The use of mobile Raman spectroscopy to compare three full-page miniatures from the breviary of Arnold of Egmond - Deneckere e.a. RAMAN Egmond Breviary

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The use of mobile Raman spectroscopy to compare three full-page miniatures

from the breviary of Arnold of Egmond

Deneckere, A.; Leeflang, M.; Bloem, M.; Chavannes-Mazel, C.A.; Vekemans, B.; Vincze, L.;

Vandenabeele, P.; Moens, L.

DOI

10.1016/j.saa.2011.08.016

Publication date

2011

Document Version

Final published version

Published in

Spectrochimica acta. Part A: Molecular and biomolecular spectroscopy

Link to publication

Citation for published version (APA):

Deneckere, A., Leeflang, M., Bloem, M., Chavannes-Mazel, C. A., Vekemans, B., Vincze, L.,

Vandenabeele, P., & Moens, L. (2011). The use of mobile Raman spectroscopy to compare

three full-page miniatures from the breviary of Arnold of Egmond. Spectrochimica acta. Part

A: Molecular and biomolecular spectroscopy, 83(1), 194-199.

https://doi.org/10.1016/j.saa.2011.08.016

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ContentslistsavailableatScienceDirect

Spectrochimica

Acta

Part

A:

Molecular

and

Biomolecular

Spectroscopy

j o ur na l h o me p ag e :w w w . e l s e v i e r . c o m / l o c a t e / s a a

The

use

of

mobile

Raman

spectroscopy

to

compare

three

full-page

miniatures

from

the

breviary

of

Arnold

of

Egmond

A.

Deneckere

a,∗

_,

_M.

_Leeflang

b

_,

_M.

_Bloem

c

_,

_C.A.

_{Chavannes-Mazel}

c

_,

_B.

_Vekemans

d

_,

L.

Vincze

d

_,

_P.

_Vandenabeele

e

_,

_L.

_Moens

a

a_{GhentUniversity,RamanSpectroscopyResearchGroup,DepartmentofAnalyticalChemistry,Krijgslaan281,S12,B-9000Ghent,Belgium} b_{MuseumCatharijneconvent,LangeNieuwstraat38,NL-3503Utrecht,TheNetherlands}

c_{UniversityofAmsterdam,LeerstoelgroepKunstgeschiedenisvandeMiddeleeuwen,Herengracht286,NL-1016Amsterdam,TheNetherlands}

d_{GhentUniversity,X-rayMicrospectroscopyandImagingResearchGroup,DepartmentofAnalyticalChemistry,Krijgslaan281,S12,B-9000Ghent,Belgium} e_{GhentUniversity,ResearchUnitinArchaeometry,DepartmentofArchaeology,Sint-Pietersnieuwstraat35,B-9000Ghent,Belgium}

a

r

t

i

c

l

e

i

n

f

o

Articlehistory: Received2May2011 Accepted10August2011 Keywords: Ramanspectroscopy Mediaevalmanuscripts Pigments Directanalysis

a

b

s

t

r

a

c

t

TheBreviaryofArnoldofEgmondisoneofthemostwealthilyilluminatedfifteenthcenturymanuscripts intheNorthernNetherlands.Themanuscriptoriginallycontainedanumberoffull-pageminiatures, whichwereallremovedatanunknowndatebefore1902.Thethreeremainingminiaturesstudiedhere, aretodaypartofdifferentcollections,buttheywerebroughttogetherforanexhibition.Althoughseveral historicalandarthistoricaldetailsofthisbreviaryhaveextensivelybeenstudied,noexaminationofthe materialsusedwasundertakenbefore.Analyticaltechniques,suchasmobileRamanspectroscopy,canbe usedtocharacteriseandidentifythesematerialsinanon-invasiveway.Thispaperpresentstheresultsof theinsituRamananalysisofthreefull-pageminiaturesoftheBreviaryofArnoldofEgmond.Duringthis study,differentpigmentscouldbeidentified,suchasleadwhite(2PbCO3·Pb(OH)2),lead–tinyellowtypeI

(Pb2SnO4),ultramarine(Na8–10Al6Si6O24S2–4),massicot(PbO),vermilion(HgS)andredlead(Pb3O4).Next

toidentificationofthepigments,visualanalysiswasusedtodetectdifferencesandsimilaritiesbetween thestylisticelementsofthethreeanalysedfolios.

