“Multiple Microanalyses of a Sample from the Vinland Map" by Sommer et al (2017)

Sommer, D. V. P.; Mühlen Axelsson, K.; Collins, M. J.; Fiddyment, S.; Bredal-Jørgensen, J.; Simonsen, K. P.; Lauridsen, C. B.; Larsen, R., “Multiple Microanalyses of a Sample from the Vinland Map", Archaeometry 59(2) (2017) 287–301.
Doi:10.1111/arcm.12249 (Wiley Online Library, restricted access)

Abstract: 

A sample of the Vinland Map remaining from the radiocarbon dating was analysed with the purpose of identifying the post-1950 contaminant and establishing other evidence on the material composition, identity and condition. The analyses revealed that the parchment originates from a bovid and contains hair remnants. The fibre structure was in poor condition, with fragmented collagen fibres and a low hydrothermal stability. Greenish and reddish particles were observed on the parchment. The greenish particles were identified as basic copper(II) chloride, most probably atacamite, and the reddish particles as rust; that is, various iron(III) oxides. The extracted modern contaminant was identified as being naturally produced glycerol monostearate.

“Correlative nonlinear optical microscopy and infrared nanoscopy reveals collagen degradation in altered parchments” by Latour et al (2016)

Latour, Gaël; Robinet, Laurianne; Dazzi, Alexandre; Portier, François; Deniset-Besseau, Ariane; Schanne-Klein, Marie-Claire, “Correlative nonlinear optical microscopy and infrared nanoscopy reveals collagen degradation in altered parchments”, Scientific Reports 6 (2016) 26344.

DOI:10.1038/srep26344 (Nature.com, open access)

Abstract:

This paper presents the correlative imaging of collagen denaturation by nonlinear optical microscopy (NLO) and nanoscale infrared (IR) spectroscopy to obtain morphological and chemical information at different length scales. Such multiscale correlated measurements are applied to the investigation of ancient parchments, which are mainly composed of dermal fibrillar collagen. The main issue is to characterize gelatinization, the ultimate and irreversible alteration corresponding to collagen denaturation to gelatin, which may also occur in biological tissues. Key information about collagen and gelatin signatures is obtained in parchments and assessed by characterizing the denaturation of pure collagen reference samples. A new absorbing band is observed near the amide I band in the IR spectra, correlated to the onset of fluorescence signals in NLO images. Meanwhile, a strong decrease is observed in Second Harmonic signals, which are a structural probe of the fibrillar organization of the collagen at the micrometer scale. NLO microscopy therefore appears as a powerful tool to reveal collagen degradation in a non-invasive way. It should provide a relevant method to assess or monitor the condition of collagen-based materials in museum and archival collections and opens avenues for a broad range of applications regarding this widespread biological material.

"Variation in the sorption properties of historic parchment evaluated by dynamic water vapour sorption" by Popescu et al (2016)

Popescu, Carmen-Mihaela; Callum A. S. Hill; Kennedy, Craig; "Variation in the sorption properties of historic parchment evaluated by dynamic water vapour sorption", Journal of Cultural Heritage 17 (2016) pp.87–94.

Doi:10.1016/j.culher.2015.06.001 (ScienceDirect, restricted access)

Abstract:

Understanding the hydration of the collagen historic parchments is of great importance to the conservation and restoration processes. In this study, modern and historic (dated 1817 and 1769) parchments were investigated using dynamic water vapour adsorption/desorption (sorption) experiments. The relationship between the equilibrium moisture content against the relative humidity at constant temperature for two consecutive sorption cycles, the hysteresis and kinetic properties were analysed for different parchments from a historic archive. It was found that historical parchment samples exhibited higher equilibrium moisture content levels throughout most of the hygroscopic range and the hysteresis was greater than that of the contemporary sample. The samples were all found to obey parallel exponential kinetics for both adsorption and desorption. By applying the parallel exponential kinetic model, it was observed that the difference in the hysteresis is apparently mostly due to changes in the collagen matrix relaxation processes.

"Degradation of collagen in parchment under the influence of heat-induced oxidation" by Mühlen Axelsson et al (2016)

Mühlen Axelsson, K.; Larsen, R.; Sommer, D. V. P.; Melin, R.; “Degradation of collagen in parchment under the influence of heat-induced oxidation: Preliminary study of changes at macroscopic, microscopic, and molecular levels”, Studies in Conservation 61(1) (2016) pp. 46–57.

