examine the scrolls themselves and discuss their degradation in light of these theories. The main DSS collection could only be surveyed by completely non-destructive means, namely multispectral imaging and Diffuse Reflected Infrared Fourier Transform (DRIFT); however, a few fragments were examined by micro-destructive means including SEM and FTIR-ATR and EPR. Despite the great variation between scrolls, we demonstrate that the browning of the scrolls and their degradation fits within the framework of those theories developed on artificially aged samples. We suggest the extreme degradation occurred when parchment was exposed to water and particularly if that water was slow to evaporate, for example saturated salt water which is slow to evaporate, and was very likely present in the caves where the scrolls were found by the Dead Sea. Hydrolysis and denaturation freed the necessary components to meet and initiate the formation of large melanoidins.

In this paper we aimed at the characterization of heat-induced changes on molecular organization of collagen within parchment in very low relative humidity conditions. Collagenous materials are intrinsically heat-sensitive and hygroscopic. Parchment documents and artefacts are heterogenous materials made from a matrix of collagen fibres whose surface is often interfaced with gelatine layers. Thus, as they age and deteriorate, parchments become even less thermally stable and more hygroscopic. Getting insight into the subtler structural alterations of collagen is critical to establishing appropriate temperature and relative humidity conditions for the preservation of parchment artefacts. To this purpose, we monitored the molecular changes induced by exposing parchment prepared according to traditional recipes to increasing temperature (e.g. 50 °C, 80 °C, 100 °C, 120 °C, 150 °C, 180 °C and 200 °C) and low relative humidity (10%) by vibrational spectroscopy (Infrared spectroscopy in ATR acquisition mode and Raman spectroscopy) whereas the macroscopic changes in collagen fibers stability were evaluated through Micro Hot Table (MHT) method. Colorimetric measurements were also performed and related to parchment deterioration processes. Artificial ageing confirmed the pattern of collagen thermally induced deterioration consisting of triple helix conversion into intermediate conformations (neither native, nor properly heat-denaturated) followed by denaturation at 120 °C and progressive gelatinisation at T ≥ 150 °C. The shrinkage behaviour of collagen fibers was detailed at molecular level by FTIR-ATR and Raman analyses through the multiple changes that occur in the position and intensities of the amide I, amide II and amide III components. Besides, significant changes were detected in the ν(C C) region associated with proline and hydroxyproline residues and protein backbone in the Raman spectra. Moreover, a set of spectral biomarkers was unequivocally assigned to collagen gelatinization. The results of this study can therefore serve as important tools towards a better understanding of ancient parchment condition.

This study aimed to evaluate for the first time the antimicrobial activity of lemongrass oil in its normal (Lg-EO) and nanoform (Lg-NE) against four microbial strains previously isolated from a historical parchment manuscript dated back to the third century AH (9th century AD). In addition, examine their impact on the aesthetic, physical, and chemical characteristics of the disinfected parchment before and after artificial aging. The nanoemulsion of the oil was prepared using the low energy emulsification technique. The antimicrobial activity of Lg-EO and Lg-NE was assessed qualitatively and quantitatively. Fourier transform infrared, scanning electron microscopy (SEM), tensile strength and elongation, and color change investigations were conducted to monitor any chemical, morphological, mechanical, or physical variations of treated parchment samples before and after artificial aging. The obtained results declared that preparing essential oils in the form of nanoemulsions improves their antimicrobial performance that facilitates achieving biocidal activity in lower concentrations without adversely affecting any of the examined characteristics of the disinfected parchment. On the other hand, using the oil in its normal state affected the optical properties of treated samples before and after aging. Additionally, while improving the mechanical properties of the disinfected parchment, the accelerated aging of the treated samples had brought about an obvious decrease in those properties. Thus, essential oils nanoemulsions which are considered an ecofriendly system can be used effectively in the disinfection of historical parchment manuscripts without any adverse effect on their distinctive characteristics.

The margins of several pages of the Aleppo codex have been found to be corroded and contaminated by diffuse maculae. In order to understand the origin of this decay these margins have been analysed by applying EVA (ethylene vinyl acetate plastic embedded with strong cation and anion exchangers and mixed with C8 and C18 hydrophobic resins) diskettes for harvesting surface material. The captured compounds have been eluted, digested with trypsin and analysed by nano-HPLC-MS. Three major strains of Aspergillus have been identified, namely Aspergillus fumigatus, Aspergillus pseudoglaucus, Aspergillus amstelodami, together with a lactobacillus strain and human keratins. The novelty of this investigation is that for the first time the EVA technology has been applied to ancient parchments in the absence of mechanical deformation or distortion that could be induced if there had been water exchange between the EVA diskettes and the parchment. These findings should help curators to find suitable restoration protocols for these precious documents belonging to the world Cultural Heritage.

