WOOD TAR IN THE DNIEPER AND ELBE COMMUNITIES: VI – II MILLENIUM BC Sławomir Pietrzak V O L U M E 17 • 2012 BALTIC-PONTIC STUDIES 61-809 Poznań (Poland) Św. Marcin 78 Tel. 618294799, Fax 618294788 E-mail: [email protected] EDITOR Aleksander Kośko EDITORIAL COMMITEE Sophia S. Berezanskaya (Kiev), Aleksandra Cofta-Broniewska (Poznań), Mikhail Charniauski (Minsk), Lucyna Domańska (Łódź), Elena G. Kalechyts (Minsk), Viktor I. Klochko (Kiev), Jan Machnik (Kraków), Vitaliy V. Otroshchenko (Kiev), Ma- rzena Szmyt (Poznań), Petro Tolochko (Kiev) SECRETARY Marzena Szmyt SECRETARY OF VOLUME Danuta Żurkiewicz ADAM MICKIEWICZ UNIVERSITY INSTITUTE OF EASTERN STUDIES INSTITUTE OF PREHISTORY Poznań 2012 ISBN 83-86094-17-6 ISSN 1231-0344 WOOD TAR IN THE DNIEPER AND ELBE COMMUNITIES: VI – II MILLENIUM BC Sławomir Pietrzak Translated by Ryszard J. Reisner V O L U M E 17 • 2012 © Copyright by BPS and Authors All rights reserved Cover Design: Eugeniusz Skorwider Sławomir Pietrzak Printed in Poland Computer typeset by PSO Sp. z o.o. w Poznaniu Printing: Zakłady Poligraficzne TMDRUK in Poznań CONTENTS Editor’s Foreword . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 Editorial Comment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 Foreword from the Author . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 1 . Study Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 2 . Material Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 3 . Chorological and Chronological Scope . . . . . . . . . . . . . . . . . . . . 13 4 . History of Research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 5 . Research Method and Methodology . . . . . . . . . . . . . . . . . . . . . . . 17 6 . Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 I . Evidence for Wood-Tar Production in Historic Times . . . . . . . . . . . . . . . . . 21 I .1 . Terminology: Definitions of the Terms ‘Wood Tar’ / ‘Wood-Tar Production’ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 I .2 . Wood Tar in Written Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 I .2 .1 . Production Process Evidence . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 I .2 .2 . Application Evidence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25 I .3 . Linguistic Evidence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 II . Techno-Archaeological Fundamentals of Wood-Tar Studies . . . . . . . . . . . . 33 II .1 . Raw Material Used in Wood-Tar Production . . . . . . . . . . . . . . . . 33 II .1 .1 . Wood Chemical Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 II .1 .2 . Chemical Structure of Bark . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37 II .2 . Tar Making Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39 II .2 .1 . The Archaeological Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . 39 II .2 .2 . The Technological and Chemical Perspective . . . . . . . . . . . . . . . 45 II .3 . Physical and Chemical Properties of Wood Pyrolysis Products . . 48 II .3 .1 . Physical and Chemical Properties of Birch Tar . . . . . . . . . . . . . . 48 II .3 .2 . Physical and Chemical Properties of Pine Tar . . . . . . . . . . . . . . . 49 II .4 . Preparing Tar and Processing Techniques . . . . . . . . . . . . . . . . . . 51 II .5 . Residues of Wood Tar – Archaeological Data . . . . . . . . . . . . . . . 54 II .5 .1 . Lumped Tar Substances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55 II .5 .1 .1 . Large Fragments Lumped Together . . . . . . . . . . . . . . . . . . . . . . . 55 II .5 .1 .2 . Small Fragments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57 II .5 .2 . Tar Substances on Pottery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57 II .5 .2 .1 . Post-production Residues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57 II .5 .2 .2 . Binding and Sealing Material . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59 II .5 .2 .3 . Colorants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63 II .5 .3 . Tar Substances on Utilitarian Objects . . . . . . . . . . . . . . . . . . . . . 66 II .5 .4 . Carbon Deposits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67 II .5 .5 . Other . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68 II .5 .5 .1 . Boat and Ship Caulking and Preservation Material . . . . . . . . . . . 68 II .5 .5 .2 . Substance Used in Mummification . . . . . . . . . . . . . . . . . . . . . . . . 69 II .5 .5 .3 . Wood Tar in Rites and Primitive Medicine . . . . . . . . . . . . . . . . . 70 II .6 . Research Procedures – Sampling . . . . . . . . . . . . . . . . . . . . . . . . . 71 III . Range and Methodology of Laboratory Tests . . . . . . . . . . . . . . . . . . . . . . . 73 III .1 . Melting Point Measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74 III .2 . Solubility Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75 III .3 . Thin-Layer Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76 III .4 . Microscopic Observations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77 III .5 . Infrared Spectrophotometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79 III .6 . Mass Spectrometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80 III .7 . Nuclear Magnetic Resonance Spectroscopy . . . . . . . . . . . . . . . . . 