ORGANIC RESIDUE ANALYSIS AND THE EARLIEST USES OF POTTERY IN THE ANCIENT MIDDLE EAST by Michael William Gregg A thesis submitted in conformity with the requirements for the degree of Doctor of Philosophy Department of Anthropology University of Toronto © Copyright by Michael William Gregg 2009 Library and Archives Bibliothèque et Canada Archives Canada Published Heritage Direction du Branch Patrimoine de l’édition 395 Wellington Street 395, rue Wellington Ottawa ON K1A 0N4 Ottawa ON K1A 0N4 Canada Canada Your file Votre référence ISBN: 978-0-494-60970-5 Our file Notre référence ISBN: 978-0-494-60970-5 NOTICE: AVIS: The author has granted a non- L’auteur a accordé une licence non exclusive exclusive license allowing Library and permettant à la Bibliothèque et Archives Archives Canada to reproduce, Canada de reproduire, publier, archiver, publish, archive, preserve, conserve, sauvegarder, conserver, transmettre au public communicate to the public by par télécommunication ou par l’Internet, prêter, telecommunication or on the Internet, distribuer et vendre des thèses partout dans le loan, distribute and sell theses monde, à des fins commerciales ou autres, sur worldwide, for commercial or non- support microforme, papier, électronique et/ou commercial purposes, in microform, autres formats. paper, electronic and/or any other formats. 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THESIS TITLE: Organic residue analysis and the earliest uses of pottery in the ancient Middle East Michael William Gregg A thesis submitted in conformity with the requirements for the degree of Doctor of Philosophy, Department of Anthropology, University of Toronto, 2009 Abstract In this dissertation, I discuss the role of organic residue analysis in identifying economic activities and subsistence practices associated with the first uses of pottery in the Middle East, and present the results of my analyses of 280 potsherds recovered from 22 Neolithic and early Chalcolithic settlements dating between 7300 and 4300 cal BC. The adoption of pottery vessels in the early agricultural villages and pastoral encampments of the Middle East was not a uniform phenomenon, with this new technology not immediately of benefit, apparently, to all human groups. Results of my analyses have demonstrated that ‘conventional’ solvent extraction and alkaline hydrolysis techniques have limited utility in the recovery of diagnostic organic compounds from pottery from early ceramic horizons in the Middle East (Gregg et al. 2007), and that increased yields can be achieved through the use of a microwave-assisted liquid chromatography protocol (Gregg et al. 2009; Gregg and Slater in press). My research has established that there is greater diversity in the fractionation of stable carbon isotopes associated with the synthesis of fatty acids in domesticated animals than has previously been reported. In many instances, the ranges of modern isotopic values that have been used to categorize animal fats in archaeological potsherds in northern Europe cannot distinguish between the 13C ratios of ancient dairy residues and ii carcass fats of ruminant and non-ruminant species in central Europe or the Middle East (Gregg et al. 2009; Gregg and Slater in press). In light of these results, I evaluate the diagnostic potential and limitations of different methodological approaches in the recovery and characterization of organic residues, and propose a series of measures that will allow more confident categorization of the substances in early pottery vessels from the Middle East. I also make a number of recommendations for archaeologists considering the use of organic residue analysis, and suggest some practical ideas on how to develop the degree of confidence necessary to assess the methods used in acquisition of molecular and isotopic data, and ultimately, to evaluate the adequacy of the analytical criteria used to address specific archaeological research questions. iii Acknowledgements I would like to thank the many people and organizations whose generous contributions, critical assessments and wealth of ideas have made my doctoral research project possible. Professors Michael Chazan, Edward Banning and Heather Miller of the Department of Anthropology at the University of Toronto have provided me with thoughtful advice and sound direction in the pursuit of my research goals. Dr. Chazan and Dr. Banning co-supervised the initial stages of my doctoral research, while Dr. Miller supervised the development of my research proposal, data collection and analytical strategy, and the writing, editing and completion of my dissertation. As my Masters advisor, Dr. Chazan instilled a fascination of prehistoric human behavior in me, and has pushed and cajoled me into investigating places, periods and topics I never dreamed I would explore. While I was completing my Masters degree, Dr. Banning introduced me to my research subject, and provided me with guidance in understanding the chronological sequence of cultural developments in the ancient Near East and the applicability of different archaeometric techniques in answering archaeological research questions. Dr. Banning also provided me with the opportunity to join his excavation team at the Late Neolithic site at al-Basatîn in northern Jordan. Details of Dr. Banning’s contribution to our multi-authored published works are detailed in section 4.1.1. Dr. Banning and Dr. Miller have also made a large financial contributions towards the molecular and isotopic analyses of organic residues examined in this study from grants provided by the Social Sciences and Humanities Research Council of Canada. While I was completing my Masters degree at the University of Toronto, Professor Matthew Collins and Dr. Oliver Craig offered me the opportunity to work on my doctoral research project under their joint supervision at the University of Newcastle. However, before the completion of Master’s degree, Dr. Collins and Dr. Craig took up positions at the Universities of York and Rome, respectively. Since the analytical equipment necessary to undertake my research was not yet available to them at either of these institutions, Dr. Collins introduced me to the head of the Department of Archaeological Sciences at the University of Bradford, Professor Carl Heron. Dr. Heron subsequently offered me the use of his laboratory and the analytical instrumentation at Bradford and provided me with instruction on the basic tenets of biomolecular archaeology and soil chemistry, and guidance in the interpretation of molecular compounds surviving in archaeological pottery. While at Bradford, Dr. Benjamin Stern instructed me on the recovery of organic residues from archaeological pottery and provided me with training in gas chromatography and mass spectrometry. Following my preliminary iv identification of molecular compounds in pottery fragments from two Neolithic sites in southwestern Iran, I collaborated with Dr. Stern and his laboratory assistant, Ms Rhea Brettell, on the subsequent molecular and isotopic analyses of these residues. Dr. Stern made a small financial contribution towards isotopic analysis of organic residues from a grant provided by the Natural and Environmental Research Council of the United Kingdom. Dr. Stern’s and Ms Brettell’s contribution to our multi-authored published work are detailed in section 3.1. Professor Andrew Moore of the Rochester Institute of Technology was the first archaeologist to provide me with pottery fragments from his excavations of the late Neolithic occupation at the site of Abu Hureyra in northern Syria. As a result of Dr. Moore’s support, many other excavators eagerly provided me with pottery fragments from early pottery horizons in the Middle East to examine. Dr. Bill Finlayson, Director of the British Council for Research in the Levant and Professor Ian Kuijt of Notre Dame University afforded me the opportunity to work with them on the excavation of the aceramic Neolithic settlement at Dhra‘ in central Jordan, and provided me with pottery from the nearby Late Neolithic occupation at the site. Dr. Ehud Gallili of the Israel Antiquities Authority provided me with pottery fragments from his excavation of the submerged Late Neolithic settlement at Newe Yam in northern Israel, and welcomed me into the warmth and hospitality of his home. Professor Yossi Garfinkel of the Hebrew University in Jerusalem provided me with pottery from the Late Neolithic sites at Munhata and Sha’ar Hagolan in Israel. Professor Asli Erim of the University of Istanbul, provided me with pottery from Çayönü in southeastern Turkey. Professor Frank Hole of Yale University provided me with pottery fragments from the earliest pottery horizons at the sites of Ali