© 2011 Elsevier B.V. All rights reserved.

1. Introduction

For art historians,it is important to have knowledge ofthe materials (pigments, binding media, substrates, etc.) and their provenance;tounderstandtheancienttechniques;tolocateand attributethemanuscripttoaparticularartistorworkshop;orto dateamanuscript.Althoughseveralhistoricaldetailsofmediaeval manuscriptshavebeenstudiedextensively,theexaminationofthe materialsusedisstillinitsinfancy.Theinvestigationofmanuscripts byspectroscopictechniquesisimportanttochecktheir conserva-tionstate,tounderstandthecausesofdegradationandtoplanan accurateconservationorrestoration.

In comparison with other spectroscopic techniques, Raman spectroscopyhasanumberofadvantages:thetechniqueis non-invasive,nopre-treatmentofthesampleisnecessaryandmixtures canbeinvestigated.DuetotheseadvantagesRamanspectroscopy wasproventobeaninterestingtoolfortheexaminationofworksof art[1],inparticularmanuscripts.TheRamanspectroscopicanalysis

∗ Correspondingauthor.Tel.:+3292644845;fax:+3292644960. E-mailaddress:Raman@ugent.be(A.Deneckere).

ofmanuscriptshasbeenmainlyconcernedwithpigment identifi-cation,gatheringinformationaboutthepigmentpalette[2,3]used fortheilluminationsorapigmentpaletteofaspecificartist[4]. Asaresultoftheidentificationofthepigments,alsoanachronisms canbetraced[5]andinformationontheevolutionofthepigment use[6]canbegathered.Nexttotheidentificationofthepigments, alotofspectroscopicresearchesfocusontheidentificationofthe degradationproductsfoundonthemanuscript,inorderto pro-tectthe manuscript againstfurtherdegradation. Someof these degradationprocessesresultinacolourchangeofthepigment:the light-induceddegradationofrealgar(red)intopararealgar(yellow)

[7],thedegradationofredleadintogalena(grey)anddegradation ofanalloyofcopper,leadandzinc(gold)intoacoppercarboxylate (green)[8,9].Nexttothespectroscopicanalysisofthepigments, alsoanalysisoftheink[10,11]canbeperformed.

Inthisstudy,amobileRamanspectrometerwasusedtoanalyse thethreedifferentfolios.Inspiteofastrongfluorescence back-ground,differentpigmentswereidentified,obtainingimportant informationonthepigmentpaletteusedfortheilluminationofthe differentfolios.Theidentificationofthepigmentswasusedasan additionalargumenttodetectdifferencesandsimilaritiesbetween thethreeanalysedfolios.

1386-1425/$–seefrontmatter © 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.saa.2011.08.016

Fig.1.Pictureoftheexperimentalset-upoftheMobileArtAnalyser(MArtA)inthe conservationdepartmentoftheMuseumHetValkhof.