DOI: 10.1179/2047058414Y.0000000140 (Taylor & Francis Online, restricted access)

Abstract:

This paper examines the impact of heat-induced oxidation for new and historical parchment with the purpose of improving diagnostic tools for use in practical parchment conservation. Oxidation was generated by heat aging at 120°C in a dry oven for 24, 48, and 96 hours, respectively. The degradation was assessed on all samples at macrolevel by measuring color changes, at microlevel by measuring the shrinkage temperature as well as by performing a visual assessment of the fibers’ morphology and determining the amount of damaged fibers, and finally, at molecular level where amino acid analysis was used to reveal changes in the oxidized collagen. The study shows that the heat-induced oxidation leads to significant color changes, decrease in hydrothermal stability, as well as changes in the amino acid composition. Surprisingly, the results show that the historical parchment is more sensitive towards dry heat oxidation on a molecular level than is the new parchment. Furthermore, for the first time, we can show that physical damage reflected in the morphological characteristics of fibers can be attributed to oxidation by dry heat.

“Detection of COL III in parchment by amino acid analysis” by Sommer and Larsen (2016)

Sommer, Dorte V. P.; Larsen, René; “Detection of COL III in parchment by amino acid analysis”, Amino Acids 48 (1) (2016) pp. 169–181.

DOI:10.1007/s00726-015-2074-2 (SpringerLink,restricted access)

Abstract:

Cultural heritage parchments made from the reticular dermis of animals have been subject to studies of deterioration and conservation by amino acid analysis. The reticular dermis contains a varying mixture of collagen I and III (COL I and III). When dealing with the results of the amino acid analyses, till now the COL III content has not been taken into account. Based on the available amino acid sequences, we present a method for determining the amount of COL III in the reticular dermis of new and historical parchments calculated from the ratio of Ile/Val. We find COL III contents between 7 and 32 % in new parchments and between 0.2 and 40 % in the historical parchments. This is consistent with results in the literature. The varying content of COL III has a significant influence on the uncertainty of the amino acid analysis. Although we have not found a simple correlation between the COL III content and the degree of deterioration, our results show that this question must be taken into consideration in future studies of the chemical and physical deterioration of parchment measured by amino acid analysis and other analytical methods.

“Proteins in Art, Archaeology, and Paleontology: from detection to identification” by Dallongeville et al (2016)

Dallongeville, Sophie; Garnier, Nicolas; Rolando, Christian; Tokarski, Caroline, “Proteins in Art, Archaeology, and Paleontology: from detection to identification”, Chemical Reviews 116(1) (2016) pp. 2–79.

DOI:10.1021/acs.chemrev.5b00037 (ACS Publications, restricted access)

“Quantifying degradation of collagen in ancient manuscripts: the case of the Dead Sea Temple Scroll” by Schütz et al (2013)

Schütz, R.; Bertinetti, L.; Rabin, I.; Fratzl, P.; Masic, A., “Quantifying degradation of collagen in ancient manuscripts: the case of the Dead Sea Temple Scroll”, Analyst 138(19) (2013) pp. 5594–5599.

DOI:10.1039/C3AN00609C (Royal Society of Chemistry, open access)

Abstract:

Since their discovery in the late 1940s, the Dead Sea Scrolls, some 900 ancient Jewish texts, have never stopped attracting the attention of scholars and the broad public alike, because they were created towards the end of the Second Temple period and the “time of Christ”. Most of the work on them has been dedicated to the information contained in the scrolls' text, leaving physical aspects of the writing materials unexamined. They are, however, crucial for both historical insight and preservation of the scrolls. Although scientific analysis requires handling, it is essential to establish the state of degradation of these valued documents. Polarized Raman Spectroscopy (PRS) is a powerful tool for obtaining information on both the composition and the level of disorder of molecular units. In this study, we developed a non-invasive and non-destructive methodology that allows a quantification of the disorder (that can be related to the degradation) of protein molecular units in collagen fibers. Not restricted to collagen, this method can be applied also to other protein-based fibrous materials such as ancient silk, wool or hair. We used PRS to quantify the degradation of the collagen fibers in a number of fragments of the Temple Scroll (11Q19a). We found that collagen fibers degrade heterogeneously, with the ones on the surface more degraded than those in the core.

