ACS SYMPOSIUM SERIES 625 Archaeological Chemistry Organic, Inorganic, and Biochemical Analysis org 001 s.w 12 | http://pubs.ac1/bk-1996-0625.f MCoalrleyg Ve oirfg Ninewia R Oorchneal,l eE DITOR 02 20 une 28, oi: 10.1 Jd Developed from a symposium sponsored on 6 | 35.42 5, 199 btyh eth De iDviisvioisnio onf oCfh tehme iHcaislt Eordyu ocaf tCiohne,m Inisct.r, y, 3.y 6a 1M the Division of Analytical Chemistry, 89.e: y at and the ACS Committees on Education and on Science bD wnloaded blication oaf tt hthee A 2m09etrhic Nana tCiohneaml iMcael eStoincgie ty, Do Pu Anaheim, California, April 2-6, 1995 American Chemical Society, Washington, DC 1996 In Archaeological Chemistry; Orna, M.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996. CC 79 .C5A73 1996 Copy 1 Archaeological chemistry Library of Congress Cataloging-in-Publication Data Archaeological chemistry: organic, inorganic, and biochemical analysis / Mary Virginia Orna, editor. p. cm.—(ACS symposium series, ISSN 0097-6156; 625) "Developed from a symposium sponsored by the Division of the History of Chemistry, the Division of Chemical Education, Inc., and the Division of Analytical Chemistry, at the 209th National Meeting of the American Chemical Society, Anaheim, California, April 2-6, 1995." org 001 Includes bibliographical references and indexes. s.w 12 | http://pubs.ac1/bk-1996-0625.f tChheII1eS ..mH BOAiiNscrrtan oc0lahr -E,ya8 M de4oou1falc o2rCagy-thi3 icVoe3anmi9lr. gi 5csihtI-nrV0eiyma ... iAsItIIrmIIy.. e— ArAicmCmaoenenrr igCiccraahennsesm CeCsihc.h aeemlm Siicocaaclil e SStyooc.c iieeDttyyiv.. isDDioiivnvi isosiifoo nn ooff 02 20 Analytical Chemistry. V. American Chemical Society. Meeting (209th: une 28, oi: 10.1 C19C957:9 .CA5nAah7e3im 19, 9C6a lif.) VI. Series. Jd 35.42 on 5, 1996 | 930.1—dc20 96-4812 CIP 3.y 6a 1M 89.e: This book is printed on acid-free, recycled paper. y at bD wnloaded blication ACmopeyrriicgahnt C©h 1e9m96ic al Society Do Pu All Rights Reserved. The appearance of the code at the bottom of the first page of each chapter in this volume indicates the copyright owner's consent that reprographic copies of the chapter may be made for personal or internal use or for the personal or internal use of specific clients. This consent is given on the condition, however, that the copier pay the stated per-copy fee through the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, for copying beyond that permitted by Sections 107 or 108 of the U.S. Copyright Law. This consent does not extend to copying or transmission by any means—graphic or electronic—for any other purpose, such as for general distribution, for advertising or promotional purposes, for creating a new collective work, for resale, or for information storage and retrieval systems. The copying fee for each chapter is indicated in the code at the bottom of the first page of the chapter. The citation of trade names and/or names of manufacturers in this publication is not to be construed as an endorsement or as approval by ACS of the commercial products or services referenced herein; nor should the mere reference herein to any drawing, specification, chemical process, or other data be regarded as a license or as a conveyance of any righto r permission to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or sell any patented invention or copyrighted work that may in any way be related thereto. Registered names, trademarks, etc., used in this publication, even without specific indication thereof, are not to be considered unprotected by law. PRINTED IN THE UNITED STATES AMERICA In Archaeological Chemistry; Orna, M.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996. 1995 Advisory Board ACS Symposium Series Robert J. Alaimo Cynthia A. Maryanoff Procter & Gamble Pharmaceuticals R. W. Johnson Pharmaceutical Research Institute Mark Arnold University of Iowa Roger A. Minear org 001 University of Illinois 12 | http://pubs.acs.1/bk-1996-0625.fw DUAPfnariizviveenrirdds Cit ayBem noatfrk TBaeleo rnR sneeess esaeerc h OAaVtT imU&nrkcTbea aBnnreatall -m PCLeah Nbacomoarrlapaataomirrgoinea s s u 02 20 Robert F. Brady, Jr. University of Michigan une 28, oi: 10.1 Naval Research Laboratory George W. Roberts on J6 | d Mary E. Castellion North Carolina State University 35.42 5, 199 ChemEdit Company John R. Shapley 3.y Margaret A. Cavanaugh University of Illinois 6a 89.1e: M National Science Foundation at Urbana-Champaign y at bD Arthur B. Ellis Douglas A. Smith wnloaded blication UGnuivnedrsai tIy. oGf Weoirscgo nsin at Madison LCo. nScourmreanstu Tnecdhanroalomgie s Corporation Do Pu University of Kansas DuPont Madeleine M. Joullie Michael D. Taylor University of Pennsylvania Parke-Davis Pharmaceutical Research Lawrence P. Klemann William C. Walker Nabisco Foods Group DuPont Douglas R. Lloyd Peter Willett The University of Texas at Austin University of Sheffield (England) In Archaeological Chemistry; Orna, M.