Iron Age Fur Skin Tanning – a Sustainable Practice?
DOI:
https://doi.org/10.7146/dja.v13i1.141323Keywords:
Bog Find, Fur Skin, Vegetable Tannins, ATR-FTIR, GC-MS, Fibre Morphological AnalysesAbstract
Tanning is among the most polluting industries in the world. Industrial-produced hides and skins are fully or pre-tanned with highly polluting chromium salts. The purpose of the study was to gain new knowledge about Iron Age tanning methods to clarify whether sustainable tanning methods can be developed based on this. Fur skin capes, uncovered in Jutland bogs, from Baunsø Mose (20-220 AD), Borremose I (365-116 BC), Huldremose I (1-174 AD) and Vindum Mose (386-203 BC) were analysed by Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy (ATR-FTIR), Gas Chromatography-Mass Spectrometry (GC-MS) and morphological assessment of the skin fibres to identify tanning substances and material condition. Analyses were supplemented with source studies of previous visual assessment of the capes and measured shrinkage temperature of leather and skins excavated from bogs. Our results show that only the samples from Baunsø Mose, Borremose I and Huldremose I contain vegetable tannins. Furthermore, Baunsø Mose contains cow fat and Borremose I, Huldremose I and Vindum sheep fat. All contain indications of the presence of aluminum and iron compounds. The samples are decomposed to varying extents. Remnants from conservation were detected on Huldremose I, Baunsø Mose and Vindum Mose.
References
Aabye, J.S., 1955. Garverbogen. København: Teknologisk Instituts Forlag.
Asingh, P. and Lynnerup, N., eds. 2007. Grauballe Man – An Iron Age Bog Body Revisited. Jutland Archaeological Society Publications vol. 49. Højbjerg: Aarhus University Press.
Badea, E., Miu, L., Budrugeac, P., Giurginca, M., Mašić, A., Badea, N. and Della Gatta, G., 2008. Study of deterioration of historical parchments by various thermal analysis techniques complemented by SEM, FTIR, UV–Vis–NIR and unilateral NMR investigations. Journal of Thermal Analysis and Calorimetry 91(1), 17-27.
Badea, E., Poulsen Sommer, D.V., Mühlen Axelsson, K., Larsen, R., Kurysheva, A., Miu, L. and Della Gatta, G., 2012. Damage ranking of historic parchment: from microscopic studies of fibre structure to collagen denaturation assessment by micro-DSC. e-preservation science 9, 97-109. https://www.morana-rtd.com/e-preservationscience/2012/Badea-31-12-2012.pdf
Ballance, S., Børsheim, K. Y., Inngjerdingen, K., Paulsen, B.S. and Christensen, B.E., 2007. A reexamination and partial characterisation of polysaccharides released by mild acid hydrolysis from the chlorite-treated leaves of Sphagnum papillosum. Carbohydrate Polymers 67(1), 104-115. https://doi.org/https://doi.org/10.1016/j.carbpol.2006.04.020
Baldassarre, M., Li, C., Eremina, N., Goormaghtigh, E. and Barth, A., 2015. Simultaneous fitting of absorption spectra and their second derivatives for an improved analysis of protein infrared spectra. Molecules 20, 12599-12622. https://doi.org/10.3390/molecules200712599
Bartoletti, A., Odlyha, M., Hudziak, S., Mühlen Axelsson, M., de Groot, J. and Bozec, L., 2017. Visibilia ex invisibilibus: seeing at the nanoscale for improved preservation of parchment. Insight-Non-Destructive Testing and Condition Monitoring 59(5), 267-269. https://doi.org/10.1784/insi.2017.59.5.265
Bell, N., Larsen, R., Patten, K., Sommer, D.V.P., Drakopoulos, M. and Wess, T., 2018. Assessing the condition of the Domesday Books from the visual to the molecular. Heritage Science 6(1), 50. https://doi.org/10.1186/s40494-018-0215-0
Boyatzis, S.C., Velivasaki, G., Malea, E., 2016. A study of the deterioration of aged parchment marked with laboratory iron gall inks using FTIR-ATR spectroscopy and micro hot table. Heritage Science 4(1), 1-17. https://doi.org/10.1186/s40494-016-0083-4
Brandt, L.Ø., Schmidt, A.L., Mannering, U., Sarret, M., Kelstrup, K., Olsen, J.V. and Cappellini, E., 2014. Species Identification of Archaeological Skin Objects from Danish Bogs: Comparison between Mass-Spectrometry-Based Peptide Sequencing and Microscopy-Based Methods. PLoS ONE 9(9), 1-10. https://doi.org/10.1371/journal.pone.0106875
Broholm, H.C. and Hald, M., 1940. Costumes of the Bronze Age in Denmark. Copenhagen: Nyt Nordisk Forlag.