1.1. TheBreviaryArnoldofEgmond

The Breviary of Arnold of Egmond is one of the most wealthilyilluminatedfifteenthcenturymanuscriptsinthe North-ernNetherlands.Themanuscriptconsists,initspresentstate,of433 folios;containingbeautifullydecoratedmargins,consistingofthin bars,inhabitedbymanysmallflowers,animals,monsters,human figures,hybridcreaturesandlushacanthusleaves[12](Fig.1). Illu-minatingthislargemanuscriptwastoomuchforoneartistoreven forasingleworkshoptohandle,thereforetheilluminationswere executedbyatleasttwodifferentworkshops:onegroupofartists workinginthestyleoftheMasterofZwedervanCulemborgand theothergroupworkinginthestyleoftheMastersofOttovan Moerdrecht.Onfolio324rinthebreviary,themalecommissioner ofthemanuscriptisdepictedkneelinginfrontofSt.Nicholas.For alongtimenobodycouldidentifythepatronofthemanuscript, exceptthathewasaGueldersduke,becauseofthearmsofGuelders andJülich,implementedinthemanuscript.Inolderliterature[12], themanuscripthasbeendatedtotheperiodbetween1420and 1430.Consideringthis period,thepatron couldbe: ReginaldIV DukeofGuelders(†1423),RupertvonBerg(†1433)andArnold ofEgmond(†1471),thehusbandofCatherineofCleves[13]. How-ever,whenlookingattheminiaturesmadebytheZwederMasters (Fig.2(b)),welldevelopedlandscapesandmasterfullyappliedfine brushstrokessuggestamaturedstyle.Furthermore,influencesof theFlemishpaintingtechniqueoftheearly1430scanbedetected, makingadatearound1435morelikely[13].

The manuscript originally contained a number of full-page miniatures,whichwereallremovedatanunknowndatebefore 1902.Threeofthemremainedandarethesubjectofthisstudy.

2. Experimental

2.1. Theanalysedfolios

Thethreeanalysedfoliosbelongtodifferentinstitutions(the FitzwilliamMuseuminCambridge(UK)(Fig.2(a)),theUniversity Libraryof Utrecht(TheNetherlands)(Fig.2(b))andtheLondon BritishLibrary(UK)(Fig.2(c)))andwerebroughttogetherforthe exhibition‘ThehoursofCatherineofCleves:devotions,demonsand dailylifeinthefifteenthcentury’(MuseumHetValkhof,Nijmegen, TheNetherlands,10/10/2009–4/01/2010).Theexaminationswere performedintheconservationdepartmentofthemuseum,during orshortlyafterthedismantlingoftheexhibition(Fig.1).

Thefirstanalysedfolio(318),originallyformingf.318inthe bre-viary,depictsKingSalomonintheTemple(FitzwilliamMuseum),

thesecondanalysedfolio(104),showsTheStoningofSaintStephen (BritishLibrary)andthelastanalysedfolio(202),presentsThe Res-urrectionofChrist(UniversityLibraryofUtrecht).

2.2. MobileRamanspectroscopy

InsituRamanspectroscopywasperformedonthethreeselected miniatures.Thepositionsoftheanalysed pointswere conscien-tiously marked on prints of the miniatures. Sampling was not allowed.Analysiswasperformedinadarkenedroominthe con-servationdepartmentofthemuseum.

RamanspectrawereobtainedusingtheMobileArtAnalyser (MArtA)[14].ThisspectrometercontainsaportableRaman imag-ingmicroscope (Spectracode,WestLafayette, IN,UnitedStates) andaSpectraPro150if.15spectrometer(Roperscientific, Prince-tonInstruments).Moredetailedinformationoftheinstrumenthas beendescribedelsewhere.

Themeasurementswereexecutedusinga600-grooves/mm dis-persiongratinganda785nmdiodelaser.Spectrawereobtainedin thespectralregionbetween100and2500cm−1.A6×objective lenswasused,givingaclearanceofapproximately5mmabove themanuscriptsurface. Theselectedmeasurement pointofthe manuscriptcouldbeobservedthroughadigitallycontrolledcolour camera incorporated in the probe head.Micro-positioning and focussingwasachievedusingtheflexiblearmandthemanually controlledmicro-positioners.Usingthe6×objectivelens,aspot sizeofapproximately50␮mwasachieved.Extremecarewastaken toavoiddamagingtheilluminationwiththelaserbeam:by adjust-ingthelasercurrent,everymeasurementstartedwithaverylow laserpower.Whennecessary,thepowerwascarefullyincreasedin ordertoimprovethesignal-to-noiseratio.

