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Analyses of Volatile Organic Compounds in Archaeological Artifacts http://lib.ulg.ac.be http://matheo.ulg.ac.be Analyses of volatile organic compounds in archaeological artifacts. Auteur : Zanella, Delphine Promoteur(s) : Focant, Jean-Francois Faculté : Faculté des Sciences Diplôme : Master en sciences chimiques, à finalité spécialisée Année académique : 2016-2017 URI/URL : http://hdl.handle.net/2268.2/2469 Avertissement à l'attention des usagers : Tous les documents placés en accès ouvert sur le site le site MatheO sont protégés par le droit d'auteur. Conformément aux principes énoncés par la "Budapest Open Access Initiative"(BOAI, 2002), l'utilisateur du site peut lire, télécharger, copier, transmettre, imprimer, chercher ou faire un lien vers le texte intégral de ces documents, les disséquer pour les indexer, s'en servir de données pour un logiciel, ou s'en servir à toute autre fin légale (ou prévue par la réglementation relative au droit d'auteur). Toute utilisation du document à des fins commerciales est strictement interdite. Par ailleurs, l'utilisateur s'engage à respecter les droits moraux de l'auteur, principalement le droit à l'intégrité de l'oeuvre et le droit de paternité et ce dans toute utilisation que l'utilisateur entreprend. Ainsi, à titre d'exemple, lorsqu'il reproduira un document par extrait ou dans son intégralité, l'utilisateur citera de manière complète les sources telles que mentionnées ci-dessus. Toute utilisation non explicitement autorisée ci-avant (telle que par exemple, la modification du document ou son résumé) nécessite l'autorisation préalable et expresse des auteurs ou de leurs ayants droit. FACULTY OF SCIENCES Chemistry Department The Organic and Biological Analytical Chemistry laboratory (OBiAChem) - The Mass Spectrometry laboratory – Prof. J-F Focant Analyses of volatile organic compounds in archaeological artifacts. Academic year 2016-2017 Dissertation presented by Delphine Zanella for the acquisition of the diploma of Master in Chemical Sciences Acknowledgments Acknowledgments This dissertation owes its existence to the help and great support I received from several people. I would like to express my sincere thanks to the following people. To my supervisor Professor Jean-François Focant for accepting me in his laboratory and for his guidance, support and suggestions during the research. To Professor E. De Pauw, Professor V. Rots and Dr. A. Giri for agreeing to constitute my reading committee. To Lena Dubois for her daily coaching in the laboratory, for her patience, for answering my numerous questions and for the revision of this dissertation. This work could not have been achieved without her encouragement and enthusiasm. To Dr. N. Reifarth for providing Qatna samples, for her advices and suggestion during the analyses. To the Traceolab laboratory, and especially to Professor V. Roots and Dries Cnuts, for supplying the numerous raw and heated resins as well as archaeological samples and for taking their time to answer my questions. To Dr. P.-H. Stefanuto and Dr. K. Perrault for their early teaching in the laboratory, for taking me under their wings and for introducing me in DSM company. To Armelinda Agnello and Lena Dubois for their sunny mood in the office making my work even more enthusiastic. To the University faculty for their quality classes given throughout my scholarship. To my friends and classmates for the great moments during these five years of intense study. These years would not have been the same without their help and enthusiasm. And finally, my deepest thanks go to my family and my boyfriend for their unconditional support throughout my studies and my life and for their unrestricted love. i Table of contents Table of contents Acknowledgments ....................................................................................................................... i Abbreviations ............................................................................................................................ iv Chapter 1: Introduction ........................................................................................................ 1 1.1 Adhesives ..................................................................................................................... 2 1.1.1 Natural plant resins ............................................................................................... 2 1.1.2 Waxes ................................................................................................................... 4 1.1.3 Tars ....................................................................................................................... 4 1.2 The use of adhesives .................................................................................................... 5 1.2.1 Tool hafting .......................................................................................................... 5 1.2.2 Funerary rituals .................................................................................................... 6 1.3 Degradation pathway of adhesives .............................................................................. 7 1.4 The Royal Tomb of Qatna ........................................................................................... 8 1.5 Chromatography in archaeology ................................................................................. 9 Chapter 2: Materials and methods ..................................................................................... 11 2.1 One dimensional gas chromatography ...................................................................... 11 2.2 Comprehensive two-dimensional gas chromatography ............................................. 11 2.3 Sampling method ....................................................................................................... 14 2.4 Injectors ..................................................................................................................... 14 2.5 Column ...................................................................................................................... 14 2.6 Modulator .................................................................................................................. 15 2.7 Detectors .................................................................................................................... 16 2.8 Sample treatments ...................................................................................................... 17 2.9 Experimental section ................................................................................................. 18 2.9.1 SPME extraction ................................................................................................ 18 2.9.2 GC×GC-HRTOFMS analysis ............................................................................ 19 2.10 Data treatment ............................................................................................................ 19 2.11 Statistical tools ........................................................................................................... 20 Chapter 3: Results and discussion ...................................................................................... 22 3.1 Traceolab samples ..................................................................................................... 22 3.1.1 Non-treated adhesive mixtures ........................................................................... 22 ii Table of contents 3.1.2 Thermally degraded adhesive mixtures .............................................................. 27 3.1.3 Archaeological samples ...................................................................................... 33 3.2 Archaeological samples from Qatna .......................................................................... 36 3.2.1 Bone samples ...................................................................................................... 39 3.2.2 Textile samples ................................................................................................... 43 Chapter 4: Conclusion ......................................................................................................... 49 Chapter 5: Perspectives ....................................................................................................... 51 Bibliography ........................................................................................................................... 52 iii Abbreviations Abbreviations Fcrit: Fisher ratio cut-off F-ratio: Fisher ratio GC: Gas chromatography GC×GC: Comprehensive two-dimensional gas chromatography GC×GC-MS: Comprehensive two-dimensional gas chromatography coupled mass spectrometry GC×GC-TOFMS: Comprehensive two-dimensional gas chromatography coupled to time-of- flight mass spectrometry HCA: Hierarchical cluster analysis HRTOF-MS: High resolution time-of-flight mass spectrometry HS-SPME: Headspace solid-phase microextraction MS: Mass spectrometry PM: Modulation period PCA: Principal component analysis TOFMS: Time-of-flight mass spectrometry VOCs: Volatile organic compounds iv Chapter 1: Introduction Chapter 1: Introduction During life cycle, most of the organic materials undergo natural biochemical decay processes leaving no evidence of their existence. However, some residues can be preserved for thousand years [1]. The analysis of those residues, their conservation and fossilization processes are essential to understand life in ancient times. Several types of organic residues have been recovered from archaeological objects, one of
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