Cameron, D. and Moffatt, D., 1987. A generalized approach to derivative spectroscopy. Applied Spectroscopy 41, 539-544.
Carsote, C., Miu, L., Petroviciu, I., Creanga, D.M., Giurginca, M. and Vetter, W., 2012. Scientifc investigation of leather in ethnographical objects by molecular spectroscopy and MHT. Leather and Footwear Journal 12(3), 183-192.
Che Man, Y.B. and Mirghan, M.E.S., 2001. Detection of Lard Mixed with Body Fats of Chicken, Lamb and Cow by Fourier Transform Infrared Spectroscopy. Journal of the American Oil Chemists’ Society 78(7), 753-761. https://doi.org/10.1007/s11746-001-0338-4
ChemicalBook. https://chemicalbook.com
Christie, W.W., 2024. The Lipid Compositions of Animal Tissues. The Lipid Web. https://www.lipidmaps.org/resources/lipidweb/lipidweb_html/lipids/basics/comp-animal/index.htm
Derrick, M., 1991. Evaluation of the State of Degradation of Dead Sea Scroll Samples using FTIR Spectroscopy. The American Institute for Conservation. http://aic.stanford.edu/sg/bpg/annual/v10/bp10-06.html
Dixit, S., Yadav, A., Dwivedi, P.D. and Das, M., 2015. Toxic hazards of leather industry and technologies to combat threat: a review. Journal of Cleaner Production 87, 39-49. https://doi.org/10.1016/j.jclepro.2014.10.017
Dong, A., Huang, P., Caughey, B. and Caughey, W., 1995. Infrared analysis of ligand and oxidation-induced conformational changes in hemoglobins and myoglobins. Archives of Biochemistry and Biophysics 316(2), 893-898. https://doi.org/10.1006/abbi.1995.1120
Ebbesen, K., 2009. En skinddragt fra Møgelmose i Jelling. Aarbøger for nordisk Oldkyndighed og Historie 2006, 37-51.
Falcao, L. and Araujo, M.E.M., 2014. Application of ATR-FTIR spectroscopy to the analysis of tannins in historic leathers: the case study of the upholstery from the 19th century Portuguese Royal Train. Vibrational Spectroscopy 74, 1-10. https://doi.org/10.1016/j.vibspec.2014.08.001
Falcao, L. and Araujo, M.E.M., 2018. Vegetable tannins used in the manufacture of historic leathers. Molecules 23(5), 1-20. https://doi.org/10.3390/molecules23051081
Farahmandjou, M., Khodadadi, A. and Yaghobi, M., 2020. Low Concentration Iron-Doped Alumina (Fe/Al2O3) Nanoparticles Using Co-Precipitation Method. Journal of Superconductivity and Novel Magnetism 33(1), 3425-3432. https://doi.org/10.1007/s10948-020-05569-0
Fischer, C., 2000. Tollundmanden. Gaven til guderne. Mosefund fra Danmarks forhistorie. Silkeborg: Hovedland.
Glob, P.V., 1966. Mosefolket. Jernalderens Mennesker bevaret i 2000 År. København: Gyldendal.
Guillen, M.D., Ruiz, N., Cabo, R., Chirinos and Pascual, G., 2003. Characterization of Sacha Inchi (Plukenetia volubilis L.) oil by FTIR spectroscopy and 1 H NMR. comparison with linseed oil. Journal of American Oil Chemists’ Society 80, 755-762. https://doi.org/10.1007/s11746-003-0768-z
Hald, M., 1980. Ancient Danish Textiles from Bogs and Burials. Archaeological-Historical Series Vol. XXI. Copenhagen: Publications of the National Museum.