81 III .8 . Electron Paramagnetic Resonance Spectroscopy . . . . . . . . . . . . . 82 IV . Interpretation of Physico-Chemical Examinations . . . . . . . . . . . . . . . . . . . 84 IV .1 . Identification of Production Technology of Examined Substances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84 IV .1 .1 . Examination Results of Wood-Tar Substances . . . . . . . . . . . . . . . 85 IV .1 .1 .1 . Technological Group I . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85 IV .1 .1 .2 . Technological Group II . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88 IV .1 .1 .3 . Technological Group III . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90 IV .1 .1 .4 . Technological Group IV . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92 IV .1 .2 . Examination Results of Bituminous Substances . . . . . . . . . . . . . 94 IV .1 .2 .1 . Technological Group V . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94 IV .1 .3 . Examination Results of Composite Substances . . . . . . . . . . . . . . 96 IV .1 .3 .1 . Technological Group VI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96 IV .2 . Identification of Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98 IV .2 .1 . Results of Studies on Post-production Residues . . . . . . . . . . . . . . 99 IV .2 .2 . Results of Studies on Binders . . . . . . . . . . . . . . . . . . . . . . . . . . . 111 IV .2 .3 . Results on Vessel Caulking Studies . . . . . . . . . . . . . . . . . . . . . . 119 IV .2 .4 . Results of Studies on Colorants . . . . . . . . . . . . . . . . . . . . . . . . . 124 IV .3 . Variety of Wood-Tar Production Technology and Application in Particular Cycles of Cultural Systems . . . . . . . . . . . . . . . . . . 131 V . Catalogue of Physico-Chemical Research Results . . . . . . . . . . . . . . . . . . . 141 V .1 . Temperature of Melting Point Measurement . . . . . . . . . . . . . . . 141 V .2 . Analysis of solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154 V .3 . Thin layer chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177 V .4 . Microscopic Observations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183 V .5 . Infered spectrophotometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225 V .6 . Mass Spectometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254 V .7 . Nuclear magnetic Spectometry . . . . . . . . . . . . . . . . . . . . . . . . . . 256 V .8 . Electron Paramagnetic Resonance Spectometry . . . . . . . . . . . . 259 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280 Catalogue of Finds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311 Editor’s Foreword The study ‘Wood Tars in the Dnieper and Elbe Communities: 6th – 2nd Mille- nium BC’ is the first European monograph of its kind in the professional literature devoted to the general question of the craft technology and application of wood tars among proto-agrarian communities across the long line of the Neolithic, Eneolithic and beginning of the Bronze Age across the vast expanse of border- lands joining Eastern and Western Europe . The research for the purpose of this monograph was undertaken at the Univer- sity of Adam Mickiewicz in Poznań in partnership with the Institute of Prehistory and the Physico-Chemical Materials and Nanotechnology Section at the Faculty of Chemistry . The study was completed with the aid of chemical analyses of a com- prehensive collection of wood tar samples documented in the course of excava- tions conducted in collaboration with a number of research-related institutions . The original work in Polish, ‘Zastosowanie i technologie wytwarzania dziegciu przez społeczeństwa międzyrzecza Dniepru i Łaby od VI do II tys BC’ [Wood Tar Crafts and Their Application Among Dnieper and Elbe Interfluvial Commu- nities: 6th – 2nd millennium BC] was published in 2010 [‘Archaeologia Bimaris Monografie’, vol . 4] and received broad-ranging ‘interdisciplinary recognition’ from many scholarly circles in Central-Eastern Europe for the issues raised in respect to wood tars and their applications among prehistoric peoples . This con- sequently saw the decision to aim for a potentially broader readership through an abridged English version in the ‘Baltic-Pontic Studies’ series . The study was supervised in respect to on-going work and research methods by Professor Jerzy J . Langer at the University of Adam Mickiewicz, who also reviewed the monograph for publication . Editorial comment 1 . All dates in the B-PS are calibrated [BC; see: Radiocarbon vol . 28, 1986, and the next volumes] . Deviations from this rule will be point out in notes [bc] . 2 . The names of the archaelogical cultures and sites are standarized to the English literature on the subject (e .g . M . Gimbutas, J .P . Mallory) . In the case of a new term, the author’s original name has been retained . 3 . The spelling of names of localities having the rank of administrative cen- tres follows official, state, English language cartographic publications (e .g . Ukraine, scale 1 : 2 000 000, Kiev: Mapa LTD, edition of 1996; Rèspublika BELARUS’, REVIEW-TOPOGRAPHIC MAP, scale 1:1 000 000, Minsk: BYELORUSSIAN CARTOGRAPHIC AN GEODETIC ENTERPISE, edition 1993) .