!! archaeometric analysis of papaloukas mural paintings in amfissa cathedrale

8/3/2019 !! Archaeometric Analysis of Papaloukas Mural Paintings in Amfissa Cathedrale

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ArchoSciencesNumro 31 (2007)

Varia

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Ioannis Liritzis et Eliza Polychroniadou

Archaeometrical analysis of muralpaintings made by Spyros Papaloukas(1892-1957) in Amfissa cathedral

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Rfrence lectroniqueIoannis Liritzis et Eliza Polychroniadou, Archaeometrical analysis of mural paintings made by Spyros Papaloukas(1892-1957) in Amfissa cathedral , ArchoSciences [En ligne], 31 | 2007, mis en ligne le 31 dcembre 2009. URL :http://archeosciences.revues.org/index803.htmlDOI : en cours d'attribution

diteur : Presses universitaires de Renneshttp://archeosciences.revues.orghttp://www.revues.org

Document accessible en ligne l'adresse suivante : http://archeosciences.revues.org/index803.htmlCe document est le fac-simil de l'dition papier.Tous droits rservs


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. Ap. 2007 ; . O. 2007 ArcheoSciences, revue darchomtrie,31, 2007, p. 97-112

Archaeometrical analysis o mural paintings

made by Spyros Papaloukas (1892-1957)

in Amfssa cathedral

Analyse archomtrique des peintures murales entreprises

par Spyros Papaloukas (1892-1957) dans la cathdrale dAmphissa

I Liritzis * E Polychroniadou **

Abstract: Cmb pp m w pp mp m pg Am C (C A p g 1926-32) Fk pv, C G, g EDXRF, FTIR, IR-PAS, RAMAN, XRD, gmgp g pgp, w w m: ) p m pgm m g pvv m, b) vg Ppk mk f vpm mvm 20 , b p w v b b m xp mpx m pg p wk v m mpm xpm. I pgm m, , m, w, P b, w, m w. Sv p w w (g), , w pgm, ( x), m. Pgm w mx w bg mm m g, gg. G mgp p gg mp m g.

Rsum :Des mthodes combines de spectromtrie EDXRF, FTIR, IR-PAS, RAMAN, XRD, chromatographie gazeuse et photographie digitale ont tappliques aux peintures murales de la cathdrale dAmphissa (glise de lAnnonciation, peinte entre 1926 et 1932) dans la province de Phocide, enGrce Centrale. Cette recherche a un double but : a) identier les techniques de peinture, les pigments de lartiste et les matriaux utiliss durant les phasesde traitement prcdentes et b) comprendre linfuence marque dans le dveloppement artistique de Papaloukas un perectionniste dont les habiletscratives lui ont permis dexplorer les tendances complexes dans la peinture contemporaine et de produire une srie doeuvres variant de limpressionisme lexpressionisme en relation avec les mouvements artistiques des artistes du xxe sicle de notre re. Les pigments identis comprennent ultramarine,anthracite, hmatite, ocre jaune, bleu de Prusse, blanc de plomb, jaune chrome. Plusieurs couches de peinture sont composes docre jaune (goethite),calcite utilise comme pigment blanc, ocre rouge (anydre oxyde de er, ultramarine. Les pigments y ont t mlangs des liants, comme la colle animale,la gouache ou lu. La chromatographie gazeuse a permis didentier la prsence de tempera lu et de colle animale.

Key words: Am C, Spp, IRPAS, FTIR, Rm, Op, Pgm, A, Av, Cv.

Mots cls :Cathdrale dAmphissa, Spectromtrie, IRPAS, FTIR, Raman, Proprits optiques, Pigments, Anthivola, Conservation.

* Laboratory o Archaeometry University o the Aegean, Dept. o Mediterranean Studies, 1 Demokratias Ave., Rhodes 85100, Greece ([email protected])** Conservation and Restoration o Works o Art and Monuments, 13 Omirou str, Neo Psihiko, Athens 15451, Greece ([email protected])


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98 Ioannis Liritzis, Eliza Polychroniadou

ArcheoSciences, revue darchomtrie,31, 2007, p. 97-112

1. IntroductIon

Amg t att w lagly tbutd t t dvl-pmt tmpay Gk at, Spy Papluka,

udubtdly a gat gu (Spt, 1982; Lambak-Plaka, 2006). Dug tud Pa bamaquatd wt t att mvmt t 20t tuy

w ad a gat u att dvlp-mt. Tugut a, Papaluka agd v tbuda patg, a tat a w tmad tv, a labatd ptt w atvablt ad t qualty abld m t xpl tmplx td md patg ad pdu a wk vad m mpm t aly xp-m. H u lu t a a mly dptv adjut tm, but a t mt ptt ma xp ad tdmat lmt mpt. Btw 1926-1932

udtk a maj att vtu, t patg tt mual t Ama Catdal (Cu t

Auat) a -dmd u bult 1868 tu a aly Cta bala. I t 1000 q mu-mtal wk, Papaluka, v tug llw t ttlytabld ul Byzat latal at, da tattmpt a vlutay appa t t att mt Byzat gapy by tdug lmt t pt-Impt1, t Fauvt 2 ad t Nab 3 (Rd, 1966;Bd, 1997) (Fg. 1). I t mual patg t AmaCatdal ma wa t vual t patgvg l valu t t tal p. av t

mbd -mgu matal ad tqu.T mual patg w p vat dt

wt xtv l pat ad vall akg. Dtvvat tatmt ad vau tvt btw1970-1994 tbutd mmly t t l a majpat t gal patg. Immdat u vattvt ad t tak pla bad t mtd