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996. Foreword THE ACS SYMPOSIUM SERIES was first published in 1974 to provide a mechanism for publishing symposia quickly in book form. The purpose of this series is to publish comprehensive org 001 books developed from symposia, which are usually "snapshots 12 | http://pubs.acs.1/bk-1996-0625.fw ipssnaor rmotypim etoBh sreeaee"fdtvo i treohtewafe ba tlmph esaey ap omteecfrurp iscroa orsblien ueontm entpn -urtbthebsasel seii seasthdr oecr pbdehivoc aio.be skwe Fqi eniuosdgir c p ktfduholoyirtns ua aernsp e doappensrooro sn psaci,ro b itnilaotett pr.ei asinc cen,ts e,sp ct lehutsoes 02 the topic and for comprehensiveness of the collection. Some 20 une 28, oi: 10.1 proaupnerds o uart et heex cslcuodpeed o fa tt hteh ivso lupmoine.t , Iann add doitthioerns, aa drrea fatd odfe eda ctho on J6 | d paper is peer-reviewed prior to final acceptance or rejection. 35.42 5, 199 Terh^is) aonf otnhyem soyumsp orseivuiemw, wphrooc ebsesc oims es utpheer veidseitdo rb(sy) tohfe t hoer gbaonoikz . 63.ay The authors then revise their papers according to the recom 1M 89.e: mendations of both the reviewers and the editors, prepare by Dat camera-ready copy, and submit the final papers to the editors, wnloaded blication who cAhse cak rtuhlaet, aolnl lnye coersisgairnya lr erveisseiaorncsh h apvaep ebrese nan mda odrei.g inal re Do Pu view papers are included in the volumes. Verbatim reproduc tions of previously published papers are not accepted. In Archaeological Chemistry; Orna, M.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996. Preface TRACING CULTURAL EVOLUTION OVER CENTURIES and even millennia is the exciting task shared by archaeologists and archaeological chemists. Seldom financially rewarding, but of perennial interest, it has been the subject of nine major symposia at national meetings of the American Chemical Society. These symposia have attracted practicing archaeolo gists, chemists, biochemists, cultural anthropologists, and members of g 1 related disciplines from all over the world. The proceedings of five of s.acs.or25.pr00 tChheesme iscyaml pSoosciiae thya v(Ae CbeSe)n, fcooullre citne dth ien vAodluvmanecse sp uinb liCshheedm bisytr tyh eS eArmieesr aicnadn b6 u0 the present volume in the Symposium Series. p://p996- New methods in analytical chemistry, particularly methods coupled to 012 | htt21/bk-1 oacncee ssainboleth eorn itnh et aunldtreamtr,a chea vleev erle nadse rinedor gbaioncihce mmaictearli aslasm hpalvese baelmeno sot vaers 20 2 on June 28, 996 | doi: 10.1 tghahrraoecvhw eap tehcaoos lntoo tgfrf ieictbwhaule t edcsdhecc eitaemodn iecsaste r. byfui.Ec rtgxIieconoin tnit nhitnhgisg a nthi eneowtmfet reiesdnspi tsh caeoicrnvce eo,tr mhiieenps ta ebnriinoeiesc stht heshmeua cisfchi ae clled dnai,sst cepaorenvecdedtrs it oeohsnfe, 163.35.4May 5, 1 wAhltahto ucghhe mnioc aoln aen aisly csilsa imcainng ttehlal t u"sJ uarbaosusitc pPraer-kC—olTuhmeb Riaena lcitiyvi"li zias trioingsh.t 89.e: around the corner, imaginations have been fired by the popularization of by Dat DNA reconstruction and replication. These developments have given rise d n to questions based on new possibilities in archaeological research. Downloade Publicatio froersuePamrlac nhfs.o rfSo prp etrcheiseae lnp irtnaevtsiieotnantt i osanynms dpw oedsriiusec muses wnsiote rnteo ionsfoi tmiathetee dosef i nthn 1ee9w f9o 2rp-e9om3sso itsboti lwcitrioeerask teeir nas in the field, and a call for papers was issued to every major venue of archaeological research worldwide. The resulting program contained papers from every major new area of archaeological research with an emphasis on the pre-Columbian and biochemical aspects. This sympo sium volume is a representative compilation of these papers. As such, it will be of interest to practicing archaeologists, archaeological chemists, anthropologists, historians of science, chemical educators, and all those interested in the story of how chemistry, not without some controversy, can help to trace the roots of humankind and the human environment through the millennia. ix In Archaeological Chemistry; Orna, M.