3. Resultsanddiscussion

3.1. Visualexaminationbasedonstyle

AsmentionedbeforetheilluminationsintheBreviaryofArnold ofEgmondwereexecutedbyatleasttwodifferentworkshops[12]

theMastersofZwedervanCulemborgandtheMastersofOttovan Moerdrecht.Bothgroupshavethesameidea,buttheilluminations oftheMoerdrechtMastersaremoreprimitiveandrigid.Theyalso makeuseofuniformcolourfields,whichmakesthefigureslooklike puppets(Fig.3(a)).Incontrary,theMastersofZwedervan Culem-borgusedifferentpaintlayerstocreatedepthandcontrast.Asa resultofthis,thefigureslookmorenaturalandhuman(Fig.3(b)).

[12]

Since the full-page miniatures were removed from the manuscripta longtimeago,theconditionof thesefolios is dif-ferentfromtheilluminationsintheBreviaryofArnoldofEgmond itself.Thepaintlayersoftheloosefolioshavesufferedsome dam-age,wherethesurfacesareworn.Thereforetheclassificationbased onlyonthestylisticexaminationofthefacesisdifficult.

Basedonthestylisticstudy,thefolioswithTheResurrectionof Christ(Fig.2(b))andTheStoningofSaintStephen(Fig.2(c)),belong tothesameworkshop,asthesamebackgroundisusedforboth miniaturesandasthepaintingstyleoftheplantsandthebuild-up ofthefacesissimilar.TheyarepaintedinthestyleoftheMasters ofZwedervanCulemborg.

Oppositetothis,folio318withKingSalomonintheTemple (Fig.2(a)),showssomewhatadifferentstyle:thefiguresattheside arerathershapeless,thefromandbuild-upofthefacesisdifferent andthereisalmostnoshadowinthefigure.

Althoughthisminiatureisalsopaintedinthestyleofthe Mas-tersofZwedervanCulemborg,itcouldhavebeenexecutedbya differenthandthanthetwootherfolios[15].

Fig.2.Picturesofthethreeanalysedminiatures:(a)KingSalomonintheTemple(FitzwilliamMuseum),(b)TheResurrectionoftheChrist(UniversityLibraryofUtrecht); and(c)TheStoningofSaintStephen(BritishLibrary).

Fig.3. Picturesoftwofoliospaintedbytwodifferentstyles:(a)thestyleoftheMastersofOttovanMoerdrecht;and(b)thestyleoftheMastersofZwedervanCulemborg. 3.2. AnalysiswithmobileRamanspectroscopy

Table1givesanoverviewoftheidentifiedpigmentonthethree analysedfolios.

3.2.1. Whitecolour

Thewhitepigmentusedforthethreefolioscouldbeidentifiedas leadwhite(2PbCO3·Pb(OH)2).Fig.4(a)showstheRamanspectrum

ofleadwhite,withthecharacteristicRamanbandofthe symmet-ricstretchvibrationofCO3−at1050cm−1.Leadwhitehasbeen

byfarthemostimportantofthewhitepigmentsusedinEurope fromtheRomanperiodtillthe19thcentury,whenitwasreplaced

bylesstoxicpigmentssuchaszincwhite.Basicleadcarbonateis thechemicalequivalentofthenaturalhydrocerrusite. However, hydrocerrusiteisextremelyrareandconsequentlybarelyusedas pigmentsource,whichimplementsthatalreadysincetheRoman periodthesyntheticequivalentwasusedaspigment[16]. 3.2.2. Yellowcolour

Lead–tinyellowtypeI(Pb2SnO4)couldbeidentifiedasthe

yel-lowpigmentusedinthethreedifferentfolios.Fig.4(b)showsthe Ramanspectrumoflead–tinyellowtypeI,withthecharacteristic Ramanbandsat:527,457,378,337,293,279,201and136cm−1. Leadtin yellowtype Iis foundwidelyin paintings throughout

Table1

Overviewoftheidentifiedpigmentsofthethreeanalysedfolios:TheStoningofSaintStephen,TheResurrectionofChristandKingSalomoninthetemple.