"Parchment production in the first millennium BC at Seglamen, Northern Ethiopia" by Phillipson (2013)

Phillipson, Laurel; "Parchment production in the first millennium BC at Seglamen, Northern Ethiopia", African Archaeological Review 30(3) (2013) 285–303.
doi:10.1007/s10437-013-9139-y (SpringerLink, restricted access)

Abstract:

Traditional Ethiopian and European processes of parchment manufacture and their associated tools are described and compared with artefacts recovered from an important pre-Aksumite site at Seglamen, in the highlands of northern Ethiopia. Many close similarities of tools used at Seglamen in both the earlier and later phases of the pre-Aksumite, from about 800 BC, to implements used by present-day Ethiopian scribes attest to the systematic production of parchment at Seglamen and to cultural continuity over a period of almost three millennia.

“Thermal characterization of new, artificially aged and historical leather and parchment” by Sebestyén et al (2015)

Sebestyén, Zoltán; Czégény, Zsuzsanna; Badea, Elena; Carsote, Cristina; Şendrea, Claudiu; Barta-Rajnai, Eszter; Bozi, János; Miu, Lucretia; Jakab, Emma; “Thermal characterization of new, artificially aged and historical leather and parchment”, Journal of Analytical and Applied Pyrolysis 115 (2015) pp.419–427.
DOI:10.1016/j.jaap.2015.08.022 (ScienceDirect, restricted access)

Abstract:

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.

“Paging through history: parchment as a reservoir of ancient DNA for next generation sequencing” by Teasdale et al (2015)

Teasdale, M. D.; van Doorn, N. L.; Fiddyment, S.; Webb, C. C.; O’Connor, T.; Hofreiter, M.; Collins, M. J.; Bradley, D. G., “Paging through history: parchment as a reservoir of ancient DNA for next generation sequencing”, Philosophical Transactions of the Royal Society of London B: Biological Science 370(1660) (2015), p.20130379.

DOI:10.1098/rstb.2013.0379 (The Royal Society Publishing)

Abstract:

Parchment represents an invaluable cultural reservoir. Retrieving an additional layer of information from these abundant, dated livestock-skins via the use of ancient DNA (aDNA) sequencing has been mooted by a number of researchers. However, prior PCR-based work has indicated that this may be challenged by cross-individual and cross-species contamination, perhaps from the bulk parchment preparation process. Here we apply next generation sequencing to two parchments of seventeenth and eighteenth century northern English provenance. Following alignment to the published sheep, goat, cow and human genomes, it is clear that the only genome displaying substantial unique homology is sheep and this species identification is confirmed by collagen peptide mass spectrometry. Only 4% of sequence reads align preferentially to a different species indicating low contamination across species. Moreover, mitochondrial DNA sequences suggest an upper bound of contamination at 5%. Over 45% of reads aligned to the sheep genome, and even this limited sequencing exercise yield 9 and 7% of each sampled sheep genome post filtering, allowing the mapping of genetic affinity to modern British sheep breeds. We conclude that parchment represents an excellent substrate for genomic analyses of historical livestock.

Alterations within the structural hierarchy of parchment induced by damage mechanisms by Thomas (2009)

Katherine Thomas, Alterations within the structural hierarchy of parchment induced by damage mechanisms, PhD Thesis on Optometry and Vision Sciences, Cardiff University, 2009.
URL / PDF (ORCA)

Abstract:

Collagen plays an important role in many biological tissues, including skin, which, once dried and treated, forms parchment and leather. The structural alterations that occur in collagenous materials due to X-ray radiation damage, fluctuation of relative humidity, and mechanical deformation (with a special focus on historical parchment) are the focus of this thesis. The primary aim of this thesis is to investigate major structural changes to collagen within parchment when exposed to inappropriate levels of relative humidity during conservation treatments, and cyclic-humidity during long-term storage in archives, museums and libraries. This study led to the discovery that each parchment sample reacted to the application and removal of moisture in a different way, indicating the fundamental need to treat individual parchment documents as in-homogeneous materials. This thesis investigates the changes that fibrillar collagen undergoes and describes the creation of computational models capable of reproducing the X-ray diffraction patterns for collagen. Previous structural models have been created that sufficiently account for native collagen, however, models created as part of this thesis succeed where previous models have failed in explaining the X-ray diffraction patterns collected from damaged collagen. This study provided the opportunity to contribute towards a large-scale international collaborative project on the hugely important historical resource, the Domesday Book. X-ray diffraction was used to provide unprecedented analysis of Domesday Book samples, providing a structural survey at a molecular level. This analysis produced the conclusion that the majority of samples displayed the presence of collagen axial structure, and were generally of a degraded state as a consequence of the method used to source them the samples were scrapings from the surface, which was less intact than the bulk of the parchment.

"Unmasking the measles-like parchment discoloration: molecular and microanalytical approach” by Piñar et al (2015)

Piñar, Guadalupe; Sterflinger, Katja; Pinzari, Flavia, “Unmasking the measles-like parchment discoloration: molecular and microanalytical approach”, Environmental Microbiology 17(2) (2015) 427–443.

DOI:10.1111/1462-2920.12471 / PDF

Abstract:

Many ancient parchments are defaced by red or purple maculae associated with localized destruction of collagen fibres. Although the main characteristics of this damage were present in most of the manuscripts analysed by many authors, no common microbial or fungal denominator has been found so far, and little or no correspondence between the microbial or fungal species isolated from materials could be addressed. In this study, culture-independent molecular methods and scanning electron microscopy (SEM) were used to identify fungal and bacterial communities on parchments affected by the purple stains. Protocols for c extraction and nucleic-acid-based strategies were selected for assays examining the community structure of fungi and bacteria on biodeteriorated parchment. Both SEM and molecular analysis detected the presence of bacterial and fungal cells in the damaged areas. Halophilic, halotolerant proteolytic bacterial species were selected by the saline environment provided by the parchment samples. As common microbial denominators, members of the Actinobacteria, mainly Saccharopolyspora spp. and species of Aspergillus, were detected in all investigated cases. It is proposed that a relationship exists between the phenomenon of purple spots on ancient parchments and that of the ‘red heat’ phenomenon, known to be present in some products manufactured with marine salt.

"Expandable polyester hinges for parchment mounting..." by Duqueyroix et al (2015)

Duqueyroix, Nadège; Robinet, Laurianne; Barbe, Coralie, “Expandable polyester hinges for parchment mounting performance in fluctuating environmental conditions”, Journal of Paper Conservation 16(1) (2015) 18–28.

DOI:10.1179/1868086015Z.0000000002 (Maney Online)

Abstract:

The high hygroscopicity and heterogeneity of parchment make it particularly sensitive to fluctuating environmental conditions. Due to this, the final housing of an artwork on parchment, including mounting, should aim to mitigate the impact of the fluctuations on the object. The conservation of two navigation maps painted on parchment from the Musée national de la Marine, Paris raised the question of finding an appropriate mounting method. Flexible mounting techniques that adapt to the movement of parchment have been developed by conservators in the past, but their behaviour and efficiency in a fluctuating environment have not been observed or tested. This study focuses on the expandable polyester hinges method developed at the Victoria and Albert Museum and evaluates the safety and performance of this mounting technique in fluctuating environmental conditions. We explore an alternative way of manufacturing reproducible hinges using laser cutting.

The elongation capacity and breaking point of the hinge are assessed. Mounted and unmounted parchment samples are exposed to different levels of relative humidity (RH) (from 9 to 75%), and their dimensions and distortions are recorded and compared. Mounting with expandable polyester hinges maintains the parchment in a reasonably flat condition and prevents the appearance of distortions. At 9% RH, it even seems to restrain the dimensional variations of the parchment. We observe that the more hinges are used for mounting, the more flat the parchment remains. We successfully apply this mounting technique to the two navigation maps. The study demonstrates that the expandable polyester hinge method is safe and efficient in mitigating the impact of humidity fluctuations on parchment.