The Dead Sea Scrolls, a two-thousand-year-old parchment corpus of manuscripts, thought to be the most important discovery of the 20th century including the first known copies of the Hebrew Bible, have darkened in parts to the point that the text is illegible. This motivated our research to try to understand the browning of parchment mechanisms. The scrolls cannot be analyzed by any destructive methods, so alternatives had to be sought. Here we describe a series of artificial aging experiments using modern parchment, prepared especially for our project, according to traditional methods, demonstrating how the different types of browning observed on the scrolls relate to environmental conditions as well as post finding treatments. Even the most extreme browning could be caused by prolonged exposure to water. This was in complete variance from controlled relative humidity exposure, where even elevated temperatures over a full five months caused only mild browning. We also confirm browning occurs at room temperature and within short periods when parchment is wet. We noted greater darkening of the flesh side in short term experiments, while browning was similar on both sides in conditions where water or humidity levels were maintained over a longer period. Artificial aging also confirmed the damage to the lower ends of many scrolls was likely caused by capillary actions when parchment was standing in water. That experiment also showed a dark tide-line phenomenon at the wet-dry interface, similar to that observed in paper substrates. Using analytical methods including FTIR, SEM, Light microscopy, UV–Vis and Fluorimetry we found the browning was always associated with denaturation, or loss of structure, mostly due to water and heat. This results in a flattening of the parchment structure which could be altering how light is reflected. However, in one artificial aging experiment the color was clearly seen to migrate and disperse over the parchment, after its initial formation. We believe this means the color is due to dark pigments; therefore, the main mechanism we suggest is melanoidin pigment formation due to a Maillard type reaction between amino acids and sugars or oxidized lipids, which are perhaps freed to react due to denaturation and hydrolysis. The results collected here can serve as an important step towards a full mechanistic understanding of parchment browning.

Surprising discoveries can happen while analyzing library materials. This paper presents four case studies focusing on four artifacts of different ages and provenances, all analyzed and studied at the Istituto Centrale per il Restauro e la Conservazione del Patrimonio Archivistico e Librario (Icrcpal). The common denominator amongst the case studies presented in this work, lies in the need for a strong interconnection between the analysis of biological issues and chemical data. The interplay between the two complementary approaches is paramount for the correct interpretation of the status of the material under examination as, as will be shown in the following case studies, chemical data could find an interpretation only in the face of biological observations and vice versa. The first case we here present, deals with two parchment codices that have been found in 2008 during a fishing expedition in the Canale di Sicilia. At that time a deep-sea fishing boat belonging to the fleet of Mazara del Vallo caught in its nets, two artifacts, leading to the first discovery of library materials in the deep sea. The Scanning Electron Microscopy and Energy Dispersive Spectroscopy (SEM/EDS) analyses allowed for the creation of a compositional map of the surface of the samples, where several microscopic encrusting sea organisms and biogenic materials were also observed. Almost nothing of the original structure of the parchment (of which the object is presumably made) could be recognized at SEM. The absence of the typical collagen features was confirmed by Raman analyses that could only collect spectra of an isoprenic-type polymer of putative biogenic origin. The second case deals with fragments of medieval manuscripts that were found in 2007 buried in the walls of the Great Mosque of Sana'a in Yemen. An outstanding discovery regarded the dark brown inks used on a Qur'ānic fragment attributed to the 10th century. SEM micrographs disclosed the presence of red blood cells mixed to ink components. The inks were also investigated with Raman spectroscopy. The third case study is the book “Libretto di appunti e memorie del Padre Francesco Zazzera”, dated 17th century that presented a peculiar modification of the black ink that appeared to be faded and turned to a white-yellowish color. Raman and SEM analyses recognized and documented a biogenic formation of jarosite on top of the ink. It was possible to remove the jarosite layer and to recover the original black ink, thus allowing an easier reading of the text. The fourth and last case analyzed and presented in this paper consists of the measurements on the invaluable Codex Purpureus Rossanensis dated 6th century. Raman spectroscopy here allowed the demonstration of the use of an elderberry lake to obtain a mauve color. This is the first experimental evidence of the use of that particular dye in such an ancient illuminated manuscript. A sort of archeological discovery was also done on this codex with respect to the past misfortunes that occurred to it; by simply observing some traces we were able to support some intriguing hypothesis on its history and vicissitudes.

This radiocarbon study aims to physically verify the critical analysis of the Torah scrolls from the National Museum of Brazil collection. Although the manuscript was formerly believed to be as old as the 10th century, the paleographic and stylistic study of the books of Genesis and Deuteronomy revealed features that could be associated to the year 1560 AD. Radiocarbon analysis was performed and a phase model limited by a Historical boundary was applied. The results are in agreement with the critical analysis of the manuscript that it is not older than the 16th century.