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996. I sincerely thank each author for the time, effort, and cooperation it took to prepare this material for publication. MARY VIRGINIA ORNA Department of Chemistry College of New Rochelle New Rochelle, NY 10805 October 15, 1995 g 1 s.acs.or25.pr00 b6 u0 p://p996- 12 | htt1/bk-1 02 20 2 on June 28, 996 | doi: 10.1 41 163.35.May 5, 89.e: by Dat d n wnloadeblicatio Do Pu x In Archaeological Chemistry; Orna, M.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996. Dedication g 1 s.acs.or25.pr00 THIS VOLUME IS DEDICATED to Lucy Roy Sibley, whose life and work b6 u0 exemplified that of a true scholar, mentor, teacher, and colleague. Her p://p996- contributions to the field of archaeological textiles continue to guide us 12 | htt1/bk-1 toward the future as we strive to understand the lifeways of the past. 02 20 2 on June 28, 996 | doi: 10.1 41 163.35.May 5, 89.e: by Dat d n wnloadeblicatio Do Pu xi In Archaeological Chemistry; Orna, M.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996. Chapter 1 New Directions in Archaeological Chemistry Mary Virginia Orna1 and Joseph B. Lambert2 1Department of Chemistry, College of New Rochelle, New Rochelle, NY 10805 2Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113 org 001 This recent symposium on archaeological chemistry emphasized cs.ch studies in new areas of interest to archaeologists and s.a25. archaeological chemists. Not only are the traditional areas of ub06 metal, glass, pottery, and stone treated, but also archaeological p://p996- soils, fibers, dyes, bone, connective tissue, DNA, and organic 12 | htt1/bk-1 residues. 02 20 on June 28, 6 | doi: 10.1 wpwSrhhoeeermdlnddi -siremnesgna. ojloFiwgro hnrmet e doux nsalea mtubhmpoelr espa, ta obtsrheti egebsa yw n om oftr eoktah noees sfB toAarfbil tlesiicxssihahen nMdltaiefubrisco eS reuacxmtooatr.mt i Weiinsn h atifthliooee r nm 1 trh9uea2sce0te u'ispvm uegsrdap vgowersee erra ietso emimn ta potihne etltuyhirs e 35.42 5, 199 cdoenpcaertrmneedn tws iothf eaxracmhaienoaltoiogny ,o fa nththerior poowlong hyo aldnidn gcsh, emmainsytr yu nfiovuenrsdi tya mlapbloer awtoorrieks biny y 89.163.ate: May elfarxobamomr atihtnoeart irieoespn oh raotssf comofn atchteeerni tabrlaiset enfdnr ioaomln i naetnexcrcineaanvtaito tminoaenlts aa lrswc,h osatreolondmew,e iptdroyet. t ecRroyenc faeenrnedtn cgreelassse saa,nr cadhs s epivenicd iaethlniezcseeedd wnloaded bblication D jAourrcnhaalse oinlo tghiec afile ldC (h1e-m3)is. try Do Pu The modern field of archaeological chemistry arose during the first thirty years after World War II as a result of the development of instrumental methods of inorganic analysis, which made it possible to develop new areas in archaeological chemistry. The methods of choice over the years have concentrated on elemental analysis, whether by atomic absorption or emission, X-ray fluorescence, plasma emission spectroscopy, X- ray powder diffraction, neutron activation analysis or mass spectrometry. These methods have lent themselves to the analysis of stone and lithic artifacts, ceramic materials, glass and metallic materials. Many of the methods of analysis, such as lead isotope provenance studies of marble or elemental provenance studies of obsidian, have passed through several generations of development. Some of the methods survived the tests of validity and of utility. Some have disappeared from the scene, either because the methods had fatal flaws or they did not really solve archaeological problems. Inorganic methods continue to be improved upon and added to, and a large body of literature has developed in this area. 0097-6156/96/0625-0001$12.00/0 © 19% American Chemical Society In Archaeological Chemistry; Orna, M.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996. 