Colour f.104 f.202 f.318

White Leadwhite Leadwhite Leadwhite

Yellow LeadtinyellowtypeI LeadtinyellowtypeI LeadtinyellowtypeI

Blue Lapislazuli / /

Green LeadtinyellowtypeI+ultramarine LeadtinyellowtypeI /

Grey / Leadwhite+leadtinyellowtypeI /

Brown / Massicot /

Red Redlead,vermilion Redlead,vermilion Redlead,vermilion

Fig.4.Ramanspectra(6× objective,1× 60s,10%laserpower)of:(a)thewhite pig-mentleadwhite(2PbCO3·Pb(OH)2),(b)theyellowpigmentlead-tinyellowtypeI

(Pb2SnO4);and(c)thebluepigmentultramarine(Na8–10Al6Si6O24S2–4).(For

inter-pretationofthereferencestocolorinthisfigurelegend,thereaderisreferredtothe webversionofthearticle.)

Europefromthe14thcenturyuntilthefirsthalfofthe18th cen-tury.Itdoesnotappeartohavebeenusedinotherplacesorcultures unlessspecifictradewithEuropetookplace[16].

3.2.3. Bluecolour

OnlyforTheStoningofSaintStephen,thepreciouspigmentlapis lazuli(Na8–10Al6Si6O24S2–4)couldbeidentified.Thispigmentwas

foundonthegarmentofthemalefiguredepictedontherightside ofthefolio(Fig.2(c)point1).Thismalefigurecouldbe identi-fiedasKingSaul[15].Theimportanceofthismalefigureisalso confirmedbythepresenceoflapislazuli,whichwasavery expen-sivepigmentinthe15thcenturyandwasonlyusedforimportant orholyfigures.Foralltheotherbluecoloursonthethreefolios wewerenotabletoidentifythebluepigmentwithRaman spec-troscopy.Probablythepigmentusedfortheseblueareasisazurite (2CuCO3·Cu(OH)2).Azuritehasasimilarcolouraslapislazuli,but

wasmuch cheaperduringthe15thcentury.Unfortunately azu-rite is a very weak Ramanscatter and is therefore difficult to detectwithRamanspectroscopy,especiallyduringinsitu measure-ments.

Fig.4(c)showstheRamanspectrumoflapislazuli,withthe char-acteristicRamanbandat547cm−1.ThisRamanbandiscausedby the␯(S–S)2−_{symmetricstretchingmode.Thepigmentlapislazuliis}

sometimesalsonamedultramarine,atermofhistoricalimportance usedsinceAntiquity.Additionally,thistermisalsousedfor artifi-ciallypreparedpigmentsofsimilarcomposition.Consequently,the qualifications‘natural’and‘synthetic’arefrequentlyusedto differ-entiatebetweenthetwotypes.Thepigmentusedforthisminiature ismostlikelynaturalultramarine,asthefirstcommercial produc-tionofsyntheticultramarinedatesfrom1828.Ramanspectroscopy isnotabletodistinguishbetweennaturalandsynthetic ultrama-rineinpaintlayers[16].

Fig.5.Ramanspectra(6×objective,1×60s,10%laserpower)of:(a)thegreen colour,whichisamixtureofultramarine(Na8–10Al6Si6O24S2–4)andlead–tinyellow

typeI(Pb2SnO4);(b)thegreycolour,whichisamixtureoflead–tinyellowtypeI

(Pb2SnO4)andleadwhite(2PbCO3·Pb(OH)2);and(c)thebrowncolour,forwhich

massicot(PbO)wasused.(Forinterpretationofthereferencestocolorinthisfigure legend,thereaderisreferredtothewebversionofthearticle.)