The aging mechanism of leather and parchment was studied by thermoanalytical methods to understand the effect of the environment on the historical manuscripts and the heritage of libraries and archives. Alkaline and acidic treatments followed by thermal dehydration were applied to achieve chemical changes in the structure of new leather and parchment similar to the slow natural aging of historical samples. Chemical and structural changes during both natural and artificial aging processes were characterized by thermoanalytical techniques. The thermal stability and the evolution profile of the decomposition products under slow heating were studied by thermogravimetry/mass spectrometry (TG/MS). The distribution of the decomposition products of these collagen-based materials under fast pyrolysis was characterized by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). It was found that the maximal rate of the thermal decomposition (DTGmax) significantly decreases by aging in case of both leather and parchment samples indicating the degree of deterioration. Py-GC/MS has been found to be a suitable technique to sensitively monitor the degradation of the polyphenolic components of the vegetable tannins under natural or artificial aging. It was established that the tannin content of leather is more significantly affected by natural aging and alkaline treatment than the main structure of the polypeptide chains. Principal component analysis (PCA) has been used to find statistical correlations between the experimental data for leather samples. The results of the PCA confirmed that the alkaline treatment and the natural aging processes similarly modify the tannin content of the vegetable tanned leather.

Parchment is the support of several documents kept in libraries and archives all around the world. Much of this cultural heritage is rapidly degrading due to different causes, in particular fungi, with the risk of being lost. In recent decades new methods have been tried to improve the conservation, protection and usability of library and archive materials. In this work we showed a cleaning method of old documents in parchment bio-deteriorated by fungi. This method is easy, not expensive, and respectful of the document characteristics. In particular, it was evaluated the effectiveness of gellan gum and titanium dioxide nanoparticles hydrogels in cleaning and disinfecting parchment samples contaminated by Penicillium chrysogenum and Cladosporium cladosporioides, which are two fungi notorious for their attacks to parchment cultural heritage. Results showed that the mechanical soft action of gellan gum hydrogels combined with the photo-catalytic activity of titanium dioxide nanoparticles allow an important cleaning and disinfection of parchment with a consequent preservation from further fungal colonization of samples over long time when compared to untreated ones.

Characterization of eleven copper alloy artifacts, dated between the 4th and 6th (or early 7th) centuries AD, retrieved from archeological excavations of remains associated with Samaritan sites along the central Coastal Plain of Israel, was performed. The assemblage includes three inscribed polygonal finger rings, four finger rings with decorated bezel (of which one bears a legend in the Samaritan script), two inscribed amulet pendants, and two thin cylindrical foils (containers of phylacteries, designated for the safekeeping of a magical or religious text written on papyri or parchment). The aim of this research is to use archeometallurgical non-destructive and destructive methods in order to determine manufacturing processes of the objects, and if possible their production place, their origin of ore and their use. The results indicate that the three polygonal rings were prestige objects made of gunmetal and manufactured by lost-wax casting followed by heat-treatment probably at the same workshop. Among the four finger rings with decorated bezel, the two with incised motifs were made of gunmetal alloy, while the one with eye-shaped bezel was made of relatively pure leaded-copper, and the other ring, with the inscribed bezel, was made of brass. These rings were manufactured by using dissimilar techniques; the two with decorated bezel by casting and then shaped by hammering and annealing cycles; the eye-shaped bezel ring by casting with no further treatment; and the inscribed bezel ring made of brass by manufacturing two different parts, hoop and bezel, that were brazed together, and then hammered and annealed. Both amulet pendants were manufactured by lost-wax casting and given their shape and composition they were probably manufactured at two different workshops. Both cylindrical foils were made of leaded-copper that was first cast into an open mold, then hammered into a thin foil and folded at a later stage, probably at the same workshop. All the examined gunmetal and brass artifacts contained 4–20 wt.% Zn, indicating that their alloys were originally manufactured by cementation, produced of recycled metal, probably due to economic considerations. The present study indicates the existence of a limited number of local metal workshops which specialized in the manufacture of copper alloy jewelries and related objects; some were apparently operated by Samaritans.

