Archaeological Chemistry VIII 1 0 0 w 7.f 4 1 1 3- 1 0 2 k- b 1/ 2 0 1 0. 1 oi: d 3 | 1 0 2 5, 1 er b o ct O b): e W e ( at D n o ati c bli u P In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013. 1 0 0 w 7.f 4 1 1 3- 1 0 2 k- b 1/ 2 0 1 0. 1 oi: d 3 | 1 0 2 5, 1 er b o ct O b): e W e ( at D n o ati c bli u P In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013. 1147 ACS SYMPOSIUM SERIES Archaeological Chemistry VIII Ruth Ann Armitage, Editor Eastern Michigan University Ypsilanti, Michigan 1 0 0 w James H. Burton, Editor 7.f 14 University of Wisconsin-Madison 1 3- Madison, Wisconsin 1 0 2 k- b 1/ 2 0 1 0. 1 oi: d 3 | 1 0 2 5, 1 er b o ct O b): e W e ( at D n atio Sponsored by the c bli ACS Division of History of Chemistry u P AmericanChemicalSociety,Washington,DC DistributedinprintbyOxfordUniversityPress In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013. LibraryofCongressCataloging-in-PublicationData ArchaeologicalChemistryVIII/RuthAnnArmitage,editor,EasternMichiganUniversity, Ypsilanti,Michigan,JamesH.Burton,editor,UniversityofWisconsin-Madison,Madison, Wisconsin. 1 0 pagescm.-- (ACSSymposiumseries;1147) 0 w "SponsoredbytheACSDivisionofHistoryofChemistry." 47.f Includesbibliographicalreferencesandindex. 1 1 ISBN978-0-8412-2924-2(alk.paper) 13- 1. Archaeologicalchemistry--Congresses. I.Armitage,RuthAnn.II.Burton,JamesH. 0 2 (JamesHutson),1950-III.AmericanChemicalSociety.DivisionoftheHistoryof k- b Chemistry. 1/ 2 CC79.C5A7342013 0 0.1 930.1--dc23 oi: 1 2013038018 d 3 | 1 0 2 5, 1 ber ThepaperusedinthispublicationmeetstheminimumrequirementsofAmericanNational o ct Standard for Information Sciences—Permanence of Paper for Printed Library Materials, O b): ANSIZ39.48n1984. e W Copyright©2013AmericanChemicalSociety e ( Dat DistributedinprintbyOxfordUniversityPress n o ati AllRightsReserved. ReprographiccopyingbeyondthatpermittedbySections107or108 c bli oftheU.S.CopyrightActisallowedforinternaluseonly,providedthataper-chapterfeeof Pu $40.25plus$0.75perpageispaidtotheCopyrightClearanceCenter,Inc.,222Rosewood Drive,Danvers,MA01923,USA.Republicationorreproductionforsaleofpagesinthis bookispermittedonlyunderlicensefromACS.Directtheseandotherpermissionrequests toACSCopyrightOffice,PublicationsDivision,115516thStreet,N.W.,Washington,DC 20036. Thecitationoftradenamesand/ornamesofmanufacturersinthispublicationisnottobe construedasanendorsementorasapprovalbyACSofthecommercialproductsorservices referenced herein; nor should the mere reference herein to any drawing, specification, chemicalprocess, orotherdataberegardedasalicenseorasaconveyanceofanyright or permission to the holder, reader, or any other person or corporation, to manufacture, reproduce,use,orsellanypatentedinventionorcopyrightedworkthatmayinanywaybe relatedthereto. Registerednames,trademarks,etc.,usedinthispublication,evenwithout specificindicationthereof,arenottobeconsideredunprotectedbylaw. PRINTEDINTHEUNITEDSTATESOFAMERICA In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013. Foreword The ACS Symposium Series was first published in 1974 to provide a mechanism for publishing symposia quickly in book form. The purpose of the series is to publish timely, comprehensive books developed from the ACS sponsoredsymposiabasedoncurrentscientificresearch. Occasionally,booksare 01 developed from symposia sponsored by other organizations when the topic is of 0 w keeninteresttothechemistryaudience. 