Haris, P.I. and Chapman, D., 1995. The conformational analysis of peptides using fourier transform IR spectroscopy. Biopolymers 37, 251-263. https://doi.org/10.1002/bip.360370404
Harris, S., 2012. Hide-working with dry scrape technique using stone and bone tools. Archaeological Leather Group Newsletter 36, 12-14. www.archleathgrp.org.uk
Hulme, E.W., Parker, J.G., Seymour-Jones, A., Davenport, C. and Willamson, F.J., 1905. Leather for Libraries. The Library Supply Co London. Leopold Classic Library. Monee, USA, 2023, 1-87. www.leopoldclassiclibrary.com
Innes, R.F., 1933. The Deterioration of Vegetable-Tanned Leather on Storage. V. Journal of the International Society of Leather Trades Chemists XVII, 725-754.
Jackson, M. and Mantsch, H.H., 1995. The use and misuse of FTIR spectroscopy in the determination of protein structure. Critical Reviews in Biochemistry and Molecular Biology 30, 95-120. https://doi.org/10.3109/10409239509085140
Jensen, J., 2003. Danmarks Oldtid. Ældre Jernalder 500 f.Kr.-400 e.Kr. København: Gyldendal.
Kern, M.S., Pataki-Hundt, A., Wouters, J. and Kirby, D.P., 2018. Accelerated Ageing of Parchment: Investigation of a Photo Catalysed, Low-Heat Approach. Restaurator 39(1), 33-69. https://doi.org/10.1515/res-2017-0013
Kinsella, J.E., 1970. Liver Lipids of Lactating Bovine: Fatty Acid Composition. Journal of Dairy Science vol. 53, no. 5, 604-606. https://www.journalofdairyscience.org/article/S0022-0302(70)86263-4/pdf
Kong, J. and Yu, S., 2007. Fourier Transform Infrared Spectroscopic Analysis of Protein Secondary Structures. Acta Biochimica et Biophysica Sinica 39(8), 549-559. https://doi.org/10.1111/j.1745-7270.2007.00320.x
Larsen, R., 1995. Fundamental aspects of the deterioration of vegetable tanned leathers, Ph.D. Thesis, University of Copenhagen. Copenhagen: The Royal Danish Academy of Fine Arts, School of Conservation, 18-20 and 105-110.
Larsen, R., 2000. Experiments and Observations in the Study of Environmental Impact on Historical Vegetable Tanned Leathers. Thermochimica Acta, 365. Special issue on Cultural Heritage and Environmental Implications, 85-99.
Larsen, R., 2007. Introduction to damage and damage assessment of parchment. In: Improved damage assessment of parchment (IDAP). Assessment, data collection and sharing of knowledge. European Commission, Research Report no. 18, European Communities, Belgium, 17-21.
Larsen, R., 2022. Report on the Analysis of Sulphur Free Calf Leather for Bookbinding. News. Online Community for the American Institute for Conservation and Foundation for Advancement in Conservation. https://community.culturalheritage.org/blogs/ren-larsen/2022/06/09/report-on-sulphur-free-calf-leather
Larsen, R. and Poulsen, D.V., 2007. Analysis of the Skin. In: Asingh, P. and Lynnerup, N., eds. Grauballe Man – An Iron Age Bog Body Revisited. Jutland Archaeological Society Publications vol. 49. Højbjerg: Aarhus University Press, 85-91.
Larsen, R., Poulsen, D.V. and Vest, M., 2002. The Hydrothermal Stability (shrinkage activity) of parchment measured by the micro hot table method (MHT). In: R. Larsen, ed. Micro Analysis of Parchment. London: Archetype Publications Ltd., 55-62.
Larsen, R., Siegel, S. and Themmen, E.R., 2021. Preliminary Report on the Development of a Sulphur Free Full Vegetable Tanned Archival Calf Leather. Leather and Related Materials Working Group Newsletter 10 (June), 6-7.
Larsen, R., Sommer, D.V.P., Mühlen Axelsson, K. and Frank, S.K., 2012. Transformation of Collagen into Gelatine in Historical Leather and Parchment Caused by Natural Deterioration and Moist Treatment. In: C. Bonnot-Diconne, C. Dignard and J. Göpfrich, eds. ICOM-CC Leather and Related Materials Workings Group. Postprints of the 10th Interim Meeting. Offenbach: Deutsches Ledermuseum Schuhmuseum, 61-68.