In the present work, the use of portable instrumentation allowing in-situ reflection FTIR analyses is exploited to identify the coloring matters of northern-Italian illuminations dating to the XVI century. In order to build a database of spectra, reference paint samples were prepared spreading the pigments on parchment with two different binders, i.e. gum arabic and egg white, used in antiquity. Pigments for the database were chosen considering their use in the Middle Ages and in the Renaissance and their response in the mid- and near-IR region. The reflection FTIR spectra obtained resulted to be dominated by the specular reflection component, allowing the use of the Kramers–Kronig transform to convert them to the more conventional absorbance FTIR spectra. Several pigments could thus be identified in ancient illuminations, even if some green details showed a spectral pattern different with respect to the most common commercial green pigments of the database. Therefore, in addition, basic copper sulfates brochantite and posnjakite were synthesized and characterized. In three green details, posnjakite was identified, both as a pure compound and together with malachite.

Neutron radiography was utilized to quantify water absorption and desorption in parchment at the High Flux Isotope Reactor CG-1D imaging facility at Oak Ridge National Laboratory (ORNL). Sequential 60s radiographs of sections of a 15 th century parchment were taken as the parchment underwent wetting and drying cycles. This provided time-resolved visualization and quantification of water absorption and transport in parchment.

A flexible, parchment paper/PDMS based platform for local wound oxygenation is fabricated and characterized. The platform consists of a PDMS microfluidic network bonded to a parchment paper substrate. Generation of oxygen occurs by flowing H2O2 through the channels and chemically decomposing it via a catalyst embedded in laser-defined regions of the parchment paper. PDMS is bonded to parchment paper using partially cured PDMS followed by a brief air plasma treatment, resulting in a strong bond. For pressures below 110 Torr the parchment paper is observed to be impermeable to water and hydrogen peroxide. The oxygen permeability of parchment paper is measured to be 1.42 μL/(Torr mm2 min). Using a peroxide flow rate of 250 μL/min, oxygen generation in the catalyst spots raises the oxygen level on the opposite side of the parchment paper from atmospheric levels (21%) to 25.6%, with a long-term (30 h) generation rate of 0.1 μL O2/min/mm2. This rate is comparable to clinically proven levels for adequate healing. Device and material in vitro biocompatibility is confirmed with NIH 3T3 fibroblast cells via alamar blue assays.

Moist heat (100 °C in closed vessels) and pollutants (SO2 or NOx, 100 °C) techniques of accelerated ageing were applied in stability investigation of iron gall inks on parchment. The measured characteristics on parchment samples coated with inks (made of iron(II) sulfate and gallic acid or tannic acid in various ratios) reflected their chemical, optical and spectroscopic attributes. Decrease of surface pH values was measured for all samples, especially after ageing with SO2. The results obtained, comparing the non-aged samples with those aged upon heat and pollutants, revealed the decrease of lightness L* and the increase of chromatic coordinate b* for all six ink layers. These differences in b* were dominantly reflected in values of total color difference ( Δ E a b * , CIE L*a*b*). The variations in UV/VIS reflectance spectra and Δ E a b * evidenced the considerable damage of inks exposed to accelerated ageing, especially for inks prepared with excess of acid to iron. FTIR spectroscopic measurements of parchment showed that accelerated ageing procedures caused changes in structure and arrangement of collagen, and the formation of oxidation products in parchment during the accelerated ageing was stimulated by presence of inks. EPR spectra of parchment coated with inks showed the paramagnetic signals of various Fe(III) species ions in different coordination.

The aim and the novelty of this work was the use of both dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC), in water and in dry state, for the investigation of the effects of temperature and relative humidity on degradation of recently manufactured parchments and vegetable-tanned leathers. The materials were subjected to accelerated ageing under action of heat and moisture for progressively increasing time lengths. The studies have proved that accelerated ageing causes a progressive decrease of the temperature of denaturation in water excess, but has no or minor effect on that in dry state. Also, under same ageing conditions parchments undergo a greater degree of deterioration than leathers, as evidenced by a more dramatic change in the DSC peaks (in water) and in the shrinkage curves (DMA). The results can be interpreted as a partial gelatinization occurring in the thermal conditions used for accelerated ageing. The paper presents the advantage of using both techniques, namely that DSC results can assist in interpretation of the DMA curves and that the good correlation of denaturation temperatures obtained by DSC and DMA ascertain these values. Such studies can be useful for understanding the processes that take place on natural ageing of historical parchments and leathers, as well as for establishing proper conditions of their storage.

A system of complementary X-ray diffraction (XRD) and fluorescence (XRF) was used for non-invasive in situ identification of inorganic materials in a highly valuable illuminated parchment, now preserved at the Archive of the Royal Chancellery in Granada (Spain), via which King Enrique IV (1425–1474) conferred nobility on Gil Fernandez and Alonso Covo. The study of organic matter, by capillary electrophoresis (CE), could not be performed without taking microsamples that had also been used to confirm – by micro-Raman spectroscopy and scanning electron microscopy (SEM–EDX) – the nature of inorganic materials that had been identified by XRD–XRF. Gold and silver were detected as well as lead tin oxide in yellow, azurite in blue, vermilion and minium in reddish colours and malachite in green. Calcite was applied to the entire sheets and gypsum to the text area. Iron-based ink was used for the parchment text. These analyses enable the document to be put into its historical context; they serve as a starting point in a comparative study with other similar documents, for the reconstruction of its documentary archaeology.

