PigmentsPigments inin ForensicForensic GeologyGeology PigmentsPigments areare thethe coloringcoloring agentsagents mixedmixed withwith aa vehiclevehicle toto makemake coatingcoating suchsuch asas paints,paints, inks,inks, andand cosmeticscosmetics TheThe vehiclevehicle isis thethe bindingbinding agentagent andand inin paintspaints isis usuallyusually anan oiloil suchsuch asas linseedlinseed oil,oil, oror acrylic,acrylic, resin,resin, casein,casein, wax,wax, gum,gum, honey,honey, eggegg yolk,yolk, andand eggegg whites.whites. InIn inksinks thethe bindingbinding agentagent isis commonlycommonly ironiron gall,gall, waterwater withwith gumgum arabicarabic,, andand solublesoluble resin.resin. InIn cosmeticscosmetics thethe binderbinder areare waxeswaxes andand oilsoils PowerPoint Presentation by J. C. Crelling, Southern Illinois University PigmentsPigments inin ForensicForensic GeologyGeology OCHREOCHRE

●● OchreOchre isis aa mineralmineral thatthat hashas beenbeen soughtsought andand usedused byby humanshumans eveneven beforebefore homohomo sapienssapiens camecame intointo existenceexistence

●● ItIt hashas beenbeen usedused as:as: BodyBody paintpaint ArtistArtist paintpaint SunSun blockerblocker MedicineMedicine (antiseptic(antiseptic andand clottingclotting agent)agent) PossiblePossible religiousreligious symbolsymbol forfor blood,blood, life,life, etcetc PigmentsPigments inin ForensicForensic GeologyGeology OCHREOCHRE ●● NaturallyNaturally occurringoccurring minerals:minerals:

HematiteHematite FeFe2OO3

MagnetiteMagnetite FeFe3OO4

LimoniteLimonite FeFe2OO3 *H*H2OO PigmentsPigments inin ForensicForensic GeologyGeology

OCHRE:OCHRE: EvidenceEvidence forfor MiningMining

OchreOchre stickssticks (crayons)(crayons) havehave beenbeen foundfound inin thethe gravesgraves ofof homohomo erectuserectus datingdating toto 1.51.5--1.61.6 millionmillion yearsyears PigmentsPigments inin ForensicForensic GeologyGeology OCHRE:OCHRE: EvidenceEvidence forfor MiningMining

●● 350,000350,000 -- 400,000400,000 yearsyears agoago atat WonderwerkWonderwerk cave,cave, S.S. AfricaAfrica ,, ––ochreochre withwith handhand axesaxes ●● TerraTerra AmataAmata site,site, FranceFrance ochreochre withwith handhand axesaxes PigmentsPigments inin ForensicForensic GeologyGeology OCHRE:OCHRE: EvidenceEvidence forfor MiningMining

●● 250,000250,000 -- 200,000200,000 yearsyears agoago atat HunsgiHunsgi inin SouthernSouthern IndiaIndia ●● 120,000120,000 yearsyears agoago atat LionLion CaveCave ,, Swaziland.Swaziland. ThisThis isis probablyprobably thethe oldestoldest minemine inin thethe world.world. PigmentsPigments inin ForensicForensic GeologyGeology OCHRE: Evidence for Mining Neanderthal Man 150,000 – 32,000 ybp ● Pech de l’Aze , France ● La Chapelle-aux-Saints, France PigmentsPigments inin ForensicForensic GeologyGeology ~35,00~35,00 --10,00010,000 ybpybp Prehistoric Cave Paintings Pigments Used HomoHomo SapiensSapiens Charcoal, lampblack (soot) C Pyrolucite, MnO

Hematite, Fe2O3

Magnetite, Fe3O4

Limonite, Fe2O3 *H2O

There is good evidence that in the cave paintings that many of the colors were a mixture of various pigments, and at the some sites there is evidence that ochre was calcined (heated) to get other colors PigmentsPigments inin ForensicForensic GeologyGeology PrehistoricPrehistoric CaveCave PaintingsPaintings PigmentsPigments inin ForensicForensic GeologyGeology PrehistoricPrehistoric CaveCave PaintingsPaintings PigmentsPigments inin ForensicForensic GeologyGeology MineralMineral PigmentsPigments inin UseUse fromfrom AncientAncient thruthru MedievalMedieval TimesTimes HematiteHematite MagnetiteMagnetite LimoniteLimonite GoethiteGoethite MalachiteMalachite AzuriteAzurite CinnabarCinnabar ChrysocolaChrysocola LapisLapis LazuliLazuli RealgarRealgar OrpimentOrpiment CinnabarCinnabar VerdigrisVerdigris (copper(copper acetateacetate -- AncientAncient Greek)Greek) VanVan DykeDyke BrownBrown (17(17th centurycentury peatpeat extract)extract) PigmentsPigments inin ForensicForensic GeologyGeology OCHREOCHRE ●● NaturallyNaturally occurringoccurring minerals:minerals:

HematiteHematite FeFe2OO3

MagnetiteMagnetite FeFe3OO4

LimoniteLimonite FeFe2OO3 *H*H2OO PigmentsPigments inin ForensicForensic GeologyGeology

GoethiteGoethite FeOFeO (OH)(OH)

CinnabarCinnabar HgSHgS PigmentsPigments inin ForensicForensic GeologyGeology

MalachiteMalachite CuCu2(CO(CO3)(OH))(OH)2

AzuriteAzurite CuCu3(CO(CO3))2(OH)(OH)2 PigmentsPigments inin ForensicForensic GeologyGeology

LapisLapis LazuliLazuli

(Na,(Na, Ca)Ca)8AlAl6SiSi6OO24(S,(S, SOSO4))

ChrysocolaChrysocola

CuSiO3 -nH2O LapisLapis PigmentsPigments MichelangoMichelango VermeerVermeer PigmentsPigments inin ForensicForensic GeologyGeology

OrpimentOrpiment AsAs2SS3

RealgarRealgar AsSAsS PigmentsPigments inin ForensicForensic GeologyGeology

TurquoiseTurquoise

CuAlCuAl6(PO(PO4))4(OH)(OH)8*5H*5H2OO PigmentsPigments inin ForensicForensic GeologyGeology

● TheThe pigmentspigments describeddescribed aboveabove werewere alsoalso usedused inin DarkDark AgeAge andand MedievalMedieval illuminatedilluminated manuscriptsmanuscripts

●● BecauseBecause thesethese mineralmineral pigmentspigments areare alreadyalready oxidizedoxidized oror otherwiseotherwise stablestable atat surfacesurface conditionsconditions theythey retainretain theirtheir originaloriginal brilliancebrilliance eveneven todaytoday

PigmentsPigments inin ForensicForensic GeologyGeology SomeSome DyeDye PigmentsPigments inin UseUse fromfrom AncientAncient thruthru MedievalMedieval TimesTimes IndigoIndigo –– blueblue Note: all dyes used were Woad – blue natural vegetable dyes Woad – blue until 1856 when Perkin PomegranatePomegranate –– yellowyellow developed the first aniline dye from coal tar. This MadderMadder –– orangeorange yellowyellow was a major achievement SaffronSaffron –– yellowyellow orangeorange and the beginning of organic chemistry MurexMurex -- purplepurple PigmentsPigments inin ForensicForensic GeologyGeology SomeSome PigmentsPigments UsesUses inin CosmeticsCosmetics AncientAncient IronIron OxidesOxides GalenaGalena PbSPbS (eye(eye shadow)shadow) MalachiteMalachite (eye(eye shadow)shadow)

CerrusiteCerrusite PbCOPbCO3 ModernModern TitaniumTitanium DioxideDioxide (yellow)(yellow) IronIron OxidesOxides MicaMica (pearlescent(pearlescent agent)agent) BismuthBismuth OxychlorideOxychloride ((pearlescentpearlescent agent)agent) PigmentsPigments inin ForensicForensic GeologyGeology

●● BecauseBecause manymany ofof thethe pigmentspigments areare mineralsminerals standardstandard geologicalgeological techniquestechniques suchsuch asas microscopy,microscopy, XX--rayray diffraction,diffraction, SEMSEM analysis,analysis, andand opticaloptical spectroscopyspectroscopy cancan bebe usedused toto discriminatediscriminate themthem

●● TheThe organicorganic vehiclevehicle oror bindersbinders cancan bebe discriminateddiscriminated byby GasGas ChromatographyChromatography –– MassMass SpectrometrySpectrometry PigmentsPigments inin ForensicForensic GeologyGeology

Thus,Thus, anyany paint,paint, inks,inks, cosmeticscosmetics etc.etc. involvedinvolved inin aa criminalcriminal casecase cancan bebe examinedexamined andand usedused asas potentialpotential evidenceevidence LocardLocard CaseCase