Larsen, R., Vest, M. and Nielsen, K., 1993. Determination of hydrothermal stability (shrinkage temperature) of historical leathers by the micro hot table technique. Journal of the Society of Leather Technologists and Chemists 77, 151-156.
Mannering, U., Possnert, G., Heinemeier, J. and Gleba, M., 2010. Dating Danish textiles and skins from bog by means of 14C AMS. Journal of Archaeological Science 37(2), 261-268.
Mills, J. and White, R., 1999. Organic Chemistry of Museum Objects (2nd ed.). New York: Routledge. https://doi.org/10.4324/9780080513355).
Mühlen Axelsson, K., Larsen, R. and Sommer, D.V.P., 2012. Dimensional studies of specific microscopic
fibre structures in deteriorated parchment before and during shrinkage. Journal of Cultural Heritage 13(2), 128-136. https://doi.org/10.1016/j.culher.2011.08.001
Mühlen Axelsson, K., Larsen, R., Sommer, D.V.P. and Melin, R., 2014. 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), 46-57. https://doi.org/10.1179/2047058414Y.0000000140
Mühlen Axelsson, K., Larsen, R., Sommer, D.V.P. and Melin, R., 2017. Establishing the relation between degradation mechanisms and fibre morphology at microscopic level in order to improve damage diagnosis for parchments – A preliminary study. In: J. Bridgland, ed. ICOM-CC 18th Triennial Conference Preprints, Copenhagen, 4-8 September 2017, art. 0507. Paris: International Council of Museums. https://www.researchgate.net/publication/319649401_Establishing_the_relation_between_degradation_mechanisms_and_fibre_morphology_at_microscopic_level_in_order_to_improve_damage_diagnosis_for_parchments_-_A_preliminary_study
Munksgaard, E., 1974. Oldtidsdragter. København: Nationalmuseet.
Nina Naquiah, A.N., Marikkar, J.M.N., Mirghani, M.E.S., Nurrulhidayah, A.F. and Yanty, N.A.M., 2017. Differentiation of Fractionated Components of Lard from Other Animal Fats Using Different Analytical Techniques. Sains Malaysiana 46(2), 209-216. http://dx.doi.org/10.17576/jsm-2017-4602-04
Odlyha, M., Theodorakopoulos, C., de Groot, J., Bozec, L. and Horton, M., 2009. Fourier Transform
Infra-Red Spectroscopy (ATR/FTIR) and Scanning Probe Microscopy of Parchment. e-Preservation Science 6, 138-144. ISSN: 1581-9280 web edition.
Ogilvie, T., 2019. Conserving Bog Bodies: The Key Questions. Journal of Wetland Archaeology 19(1–2), 67-88. https://doi.org/10.1080/14732971.2020.1826196
Painter, T.J., 1991. Lindow man, Tolllund man and other peat-bog bodies: The preservative and antimicrobial action of Spagnan, a reactive glycuronoglycan with tanning and sequestering properties. Review paper. Carbohydrate Polymers 15, 123-142. https://doi.org/10.1016/0144-8617(91)90028-B
Peacock, E., 2001. Water-degraded Archaeological Leather: An Overview of Treatments Used at Vitenskapsmuseum (Trondheim). In: B. Wills, ed. Leather Wet and Dry. Current treatments in the Conservation of Waterlogged and Desiccated Archaeological Leather, 12-25. London: Archetype Publications.
Plavan, V., Giurginca, M., Budrugeac, P., Vilsan, M. and Miu, L., 2010. Evaluation of the physico-chemical characteristics of leather samples of some historical objects from Kiev. Revistade Chimie 61(7), 627-631.
Poitelon, Y., Kopec, A.M. and Belin, S., 2020. Myelin Fat Facts: An Overview of Lipids and Fatty Acid Metabolism. Cells 9(4), 2-17. https://doi.org/10.3390/cells9040812
Portaccio, M., Faramarzi, B. and Lepore, M., 2023. Probing Biochemical Differences in Lipid Components of Human Cells by Means of ATR-FTIR Spectroscopy. Biophysica 3, 524-538. https://doi.org/10.3390/biophysica3030035
Rahme, L., 1991. Skinn och beredning med traditionella metoder. Stockholm: LTs Förlag.