In the illuminated foral charters commissioned by D. Manuel I, King of Portugal (1495–1521), heraldry played a prominent role. In this work, royal emblems corresponding to the third heraldic design, applied to the Charter of Couto de Teixedo, are studied by means of EDXRF, SEM–EDS, micro-Raman, micro-FTIR and HPLC–DAD to characterize the materials and techniques used to produce this masterpiece of Portuguese Renaissance. By comparing this data with the results previously obtained in other three charters, this research allows for the first time an accurate insight into the reformed manuscripts production, especially since the illuminated charters under consideration were all investigated on the basis of similar micro-spectroscopic techniques. Inks, metal coatings, pigments, organic dyes, fillers or extenders, and binding media are discussed, and their use enlightened by the politic and legal messages the foral charters had to convey. Parchment analysis allowed us to identify the animal species, and all undertaken processes along its preparation. HPLC–DAD allowed us to differentiate the gums used. CaSO4 was observed in the parchment as a degradation product of CaCO3 used in parchment production in the presence of metal sulfates coming from the ink. Pigments used in the different colors as well as some specific phases for some colors were identified. Silvering and gilding processes, metal caratage and silver oxidation compounds were also objects of the present study.

Parchment documents are part of our cultural heritage and, as historical artifacts that they are, should be preserved. The aim of this study was to validate an appropriate methodology to characterize the bioburden of parchment documents, and to assess the growth and gamma radiation inactivation patterns of the microbiota present in that material. Another goal was to estimate the minimum gamma radiation dose ( D min ) to be applied for the decontamination of parchment as an alternative treatment to the current toxic chemical and non-chemical decontamination methods. Two bioburden assessment methodologies were evaluated: the Swab Method (SM) and the Destructive Method (DM). The recovery efficiency of each method was estimated by artificial contamination, using a Cladosporium cladosporioides spore suspension. The parchment samples' microbiota was typified using morphological methods and the fungal isolates were identified by ITS-DNA sequencing. The inactivation pattern was assessed using the DM after exposure to different gamma radiation doses, and using C. cladosporioides as reference. Based on the applied methodology, parchment samples presented bioburden values lower than 5×10 3 CFU/cm 2 for total microbiota, and lower than 10 CFU/cm 2 for fungal propagules. The results suggest no evident inactivation trend for the natural parchment microbiota, especially regarding the fungal community. A minimum gamma radiation dose ( D min ) of 5 kGy is proposed for the decontamination treatment of parchment. Determining the minimal decontamination dose in parchment is essential for a correct application of gamma radiation as an alternative decontamination treatment for this type of documents avoiding the toxicity and the degradation promoted by the traditional chemical and non-chemical treatments.

International audience; This paper aims at contributing to identify the eventual regions where fungus Aspergillus ochraceus could grow and produce ochratoxin A (OTA) during drying of coffee beans. Internal structure of coffee bean was analyzed by optical microscopy for endosperm and parchment. From the expression of the dissipation in the grain due to the water transport, we show that a relationship formally analogous to an equation of diffusion governs the water transport. Three structures with mass transfer resistance potential are studied: parchment, silver skin and endosperm. An experimental technique to study the water transfer into the parchment was proposed. In the endosperm, for moisture contents above 65%, a constant transport coefficient controls the drying kinetics of the whole bean. Below this moisture content, water transport coefficient (with and without silver skin) were significantly lesser than those for the whole bean. This is firstly due to the reduction of the pore space occupied by water and second to the increasing bonding energy between solid structure and water as moisture content decreases. The contribution of parchment to the protection of the endosperm is highlighted.

Parchments are important documents that give testimony for History; therefore these materials should be respected and preserved. Considering incremental biodeterioration problems that have to be faced daily, the Archive of the University of Coimbra (AUC) is involved in different scientific projects in order to evaluate and determine new methods for document decontamination and preservation. The aim of this study was to evaluate gamma radiation effects on the colour and texture of the AUC parchment documents. The assessment of these effects was used to estimate the maximum gamma radiation dose ( D max ) that could guarantee parchment documents′ decontamination treatment, without significant alteration of their physical properties. Parchment samples were exposed to gamma radiation doses ranging from 10 to 30 kGy. The texture and colour of samples were assessed before and after the irradiation procedure, using a texture analyser and an electronic colorimeter. Hardness and springiness were determined based on texture spectra. Lightness (L⁎), Chroma (C), greenness vs. redness (a*) and yellowness vs. blueness (b*) values were obtained from colorimetric measures. Results indicate no significant effects of gamma radiation on the texture and colour of parchment for the studied doses.