2 ARCHAEOLOGICAL CHEMISTRY The task of the archaeological chemist has become more complex than ever over the past decade. Once the domain of analytical chemists turned "amateur archaeologists," effective work in this area demands increasingly sophisticated equipment by way of advanced instrumentation, increased knowledge of statistical software packages for the assembling, processing and interpretation of coherent data- sets, increased interaction with members of related disciplines, awareness of the ever- burgeoning literature of archaeometry, archaeology and anthropology, and perhaps more important than ever, continual interaction and collaboration with members of related disciplines. Chemists working in this area must be aware of the fact that analytical data can be completely meaningless unless it is interpreted within the matrix surrounding the artifact or sample being investigated: professionally executed field work, well-documented excavation, proper sampling technique and meaningful scientific interpretation of the resulting data. Indeed, in the words of Ε. M. Jope (4), in order for any type of work in archaeological chemistry "to be effective, it must be collaborative. Integrations between excavators, investigators of excavated material, g 1 prehistorians and historians, and scientists of all sorts, is now growing, so that we are s.acs.or25.ch00 ifnocrmre.a"s ingly all one family seeking to present the past in a systematized and intelligible b6 u0 p://p996- The Present Symposium 12 | htt1/bk-1 Wthihsi lev molaunmye o, f nthaem geolya,l st ohfe pamstu tvuoalul meedsu cina ttihoins seorfie sc h(5em, (5is)t sc,o ianrccihdaee woiltohg tihstes goanalds of 02 20 anthropologists in the use of new techniques on archaeological substrates and in the on June 28, 6 | doi: 10.1 imcsnuotabneksrterptirsrba eutttehatesitsi do oc nntoo lotl heafce dts ialpoatananr ttoo bfion tpfa atimnhpeieasdrn s dyt hui roenerficeq ttfuhirooeenm. T isn,h ivnietec sisestoi golthiancetlioty acr tshii noorn ievcp oeerre foy spfe a rnoeptrceegedrans n tifi nocy r eta hatnhirdsiss bv hsioaoylscmu hmipetm oebs ieitcuehanmal t 35.42 5, 199 pdoetsescitbiolen tloim aitnsa tlhyazte e bniaoblloegs itchaels ean md eothrogdasn itco mlenadte trhiaelms swelivtehs tuhnei qsuigelnyif tioca snotllvyi nlgo wsoemr e 163.May difficult archaeological problems. 89.e: Hence, the characteristic of the symposium represented by the papers collected y at in this volume was the virtual disappearance of many of the traditional materials wnloaded bblication D ppnDrooiovrttcmieesraieyoldl,niy n so gtrfoes npt hooefer tt aehHndedi s o Stognerlv ayaes tons .fta hrFCc Sohhyream meeoxpilsaootmsrgyiuip'csmla eSl ,o u ainbnnd dA iA vraricrschcihohaaenaoee olooofml goAiegcrtarciiclhc aCa lemh oeCelmoehgtiiesinctmrgaysli s,Co tnrrhgayeam mn-iei zsl/eyt/rd/,y (,bm5 yf)eu ,ttl hlatyhle, e Do Pu two-thirds of the papers were devoted to inorganic materials, whereas only one-half of the papers in Archaeological Chemistry - IV (proceedings of the Eighth Symposium; 6) had inorganic materials as their subject. Of overwhelming interest to the contributors of the symposium that forms the basis of this volume were fibers, dyes, bone, collagen, archaeological soils, DNA analysis, and organic residues from a variety of artifacts including rock paintings and pottery. Two papers dealt with archaeological mineralized plant fiber. Three papers studied the identification of natural dyestuffs used for ancient textiles from Western and Eastern Asia. Ten papers dealt with archaeological bone and collagen, including dating, degradation determinations, analysis of lipid biomarkers, and quantitative measurements to reconstruct paleodiets. Six papers examined nucleotides in archaeological materials, including such technical difficulties as need for extraction, purification and isolation of high molecular weight fragments. The remainder of the papers reported on soil analysis, natural products, copper-based artifacts and pigments, and inorganic and organic residues on artifacts. Two papers each were presented on glass and metals; one paper each was presented on clay, flint, and obsidian. In summary, fully thirty-four of the forty-eight papers submitted for In Archaeological Chemistry; Orna, M.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996.