3.2.4. Greenandgreycolour

ThegreencolourusedonTheStoningofSaintStephen(Fig.2(c) point2),couldbeidentifiedasamixtureoflapislazuliandlead–tin yellowtypeI.TheRamanspectrum(Fig.5(a))showsthe character-isticRamanbandat547cm−1ofultramarineandtheRamanbands oflead–tinyellowtypeI:279,201and136cm−1.

ForthegreycolouronTheResurrectionofChrist(Fig.2(b)point 1),amixtureoflead–tinyellowtypeIandleadwhitecouldbe iden-tified.TheRamanspectrum(Fig.5(b))showsacombinationofthe mostintenseRamanbandoflead–tinyellowtypeI(136cm−1)and thecharacteristicRamanbandsofleadwhite(1050and110cm−1). 3.2.5. Browncolour

ThepigmentusedforthebrowncolouronTheResurrectionof Christ(Fig.2(b)point2),couldbeidentifiedastheyellowpigment massicot(PbO).Theredpigmentusedinthemixturetogetthe browncolourhuecouldnotbeenidentified.Massicothas charac-teristicRamanbandsat276and142cm−1(Fig.5(c)).Itoccursassoft yellowearthymassesinassociationwithleadoredeposits world-wide[16].Massicotiscurrentlyusedtorefertotheorthorhombic lead(II)oxidemineralwithcompositionPbO.Incontrary,litharge

[16]isusedtoreferthetetragonallead(II)oxidemineralwith com-positionPbO.Lithargehasalsoayellowcolour,butisinthecontext ofpaintingtechnique,itismentionedasdriersaddedtooil.Traces oflithargewerealsofoundasimpuritiesinredlead[17].Redlead referstotheredlead(II,IV)oxidemineralwithcompositionPb3O4

(minium)[16].

3.2.6. Redcolourandincarnation

Fortheredcolourtwopigmentscouldbeidentified:redlead (Pb3O4)(Fig.6(a))andvermilion(HgS)(Fig.6(b)).Vermilionwas

perhapstheRomans’mostvaluablepigment,itwasusedin ambi-tious works and proved great wealth [16]. During the Middle

Fig.6.Ramanspectra(6× objective,1×60s,10%laserpower)oftwoidentifiedred pigments:(a)vermilion(HgS)and(b)redlead(Pb3O4).(Forinterpretationofthe

referencestocolorinthisfigurelegend,thereaderisreferredtothewebversionof thearticle.)

Agestheexpensivepigmentvermilionwasthereforesometimes replacedbya cheaperpigment,namelyredlead.Redlead com-monlyoccursinsmallamountsasabrightredororangepowderor crustformedasasecondarymineralintheweatheringzonearound leadoredeposits.Themineralmayhavebeenusedasapigment inancienttimesalthoughthesyntheticanaloguewasoneofthe firstpigmentstobemanufactured[16].Thepreparationofthe syn-theticredleadfromleadwhitewasalreadyknownintheGreekand Romantimes.Inthe15thcenturyredleadwasderivedfromlead metalinatwostageprocessofwhichlithargewastheintermediate product[18].

OnKingSalomonintheTemple,vermilionwasonlyfoundonthe altar(Fig.1(a)point1).Foralltheotherredpartsofthefolio,redlead wasidentifiedasredpigment.Theseresultsleadtothe assump-tionthatthemoreexpensivevermilionwasonlyusedfortheholy objects,suchasthealtar.OnTheResurrection,thesame assump-tioncouldbemade:themoreexpensivevermilionwasfoundin thewoundsofChrist(mixedwithleadwhite)(Fig.2(b)point3and 4).