Two Byzantine VI century manuscripts known as Vienna Dioskurides and Vienna Genesis, held in the Austrian National Library at Vienna, were analysed with in situ non-invasive techniques. Raman spectroscopy, UV-Vis diffuse reflectance spectrophotometry with optic fibres and X-ray fluorescence spectrometry were used to characterise the palette of these early Middle Ages manuscripts. The analytical study was performed to have a better knowledge on the colourants used by ancient miniature painters, a subject known more on the basis of traditional sources (i.e. medieval treatises) than of analytical evidences. Indeed these illuminated manuscripts are, to the authors' knowledge, among the oldest ever being analysed, so that the colourants found in them can be considered among the oldest evidences of their use. The main feature of Vienna Dioskurides and Vienna Genesis palettes is their richness, exemplified by the simultaneous presence of gold and ultramarine blue; in Vienna Dioskurides cinnabar is also present. Information regarding ultramarine blue is surprising, being the analytical evidence of the use of this precious pigment at least three centuries before its use in Western manuscripts, a feature justified by the fact that the Byzantine Empire was the dominant culture in early Middle Ages in the Mediterranean World. Other colourants include azurite and indigo, red lead, orpiment, red and yellow ochres, while a mixture of blue and yellow colourants, known as vergaut, was used to render green hues. Organic colourants were also used, such as madder and Tyrian purple, the latter employed to dye the parchment of Vienna Genesis.

This paper reports the first systematic study of the dimensions of morphological changed microscopic collagen fibres in historical and new reference parchments with the aim to improve the knowledge on deterioration and the diagnosis of their damage in connection with conservation activities. The dimensions of fibres from the parchments were measured before and during shrinkage, with special emphasis on fibres with degradation characteristics designated as “pearls on a string” and “butterflies”. In addition, measurements of the total shrinkage of the length of fibres and pieces of parchment were also carried out. The observations support the assumption that in vivo transformation of the fibre structure by natural ageing is similar to that taking place when heating parchment and fibres in water. Based on statistical cluster analysis, four subpopulations of pearls representing different stages of deterioration are found. Moreover, the dimensional changes in the specific structures observed at room temperature can be related to specific temperatures in the interval of shrinkage suggesting that the hydrothermal stability of the fibres may be predicted on the basis of the ratio between length and width of the so-called pearls (P l /P w ). The total shrinkage measured is drastic, in average around 56% for fibres and 43 to 48% for pieces of parchment depending on the direction of the skin. The total shrinkage of fibres corresponds to a mean change in the ratio P l /P w from around 10 to around 2.3. Finally, relations between the measured dimensions at the microscopic level with those of collagen at nanoscopic and molecular levels including known and potential chemical splitting points strongly indicate that the formation of the butterfly-like fragments formed by cleavage of two adjacent pearls in the fibre can be ascribed to chemical modification of specific tripeptides in the collagen molecule.

This paper describes moisture diffusivity, shrinkage, equilibrium moisture content and finite element simulated drying of coffee. The moisture diffusivities in different components of parchment coffee were determined by minimizing the sum of square of deviations between the predicted and the experimental values of moisture contents during thin layer drying under controlled conditions of drying air temperature and relative humidity. The drying of coffee bean and parchment was conducted in thin layers at a temperature of 40, 50 and 60 °C with relative humidity in the range of 14–25%. The mean diffusivity values of coffee bean and parchment are related to the temperatures and are expressed by Arrhenius-type equations. The moisture diffusivities of parchment are lower than those of the coffee bean. The shrinkage of coffee bean derived from experiments is expressed as a function of moisture reduction. GAB model is sufficient for the prediction for sorption isotherm of parchment coffee and the parameters of the GAB model are a function of temperature and it is expressed by Arrhenius-type equations. Sensory evaluation of the coffee dried at 40, 50 and 60 °C shows that the overall acceptance by coffee cupping test and the concentration of caffeine is within the acceptable limit. A two-dimensional finite element model was developed for simulate moisture diffusion during drying process of parchment coffee. The finite element model was programmed in Compaq Visual FORTRAN version 6.5. The model simulates the moisture contents in different components of parchment coffee well and it provides a better understanding of the transport processes in the different components of the parchment coffee.