7.f 4 1 1 Beforeagreeingtopublishabook,theproposedtableofcontentsisreviewed 3- 1 forappropriateandcomprehensivecoverageandforinteresttotheaudience. Some 0 2 k- papersmaybeexcludedtobetterfocusthebook;othersmaybeaddedtoprovide b 1/ comprehensiveness. When appropriate, overview or introductory chapters are 2 0 1 added. Draftsofchaptersarepeer-reviewedpriortofinalacceptanceorrejection, 0. oi: 1 andmanuscriptsarepreparedincamera-readyformat. d 3 | As a rule, only original research papers and original review papers are 1 20 included in the volumes. Verbatim reproductions of previous published papers 15, arenotaccepted. er b o ct O eb): ACSBooksDepartment W e ( at D n o ati c bli u P In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013. Preface The 12th Archaeological Chemistry Symposium was held as part of the Spring ACS National Meeting in New Orleans, Louisiana, April 7–11, 2013. ThisvolumeisacompilationofpresentationsfromtheSymposium,thelatestin alongtraditionthatbeganattheACSNationalMeetinginPhiladelphiain1950. 1 The numbering of the symposia is, however, somewhat in question. According 0 0 pr to Brill (1), “…memories of only the First and Third Symposia remained clear 7. 4 [atthe4thSymposium]…Weleaveit(withablush)tothehistorians…todecide 1 1 3- upontherealityoftheSecondSymposium…” 1 20 The symposium consisted of four half-day symposia, an evening poster bk- session,andakeynoteaddressbyDr. A.MarkPollard,EdwardHallProfessorof 1/ 2 ArchaeologicalScienceandDirectoroftheResearchLaboratoryforArchaeology 0 1 0. and the History of Art at the University of Oxford. We choose four broad 1 oi: categories for the symposia: Pigments, Residues and Material Analysis, X-Ray d 3 | Fluorescence Spectroscopy, and Isotopes in Archaeology. These categories are 01 by no means comprehensive. Rather, they serve as a snapshot perspective of 2 5, archaeological chemistry today and are necessarily biased toward our areas 1 er of expertise and those of the participants in a chemistry meeting. Notably, b cto studies of ancient DNA and other advances in biomolecular archaeology are O b): underrepresentedinthisvolume. e Thepapershereinshowthatarchaeologicalchemistrytodayismorethanthe W e ( usualstudiesoftraceelementsinpotteryandlithics,whichcontinuetocontribute Dat to our understanding of human behavior in the past. New areas of research on include more focus on portability to analyze pigments in situ and artifacts in cati museums, nascent developments in non- and minimally destructive chemical ubli characterization,newapplicationsofisotopicanalyses,andanincreasinginterest P inarchaeologicalbiomolecules. This volume is divided into sections that roughly follow those of the Symposium. The first section, Pigments and Dyes, begins with a review of manuscript pigments by Dr. Mary Virginia Orna, the organizer of the 9th Archaeological Chemistry Symposium and Editor of Archaeological Chemistry: Organic,Inorganic,andBiochemicalAnalysis(2). Eachofthefollowingsections beginswithareviewpaperfromoneofourinvitedspeakers. Dr. ValerieSteele, nowattheUniversityofBradfordintheDepartmentofArchaeologicalScience, provides an overview of the state — for better and for worse — of analyses of archaeological residues. Portable X-ray fluorescence instruments are becoming extremely common in archaeological chemistry investigations; Dr. Aaron ShugarofBuffaloStateUniversityprovidesinhischaptersomeperspectivesand warningsagainsttheindiscriminateuseofthistechnology. Finally,Dr. Matthew xi In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013. Sponheimer gives an overview of the contributions of stable carbon isotope and tracemetalstudiesinunderstandingearlyhominindiets. The final chapter of the book provides a perspective on the earliest work in archaeological chemistry in the 18th century and brings us up to today’s challenges. We find ourselves in Dr. Pollard’s text, carrying out our own research“onawingandaprayer,”asboththesolitarychemistsupportedbyher institution in part for the accessible public interest aspect of her research and a scientist within an anthropology department, fighting for funding in this era of sequestration and downsizing. We hope that this volume contributes toward the “open,respectful,meaningfulanditerativedialogueacrossthemanydisciplinary boundaries”encounteredinarchaeologicalchemistry(3). We thank all of the contributors and reviewers for their time and effort. We especially thank technical editor Arlene Furman of ACS Books for her 1 0 0 patience and help in producing this volume, and Seth Rasmussen, Tom Strom, pr 7. andVeraMainzfromtheDivisionoftheHistoryofChemistry(HIST)foralltheir 4 1 1 help in organizing and running the Symposium. HIST and the ACS Divisional 3- 1 Activities Committee provided the majority of the funding for the Symposium, 0 2 k- withadditionalsupportfromtheSocietyforArchaeologicalSciencesandBruker b 1/ Corporation. 