• In 1912 a bank clerk Emile Gourbin in Lyons, France was suspected of the strangulation murder of his girlfriend, Marie Latelle, but he had a good alibi

• Edmond Locard took scrapings from under Gourbin’s fingernails and analyzed them LocardLocard CaseCase • He found rice starch and magnesium sterate (binders?) with bismuth,, zinc oxide, iron oxide, Venetian red pigment

• He then found a druggist in Lyon who had mixed these same ingredients in a custom face powder for Marie Latelle

• When confronted with the evidence Gourbin confessed PigmentsPigments inin ForensicForensic GeologyGeology DatesDates ofof FirstFirst UseUse forfor PaintPaint PigmentsPigments OripmentOripment (yellow)(yellow) ancientancient RedRed OchreOchre ancientancient SmaltSmalt (cobalt(cobalt blue)blue) 15501550 VanVan DykeDyke BrownBrown 16901690 PrussianPrussian BlueBlue 17041704 AlizarinAlizarin (Madder)(Madder) 18301830 ZincZinc WhiteWhite 18501850 TitaniumTitanium WhiteWhite 19201920 ManganeseManganese BlueBlue 19501950 GardnerGardner MuseumMuseum CaseCase

• On 18 March 1990 two white male dressed as Boston Police Officers stole 13 paintings worth over $300 million

• The investigation went cold until two men offered to be intermediaries in getting the paintings back. The offered a few paint chips reportedly from one of the Rembrandt’s as evidence that they were in contact with the thieves GardnerGardner MuseumMuseum CaseCase

• Walter McCrone the head of the famous McCrone labs in Chicago examined the paint chips. He concluded that the paint was consistent with those used by Rembrandt but would not confirm that they were indeed Rembrandt’s

• The case is still unsolved and the 13 paintings are still missing 15001500 ForgeriesForgeries

• In 1985 a trunk containing ~pastels drawings by the modern Russian painter Larionov was discovered

• Larionov left Russia for France in 1915 and these paintings were apparently left behind and forgotten

• When some 200 of these paintings were exhibited in in Germany in 1987 some questions about their authenticity were raised 15001500 ForgeriesForgeries

• A few of the paintings were sent to the McCrone Labs • They were examined by optical microscopy and SEM X-ray analysis

• The paintings were found to have pure rutile TiO2 as a pigment which was not used until at least 1940, thus the paintings were produced after that year and not before 1915 as purported TheThe CaseCase ofof thethe VinelandVineland MapMap

•• InIn 19571957 aa manuscriptmanuscript ““TheThe VinelandVineland MapMap andand thethe TartarTartar RelationRelation waswas offeredoffered forfor salesale inin Geneva,Geneva, Switzerland.Switzerland. ItIt waswas boughtbought byby aa rarerare bookbook dealerdealer whowho soldsold itit toto thethe YaleYale UniversityUniversity librarylibrary

•• TheThe startlingstartling thingthing aboutabout thethe mapmap dateddated atat 14401440 waswas thatthat itit showedshowed NorthNorth AmericaAmerica 5252 yearsyears beforebefore thethe firstfirst voyagevoyage ofof ColumbusColumbus

TheThe CaseCase ofof thethe VinelandVineland MapMap

•• YaleYale publishedpublished thethe manuscriptmanuscript inin 19651965 andand itit waswas anan instantinstant bestbest sellerseller andand aa bookbook--ofof--monthmonth clubclub selectionselection

•• AA newnew editionedition isis stillstill inin printprint TheThe CaseCase ofof thethe VinelandVineland MapMap TheThe mapmap waswas immediatelyimmediately questionedquestioned andand thenthen studiedstudied intenselyintensely PointsPoints puttingputting thethe mapmap inin thethe 1515th centurycentury

1.1. TheThe bindingbinding 2.2. TheThe paperpaper 3.3. TheThe paleographypaleography (writing(writing style)style) 4.4. RadiocarbonRadiocarbon datingdating (1434+/(1434+/-- 11years)11years) 5.5. PIXIEPIXIE analysisanalysis ofof inkink TheThe CaseCase ofof thethe VinelandVineland MapMap

Points questioning the authenticity of the map:

1. McCrone analysis finding anatase a titanium mineral not in use until recently 2. A separate analysis by Raman spectroscopy showing the ink lines with a yellow line containing anatase under the carbon line