Micro DSC measurements were used to investigate the synergistic effects of temperature and relative humidity on deterioration of parchment. Samples were obtained by exposing new parchments to various temperature and relative humidity atmospheres for increasing times in controlled test chambers. The impact of this accelerated ageing was assessed by measuring the thermodynamic parameters associated with the thermal denaturation of fibrillar collagen: variation of denaturation temperature, Tmax, indicated changes in collagen thermal stability, increases of DSC peak half-width, ΔT1/2, revealed greater thermal heterogeneity and structural disorder, whereas parallel decrease of denaturation enthalpy, ΔH, and DSC peak maximum height, Cpex max, measured the loss of fibrillar structure. Deconvolution of DSC denaturation peaks provided a valuable illustration of both the dynamics and the pattern of the deterioration of fibrillar collagen. Impact of temperature and relative humidity on parchment integrity and stability is discussed in terms of their implications for conservation science.

Membranaceous substrates – widely found in library heritage – are truly challenging, due to the variety of manufacturing traditions, the intrinsic variability of the animal's skin and the different degradation patterns affecting documents along ageing. Moreover, when dealing with unique and delicate objects as cultural heritage specimens, sampling is never recommended and often explicitly forbidden. Aim of the research presented in this work is to achieve correct protocols for unambiguous characterization of the document's materials chemical structure and of the possible surface treatments. Experimental results allow us to evidence that the chosen non-destructive techniques (Raman, ATR-FTIR and SEM/EDS) provide a good differentiation between parchment manufacturing procedures, western with lime and eastern with enzymatic treatment. Incrustations of salts on the surface as well as superficial treatment with tannin can be clearly detected. Origin of tannin – from the surface or in ink – can also be distinguished. Choice of the better technique is sample-dependent, since preparation methods, degradation, presence of incrustations, amount of tannin, dehairing method can differently affect the spectral features. For instance, Raman appears to be the most effective molecular technique on western parchment, whereas ATR-FTIR allows distinguishing the enzymatic dehairing procedure from the chemical one.

This study deals with establishing of a PCR-based strategy with the aim to recognize the animal origin of different historical parchments. This is one of relatively rare studies on the analysis of ancient DNA from parchments. Robustness of the PCR technology is demonstrated by successful identification of the animal species using only a small amount of DNA isolated from 12 parchment samples. Ten PCR-based assays specific for the detection of different animal species (Bos taurus, Ovis aries, Capra hircus, Sus scrofa, Oryctolagus domestica, Cervus elaphus, Capreolus capreolus, Dama dama) and two PCR assays utilizing universal primers were evaluated and optimized with the aim to find a rapid parchment identification method, which would be more reliable than the classical microscopic examination. The optimized PCR methods produced satisfactory results. Out of 12 investigated parchments, 9 items were unambiguously identified, DNA from 2 samples could not be amplified with any of the species-specific PCR assays, and only one parchment produced controversial results. The species-specific PCR results were confirmed by direct sequencing and PCR cloning with consequent sequencing. Our approach, including isolation of parchment DNA by chaotropic solid-phase extraction, optimization of the PCR programs and high-stringency annealing temperatures, demonstrated to be effective, easy and reliable for the analysis of historical parchment DNA. We consider this PCR-based strategy potentially useful also for investigation of other types of animal items conserved in museums, galleries or libraries.

Parchments comprise one of the most common and valuable sources of archaeological and historical data. Previous studies have shown that parchment also preserves genetic data. These data could be valuable for population studies, to understand past animal husbandry, the development of breeds and varieties and to comment on the provenance of parchments. To improve our understanding of DNA contained in parchments, we analysed genetic data, including both mitochondrial and autosomal loci, from 18th to 19th century English parchments which stable isotope analysis had indicated were well-preserved. DNA results were unexpected. All but one of the parchments produced multiple sequences matching several different species. Ion beam analysis ruled out surface treatments of the parchments (including ink and animal glues) as the origin of these multiple sequences. Our results suggest that the DNA content of parchment is more complex than previous research has suggested and that multiple stages of parchment manufacture, treatment and storage are preserved in parchment DNA extracts.

Fungi play a considerable role for the deterioration of cultural heritage. Due to their enormous enzymatic activity and their ability to grow at low aw values fungi are able to inhabit and to decay paintings, textiles, paper, parchment, leather, oil, casein, glue and other materials used for historical art objects. The weathering of stone monuments is significantly increased by epi- and endolitic fungi. In museums and their storage rooms, climate control, regular cleaning and microbiological monitoring are essential in order to prevent fungal contamination. Education and close collaboration of mycologists and restorers are needed to develop object specific methods for the conservation and treatment of contaminated objects.