2 0 1 0. 1 oi: d References 3 | 1 0 2 5, 1. Brill, R. H. In Science and Archaeology; Brill, R. H., Ed.; MIT Press: 1 er Cambridge,MA,1968,px−xi. ob 2. Archaeological Chemistry: Organic, Inorganic, and Biochemical Analysis; ct O Orna,M.V.,Ed.;ACSSymposiumSeries625;AmericanChemicalSociety: b): Washington, DC,1996. e W e ( 3. Pollard, A. M. In Archaeological Chemistry VIII; Armitage, R. A., Burton at J. H., Eds.; ACS Symposium Series 1147; American Chemical Society: D n Washington, DC,2013. o ati c bli u P RuthAnnArmitage Professor,DepartmentofChemistry,EasternMichiganUniversity Ypsilanti, Michigan48197 734-487-0290(telephone) [email protected](e-mail) JamesH.Burton Director,LaboratoryforArchaeologicalChemistry,DepartmentofAnthropology 1180ObservatoryDrive,UniversityofWisconsin-Madison Madison, Wisconsin53706 608-262-4505(telephone) [email protected](e-mail) xii In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013. ©2013AmericanChemicalSociety inmanuscriptsbetweenthe10thand16thcenturiesforthefollowingpurposes: theirera. Thispaperwillreviewthescientificidentificationofartists’colorsused pursuitofcraftingthemanuscriptstheyhandedontousasprecioustreasuresof yet to come, color, for them, was the most visual and pervasive reality in their observationsincetheformaldisciplineofchemistrywouldnotexistforcenturies ourlives”(1). Thoughmedievalartistscouldnothaverealizednorexpressedthis “Coloristhemostvisual,pervasiveexampleoftheimportanceofchemistryto Introduction medievalmanuscriptsisalsodiscussed. pigment usage. The technical future of chemical analysis of 01 involvedwithhandlingmanuscriptsdirectly,andanachronistic 0 ch usage between Armenian and Byzantine artists, the problems 7. 4 several important artists’ pigments, the difference in pigment 1 1 3- manuscript production, clarifying periods of known usage of 1 20 influence and interconnection between medieval centers of bk- collaborative building of a pigment database, tracing lines of 1/ 2 more about the artistic process itself. This paper reviews the 0 1 0. profound,importancetothehistorianasatoolforunderstanding 1 oi: analysis of pigments can have a broader, and perhaps a more d 3 | painting practices of the artist or period. In addition, the 01 or dating of a painting based on comparison with the known 2 5, main purposes. It can confirm or deny the alleged attribution 1 er Forthearthistorian,chemicalanalysisofpigmentsservestwo b o ct O b): e W e ( *E-mail: [email protected] Dat NewRochelle,NewYork10805,U.S.A. on DepartmentofChemistry,TheCollegeofNewRochelle, ati c Publi Mary Virginia Orna* Connections—A Review Manuscripts: Tracing Artistic Influences and Artists’ Pigments in Illuminated Medieval Chapter 1 In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013. 