Leather and parchment communications at CRCC50 International Conference, Paris (2013)

"Cultural heritage conservation science and sustainable development: experience, research, innovation", International conference in the frame of the 50th anniversary of the Centre de Recherche sur la Conservation des Collections - CRCC50, held at Paris, 23-25 October 2013

Oral communications on leather and parchment:
- Claire Chahine
"Le cuir: enjeux pour la conservation et l'environnement"
Video presentation (URL)

- Elena Badea
"Identification of environmentally sensitive archival parchment for lower energy storage"
Video presentation (URL)

COLLAGE Project website

COLLAGE

Intelligent system for the analysis and diagnosis of collagen based artefacts

Website

COLLAGE is a Romanian Joint Applied Research Project (Project No. 224/2012) carried out in the PN-II-PT-PCCA Programme and funded by the Executive Unit for Financing Higher Education, Research, Development and Innovation (UEFISCDI). The project is aiming at developing and modify existing techniques for the analysis of collagen-based historical materials and objects to achieve both high accuracy and micro- or non-invasivity characteristics requested in the evaluation of cultural heritage.

CHEMCH 2014, Vienna (Austria), online posters on parchment and leather

The 3^rd International Congress on Chemistry for Cultural Heritage, CHEMCH 2014, that took place last July in Austria, was hosted by the Institute of Science and Technology in Art of the Academy of Fine Arts of Vienna (book of abstracts is available here).

Some of the posters presentations on leather and parchment are available online at the Congress website. The titles, the authors and the posters pdf files are as follows:

P14
"EXAMINATION OF HISTORIC PARCHMENT MANUSCRIPTS BY NON-INVASIVE REFLECTION-FTIR – POSSIBILITIES LIMITATIONS"
W. Vetter, G. Pöllnitz, M. Schreiner
PDF

P19

"DETERIORATION OF VEGETABLE-TANNED LEATHER INVESTIGATED BY UNILATERAL NMR: EFFECTS OF HYDROLYSIS AND THERMAL TREATMENTS"

C. Sendrea, E. Badea, H. Iovu
PDF

P21
"ARTIFICIALLY AGED PARCHMENT INVESTIGATED BY FTIR"
I. Petroviciu, C. Carsote, W. Vetter, L. Miu, M. Schreiner
PDF

Why Leather? The Material and Cultural Dimensions of Leather by AA.VV. (2014)

Veldmeijer, A. J.; Harris, S. (eds.), Why Leather? The Material and Cultural Dimensions of Leather, Proceedings of the Archaeological Leather Group conference held in 2011, Leiden, Sidestone Press (2014).

URL

"Identification of collagen-based materials in cultural heritage" by Kirby et al (2013)

Kirby, D. P.; Buckley, M.; Promise, E.; Trauger, S. A.; Holdcraft, T. R.; “Identification of collagen-based materials in cultural heritage”, Analyst 138(17) (2013) 4849–4858.

DOI:10.1039/C3AN00925D (restricted access)

Abstract:

All stakeholders in cultural heritage share an interest in fabrication methods and material technology. Until now methods for analysis of organic materials, particularly proteins, have not been widely available to researchers at cultural institutions. This paper will describe an analytical method for the identification of collagen-based materials from soft tissue sources and show examples of its application to diverse museum objects. The method, peptide mass fingerprinting (PMF), uses enzymatic digestion of extracted proteins to produce a mixture of peptides. The mass spectrum of the mixture contains characteristic marker ions—a peptide mass fingerprint—which are compared to species-specific markers from references as the basis of identification. Preliminary results indicate that analysis of materials from aged samples, several different tissue types, and tanned or untanned materials yields comparable PMF results. Significantly, PMF is simple, rapid, sensitive and specific, has been implemented in a museum laboratory, and is being practiced successfully by non-specialists.

"The secrets in skin: species identification of treated skins through proteomic analysis" by van Doorn & Fiddyment (2014)

Nienke van Doorn & Sarah Fiddyment, "The secrets in skin: species identification of treated skins through proteomic analysis", 117th SLTC Conference 2014, 26th April 2014, University of Northampton, Northampton.

URL (Video and PowerPoint presentation)

Bibliographies sur conservation du parchemin: médiathèque numérique de l’Institut National du Patrimoine, France

- Altération des parchemins (2012)
PDF

- Technique de montage de conservation des parchemins (2009)
PDF