Historic parchment is a macromolecular material, which is complex due to its natural origin, inhomogeneity of the skin structure, unknown environmental history and potential localised degradation. Most research into its stability has so far focussed on thermal and structural methods of analyses. Using gas chromatographic analysis of the atmosphere surrounding parchment during oxidation, we provide the experimental evidence on the production of volatile aldehydes, which can be the products of lipid autoxidation. Oxidation of parchment with different aldehyde emissions was additionally followed in situ using chemiluminometry and the same techniques were used to evaluate the oxidation of differently delipidised parchment. It was shown that the production of peroxides and the emission of aldehydes from the material decrease with lower lipid content. Building on this evidence, we can conclude that the presence of lipids (either initially present in the skin or resulting from conservation intervention) leads to oxidative degradation of collagen and that the non-destructive analysis of the emission of volatiles could be used as a quick tool for evaluation of parchment stability.

The thermal degradation of collagen-based materials, viz. collagen, recently manufactured parchments and tanned leathers, a heritage parchment and patrimonial (historical) leathers, was investigated by thermal analysis methods. With progressive heating, all these materials exhibit three main successive processes, associated with dehydration, protein denaturation and pyrolysis/oxidation. The analysis of both denaturation and thermo-oxidation revealed significant differences between aged leather, collagen, recently manufactured parchments and tanned leathers in terms of the number of overlapping processes (reflected in the number of peaks recorded at denaturation) and of the oxidative degradation rates, given by the normalised curves of differential thermal gravimetry (DTG). The various observations are proposed as qualitative indices for assessing the age and storage conditions of leather. A three-phase model was used for explaining the results. This consists of crystalline collagen filaments that are embedded in an amorphous matrix with an interface zone between the crystalline and amorphous regions. Solid-state 1 H NMR investigations corroborate the thermal analysis results and enhance the understanding of the ageing processes.

The objective of this work was to evaluate and compare the alterations in the structure of coffee seed endosperm subjected to different temperatures and drying conditions. The seeds were dried at 40, 50 and 60, with an airflow of 0.33 m3 s−1 m−2. After drying, 10 seeds were randomly selected and prepared for the histochemical tests with Sudan IV and scanning and transmission electron microscopy, according to the laboratory's routine techniques. The histochemical results showed that, for the coffee parchment beans dried at 40 °C, there was no change in the cellular integrity of the plasma membrane and vesicles. In contrast, in the endosperm of parchment coffee beans dried at 60 °C, fused oil bodies that gave rise to large droplets in the intercellular space were observed, indicating a rupture of the vesicles and plasma membrane. Scanning electron microscopy showed that, for the parchment Arabica coffee beans dried at 40 °C, the internal cellular content remained intact and full of cellular material and the space between the plasma membrane and the cell wall was empty. However, in seeds dried at 60 °C, a rupture of the cells was observed, represented by occluded intercellular spaces, indicating a leaking of part of the protoplasm. The results from the transmission electron microscopy corroborated the undamaged and the damaged structure of the coffee parchment beans dried at 40 and 60 °C, respectively.

This variorum of the Constitution of the United States contains readings from four early versions of the text:–Text P is the famous parchment signed by the delegates to the Philadelphia Convention.–Text F is the September 18 print struck off by John Dunlap and David C. Claypoole at the Philadelphia Convention's behest.–Text C is the September 28 print forwarded by the Confederation Congress to the states.–Text CS is the form of the text Francis Childs and John Swaine, official "Printers to the United States," included in their 1789 session-laws volume, Acts Passed at a Congress of the United States of America, Begun and Held at the City of New‐York, on Wednesday the Fourth of March, in the Year 1789.For a discussion of the variants and their significance, see my essay "How Different Are the Early Versions of the United States Constitution? An Examination" (forthcoming).

The pictorial materials used in the decoration of the front page of a Renaissance Portuguese Charter, 1512, were studied. The front page is an illuminated manuscript incorporating a decorative border, and begins with a gilded initial; it presents iron gall calligraphy and also a red decorated initial A. The colours, applied on parchment, are orange, red, green, blue, gold and a reddish brown. They were applied with a common binding medium, a vegetal gum. With the exception of the brownish red, all the colorants were of inorganic origin, synthetic or mineral: vermilion, red lead, azurite and malachite. In the synthetic colours, fillers such as calcium carbonate and lead white were added. The reddish brown used in the background of the main initial is an organic dye. Gold was used in the main initial as well as in some details in the decorative border. The gold was applied on a substrate of gypsum and lead white in a proteinaceous medium. The materials were characterized by non-destructive techniques, in situ (microEDXRF, UV-VIS emission fluorescence, colorimetry), or, when needed, by micro-sampling (microFTIR), and the results were compared to what is described in medieval treatises on the Art of illumination, as De Arte Illuminandi and The book on how one makes colours.