4 workshops: oneusedazurite(basiccopper(II)carbonate)andhighqualitynatural theemploymentofthebluepigmentsindicatedtheinvolvementoftwodifferent specifyingattributionsamongdifferentpaintersinthemanuscript. Differencesin onlyyieldedhelpfulinformationregardingconservation, butalsowashelpfulin Analysis of the Gladzor (Glajor is an alternative spelling) Gospel Book not preciousdocuments. helpful to curators and conservators who must control the handling of such virtuallylightfastoverindefiniteperiodsoftime. Suchanalysesareenormously work from light would not be a principal concern since mineral pigments are was used extensively in the manuscript, one could safely say that shielding the usedextensivelyfromancienttimes(6). Sinceneitheroftheseorganicpigments colorant taken from the sap or ooze of trees of the genus Garcinia. It, too, was substrate such as aluminum hydroxide (5). Gamboge was another plant-derived often used as a dye, it could also be used as a pigment if precipitated on a solid 1 0 0 describedbyStrabo,PlinytheElder,DioscoridesandtheTalmud. Thoughmost h c 7. of the Rubiaceae family. It has been known from ancient times, having been 4 11 MadderwasderivedfromtherootsoftheRubiatinctorumandothermembers 3- 1 TableI;examplesoftwoofthepigmentsisshownbelowinFigure1. 0 k-2 thetwomasterpainters(3,4). Asummaryofpigmentusagebyatelierisgivenin b 1/ usedbythethree“apprentice”artistswhoworkedinanatelierotherthanthatof 2 10 employedbyallfiveoftheartistswhoworkedonthemanuscript,andofgamboge, 0. 1 were of mineral origin with the exception of red (madder) lake, which was doi: ratherstartlinginformation: virtuallyallofthepigmentsusedinitsmanufacture 3 | transforminfraredspectroscopyandrefractiveindexmeasurementsyieldedsome 1 0 2 of very extensive study. Analysis of its palette by X-ray diffraction, Fourier 5, 1 The Gladzor Gospel Book (Armenian MS 1, UCLA) has been the subject er b o ct Pilot Project: The Gladzor (Glajor) Gospel Book of UCLA O b): e W ate ( early10thcenturytothelate16thcentury. D n Armenian and Byzantine workshops; the dates of their creation range from the o ati Themanuscriptsdescribedandanalyzedinthisworkcamefromavarietyof c bli insitu. Thevalueofthesemethodswillbediscussedlaterinthispaper. u P ofnewer,non-invasivetechniquesthatallowtheanalystaccesstothemanuscript of refractive index, this approach is now questionable in light of the availability analysis by means of X-ray diffraction, infrared spectroscopy and measurement method used and described here consisted of extracting minute samples for objective description of method, and restoration. Although the identification In addition to these objectives, Robert Feller (2) lists two additional ones: • Tospecifyattributionsamongdifferentpaintersinamanuscript. • Touncoverforgeries(de-authentication); • Torecommendconservation&handlingpracticebasedonthecontent; cultures; • To trace lines of influence between and among painting schools and • Todetermineorconfirmplaceoforiginanddate; In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013. 5 orpiment,gambogeandmassicot massicot,orrealgarmixedwith Yellow Orpiment Gamboge,ororpimentmixedwith White Calcinedbonemixedwithquartz Whitelead Red Vermilion Vermilion Purple Ultramarinemixedwithredlake 01 minium 0 h Orange Miniumororpimentmixedwith c 7. 4 1 Olive Gamboge 1 3- 1 whitelead 0 k-2 Magenta Redlakeorredlakemixedwith Redlake b 21/ traceofvermilion 0 1 withultramarine ultramarineplusanhydriteanda 0. 1 Green Orpimentmixedwithazuriteor Orpimentmixedwithgambogeor oi: 3 | d Gold Gold Gold 1 0 gamboge,gypsumandanhydrite 2 5, Flesh Orpimentmixedwithrealgar Orpimentmixedwithrealgar, 1 ber whitingandhydratedironoxide o ct gypsumandcharcoalblack orpiment,gypsum,charcoalblack, O b): Brown Vermilionmixedwithorpiment, Vermilionmixedvariouslywith e W Blue Azurite;Ultramarine Ultramarine+UltramarineAsh e ( at Black Charcoalblack Charcoalblack D n o Hue “MasterPainter”Atelier “Apprentice”Atelier ati c bli TableI.PigmentsListedbyAtelierasUsedintheGladzorGospelBook(3,4) u P amongthepigmentsofthefirstworkshop(4). workshop. Likewise, gamboge, used in the second workshop was not found and ultramarine; this occurred nowhere in the miniatures attributed to the first workshop also used a purple pigment that consisted of a mixture of red lake ultramine, while the other used lesser quality natural ultramarine. The second In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.