Reed, R., 1972. Ancient Skins Parchments and Leather. London and New York: Seminar Press.
Ricci, A., Olejar, K.J, Parpinello, G.P., Kilmartin, P.A and Versari, A., 2015. Application of fourier transform infrared (FTIR) spectroscopy in the characterization of tannins. Applied Spectroscopy Reviews 50(5), 407-442. https://doi.org/10.1080/05704928.2014.1000461
Rohman, A. and Che Man, Y.B., 2010. FTIR spectroscopy combined with chemometrics for analysis of lard in the mixtures with body fats of lamb, cow and chicken. International Food Research Journal 17, 519-526. https://doi.org/10.1080/19476331003774639
Rowe, S., Ravaioli, F., Tully, C. and Narvey, M., 2018. Conservation and Analysis on a Shoestring: Displaying Gut Parkas at the Polar Museum, Cambridge. Journal of Conservation and Museum Studies 16(1), 1-11. https://doi.org/10.5334/jcms.157
Safar, M.D., Bertrand, P., Robert, M.F. and Devaux Genot, C., 1994. Characterization of edible oils, butters and margarines by fourier transform infrared spectroscopy with attenuated total reflectance. Journal of American Oil Chemists’ Society 71, 371-377. https://doi.org/10.1007/BF02540516
Schmidt, O., 2001. Insecticide Contamination at the National Museum of Denmark: A Case Study. Collection Forum 16(1-2), 92-95.
Sivaram, N.M. and Barik, D., 2019. Chapter 5 – Toxic Waste from Leather Industries. In: Energy from Toxic Organic Waste for Heat and Power Generation. Woodhead Publishing Series in Energy, 55-67. https://doi.org/10.1016/B978-0-08-102528-4.00005-5
Sommer, D.V.P., Botfeldt, K., Gelting, U. and Hovmand, I., 2013. The state of preservation of two skins from Danish peat bogs – an investigation of archaeological waterlogged skin from the peat bogs Vindum Mose and Vester Torsted Mose examined using four types of analysis. Proceedings of the 12th ICOM-CC Group of Wet Organic Archaeological Materials Conference. Istanbul 2013. Printed in Canada by Lulu.com, 342-349.
Sommer, D., Mühlen Axelsson, K., Collins, M., Fiddyment, S., Bredal‐Jørgensen, J., Simonsen, K.P., Lauridsen, C. and Larsen, R., 2017. Multiple Microanalyses of a Sample from the Vinland Map. Archaeometry 2(59), 287-301. https://doi.org/10.1111/arcm.12249
Stankiewicz, B.A., Hutchins, J.C., Thomson, R., Briggs, D.E. and Evershed, R.P., 1997. Assessment of bog-body tissue preservation by pyrolysis-gas chromatography/mass spectrometry. Rapid Commun Mass Spectrom 11(17), 1884-1890. https://doi.org/10.1002/(sici)1097-0231(199711)11:17<1884::Aid-rcm62>3.0.Co;2-5
Strehle, H. 2007. The Conservation of Grauballe Man. In: P. Asingh and N. Lynnerup, eds. Grauballe Man – An Iron Age Bog Body Revisited. Jutland Archaeological Society Publications vol. 49. Højbjerg: Aarhus University Press, 33-50.
Susi, H. and Byler, M., 1988. Protein structure by Fourier Transform Infrared Spectroscopy: second derivative spectra. Biochemical and Biophysical Research Communications 115(1), 391-397. https://doi.org/10.1016/0006-291X(83)91016-1
Syed, M., Saleem, T., Shuja-ur-Rehman, Iqbal, M.A., Javed, F., Khan, M.B.S. and Sadiq, K., 2010. Effects of Leather Industry on Health and Recommendations for Improving the Situation in Pakistan. Archives of Environmental & Occupational Health 65(3), 163-172. https://doi.org/10.1080/19338241003730895
Tatulian, S.A., 2019. FTIR analysis of proteins and protein-membrane interactions. In: J.H. Kleinschmidt, ed. Lipid-Protein Interactions: Methods and Protocols. New York: Springer New York, 281-325. https://doi.org/10.1007/978-1-4939-9512-7_13
Thomson, R., 2007. Chapter 5: Leather. In: E. May and M. Jones (eds) Conservation Science, 92-120. Cambridge: Royal Society of Chemistry. https://doi.org/10.1039/9781847557629-00092.