BasedonthisinformationweassumedthatonTheStoningof SaintStephen(Fig.2(c))notracesofvermilionwouldbe identi-fied,becausenoredcolourwasusedfortheHolyfiguresKingSaul (depictedontheleft)andSaintStephen(depictedinthemiddle). Nevertheless,vermilionwasfoundforthecolouringofthegarment layingontheground,whichisdepictedinthebackoftheminiature (Fig.2(c)point3).Foralltheotherredpartsredleadwasidentified aspigment.

Thehierarchicalcolourusecanonlybefoundonthefirsttwo folios,whileforthe3rdfolioagarmentlayinginthebackofthe foliowaspaintedwiththemoreexpensivevermilion.This infor-mationabouttheidentificationoftheredpigments,maypointin thedirectionthatonlyKingSalomonintheTempleandThe Resur-rectionofChrist,weremadebythesameworkshopandthatfolio 104,TheStoningofSaintStephen,waseventuallymadebyanother hand.

3.3. Interpretationoftheresults

BasedonstylisticexaminationTheResurrectionofChristand TheStoningofSaintStephen,wereassignedtothesamehandin theworkshop, whileKingSalomonintheTempleprobablywas madebyadifferenthand,workinginthestyleoftheMastersof ZwedervanCulemborg.However,basedontheidentificationofthe redpigmentsbyRamanspectroscopy,KingSalomonintheTemple andTheResurrectionofChristweremadebythesamehand,while

TheStoningofSaintStephen,mightbemadeinanotherhand.Next tothehierarchalcolouruseoftheredpigments,alsohierarchical colouruseofthebluepigmentscanberetrieved.For The Ston-ingofSaintStephen,thebluepigmentusedforthegarmentofthe KingSaulisthemoreexpensiveultramarine.Thisresultsin con-tradictionintheclassificationbasedontheidentificationofthered pigmentsand,evenmoreimportant,differentoftheclassification basedonstylisticcomparisons.

The possible explanation for this difference in classification couldbefoundinapassageonthestoningofSaintStepheninthe Bible:58Thentheycasthimoutofthecityandstonedhim.Andthe

witnesseslaiddowntheirgarmentsatthefeetofayoungman

namedSaul.59AndastheywerestoningStephen,hecalledout,“Lord Jesus,receivemyspirit.”60Andfallingtohiskneeshecriedoutwitha loudvoice,“Lord,donotholdthissinagainsthim.”Andwhenhehad saidthis,hefellasleep[Acts7:54].

Inthispassage,onlythewitnesseslaiddowntheirgarment,but itcouldbethatthegarmentinthebackvisualisesthegarmentof theHolyStephen,andthereforethemoreexpensivevermilionwas used.

Combiningalltheseresultsleadtothefollowingconclusion: thethreefoliosareprobablymadeinthesameworkshop, follow-ingthestyleoftheMastersofZwedervanCulemborg,wherethe artistsrespectedthehierarchalcolouruse. KingSalomonin the Temple,showssignificantstylisticdifferenceswiththetwoother folios.Ramanspectroscopicanalysiswasnotabletoidentify differ-encesbetweenthedifferenthands.Furtherresearchonthepigment useinworkshopshastobeperformed.

4. Conclusions

Inthiswork,insituRamanspectroscopywasusedto investi-gatethecolourpaletteofthreedifferentfull-pageminiaturesfrom theBreviaryofArnoldofEgmond.Althoughitisclearthatonce theseminiatureswerepartofthesamemanuscript,atsomepoint inthepasttheywereseparatedandtoday,theybelongtothethree differentcollections. Byperformingin situRamanspectroscopy measurementsinthedarkenedroomintheconservation depart-ment,itwaspossibletoidentifythepigmentsleadwhite,leadtin yellowtypeI,lapislazuli,massicot,redleadandvermilion.When studyingtheblueandredpigmentshierarchicalpigmentusecould bedemonstrated.

Acknowledgement

ThisworkissupportedbytheBELSPOInteruniversityAttraction PoleProgramP6/16(Belgium).

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