Thorvildsen, E., 1952. Menneskeofringer i oldtiden. Jernalderligene fra Borremose i Himmerland. KUML, 32-48.
Thorvildsen, K., n.d. Konserveringsnoter 1935-1952. Danish National Museum in Brede, Conservation Archive.
United Nations. Department of Economic and Social Affairs. Sustainable Development. The 17 Goals. https://sdgs.un.org/goals.
Usoltsev, D., Sitnikova, V., Kajava, A. and Uspenskaya, M., 2019. Systematic FTIR Spectroscopy Study of the Secondary Structure Changes in Human Serum Albumin under Various Denaturation Conditions. Biomolecules 9, 359. https://doi.org/10.3390/biom9080359
Vadrucci, M., De Bellis, G., Mazzuca, C., Mercuri, F., Borgognoni, F., Schifano, E., Uccelletti, D. and Cicero, C., 2020. Effects of the Ionizing Radiation Disinfection Treatment on Historical Leather. Frontiers in Materials 7(21), 1-9. https://doi.org/10.3389/fmats.2020.00021
van der Sanden, W., 1996. Through nature to eternity. The bog bodies of northwest Europe. Amsterdam: Batavian Lion International.
Van de Voort, F.R. and Sedman, J., 2000. FTIR Spectroscopy: The new generation of oil analysis methodologies. INFORM 11, 614-620.
Veneranda, M., Aramendia, J., Bellot-Gurlet, L., Colomban, P., Castro, K., Madariaga, J.M., 2018. FTIR spectroscopic semi-quantification of iron phases: A new method to evaluate the protection ability index (PAI) of archaeological artefacts corrosion systems. Corrosion Science 133, 68-77. https://doi.org/10.1016/j.corsci.2018.01.016
Vyskocilová, G., Ebersbach, M., Kopecká, R., Prokeš, L. and Príhoda, J., 2019. Model study of the leather degradation by oxidation and hydrolysis. Heritage Science 7, 26. https://doi.org/10.1186/s40494-019-0269-7
Warming, R.F., Larsen, R., Sommer D.V.P., Ørsted Brandt, L. and Jensen, X.P., 2020. Shields and hide – On the use of hide in Germanic shields of the Iron Age and Viking Age. Bericht der Römisch-Germanischen Kommission 97, 155-225. https://doi.org/10.11588/berrgk.2016.0.76641
Wiley spectra base. https://spectrabase.com
Young, G., 1990. Microscopical hydrothermal stability measurements of skin and semi-tanned leather. Preprints of the ICOM Committee for Conservation, 9th triennial Dresden 1990, 626-630. Los Angeles: ICOM.
Downloads
Published
How to Cite
Issue
Section
License
Copyright (c) 2024 René Larsen, Anne Lisbeth Schmidt, Martin N. Mortensen, Yvonne Shashoua, Henning Matthiesen, Dorte Vestergaard Poulsen Sommer, Jane Richter
This work is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International License.
Counting from volume 11 (2022), articles published in DJA are licensed under Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0). The editorial board may accept other Creative Commons licenses for individual articles, if required by funding bodies e.g. the European Research Council. With the publication of volume 11, authors retain copyright to their articles and give DJA the right to the first publication. The authors retain copyright to earlier versions of the articles, such as the submitted and the accepted manuscript.
Articles in volume 1-8 are not licensed under Creative Commons. In these volumes, all rights are reserved to DJA. This implies that readers can download, read, and link to the articles, but they cannot republish the articles. Authors can upload their articles in an institutional repository as a part of a green open access policy.
Articles in volume 9-10 are not licensed under Creative Commons. In these volumes, all rights are reserved to the authors of the articles respectively. This implies that readers can download, read, and link to the articles, but they cannot republish the articles. Authors can upload their articles in an institutional repository.