1. Att mvmt Fa (1880-1900) a xt mp-m. T tm Pt-Impm appld t t wk lat 19t-tuy pat a Paul Cza, Gg Suat, Paul Gaugu, Vtva Gg , H d ulu-Laut, ad t

2. A mall gup att, t wld bat a ty w alld, w,tly at t tu t tuy, xpldd t t wt a

wld, vbat tyl xpt at. Fauvm (1898-1908) gw ut Ptllm ad gal Pt-Impm, but aatzd by am pmtv ad l atualt tyl. Paul Gaugu tyl ad u lu w pally tg u. Fauvm wa t pat t btubm ad md xpm.

3. L Nab (1891-1899) w a Paa gup Pt-Imptatt ad llutat w bam vy utal t ld gapat. T mpa dg wa ad by t paalll At Nuvaumvmt. Bt gup al ad l t t t Symblt. T L Nab wa P Bad, Mau D, K Xav Rul, FlxValltt, ad Eduad Vullad.

aaly, tat wuld lp gud d abut a advat tatmt.

Ou pt wk t t a btad ult maamtal tqu appld t mut ampl ad a -dtutv ma ad ttg appld dtly t mual patg d t dty pgmt, bdad ubtat matt, a p-qut tp t ay ut -vat wk (Ctt et al., 2007; Swa, 1998; Bauma

et al., 1998; Ma et al., 1984).

2. ModernscIenceandconteMporaryMuralpaIntIngs

Amgt t qutly ud mtd wall pat-g, pgmt, laqu ad mda, a, Plazg LgtMpy (PLM), Sag Elt Mpy (SEM)ad SEM-EDS, X-ay u (XRF), X-ay da-t (XRD), Bula Mpy, Fu amIad Sptpy (FIR), Ga-Cmatgapy-Ma Sptmty (GC-MS), Hg Pma LqudCmatgapy (HPLC), Idutvly Cupld Plama-Optal Em Sptpy (ICP-OES), ultavlt/vbl abpt ptpy (UVS), vbl abptptpy (VS), Rama Sptpy (Wlmm et al.,2007; Kakul, 2002; Lau, 1910 a, b; Mll ad Wt,1994, 1977; Lua ad Ha, 1962; Lu ad Spa,2001; Ftt, 1993).

Fgu 1: T Ama Catdal: Upp t wall, gt al.Dtal amtal mpt ud by Mat. Sz:46 x 49m.

Figure 1 : Cathdrale dAmssa. Mur nord suprieur, aile droite.Dtail de la composition ornementale inluence par Matisse.Dimensions 46 x 49 cm.


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Archaeometrical analysis o mural paintings made by Spyros Papaloukas 99


I patula XRF, XRD ad malgal mpxamat wall patg av b ptd (.g.La ad Wt, 2001; Fllpak et al., 1976, 1979;Cam et al., 1977, Calamtu et al., 1983).

Pjt g aatzat wall patgag m pt gt tug Claal, Hlltt Rma, Mdval ad tmpay ad md tm(.g. Lua ad Ha, 1962; Matl & S, 2001;

Wallt, 1995; La ad Wt, 2001).Ealy wk ad tal pt, u a Lua

Egypta matal, Cu ad Lau ad C at-t tqu, t 19t tuy xplat aly mau-pt ad ptd wk by Mld ad by Eatlak, a

wll a, gal u tmlv, u a, Tplu adPly; all t a valuabl gud a t wat ga mat-al mgt b xptd t b ud muum bjt admual patg (Lua ad Ha, 1962; Cu, 1915;

Mld, 1849; Eatlak, 1967; Hawt ad Smt,1963; C 14t talatd 1933; Ply).

Dug t wl t 20t tuy, t a b a uualpat tat t att tually dd t pt wat ttut at, a p tat ludd a pla-t t mplymt matal t pvuly kw ud. S v b ty, att av ad att dpal a tmdu atmt atual ad y-tt matal, ad mv t l t u tm. Tpu pdut a b wlatdly mbadby md att. At w pat w mataltat lud pgmt wt updtd vaty, plu a

plta ytt pat mda, xqutly tapatplat, ab, xt mtal ally, quk-ttg adv,ad lt dv, t am mly a w.

Mv, t lg-tabld ld patg a aag. F xampl, patg atd al a -td a latvly lmtd upply att matal, t- t ly avalabl pat mda w wax, plat gum,gg, mlk, amal d, vgtabl l, ad plat .Pgmt am m mal dpt pply pd( Tplu ad Ply tat t) w xta-td m plat, t, ad amal. day, wv, atta t lmtd t t tadtal matal ad pgtqu but may al m a vaty mm-al pat mda, a wll a a pu w yttpgmt.

ak gatd tat a t att matal adt u play a mptat l vat pjt,t tmdu a t umb avalabl matala atd w allg vat pal(Gatta, 1993).

T yldd mat, m t xamat ad aa-ly att pat, abut att tqu ad matallp t takg d abut a ad vattatmt. T, vat md at al tak

a k tt at a a p, aully ag tda bd t p tqu tat t att udt at t wk. T allg dg vatlut tat pv a patg wtut dgadg tatt tt.

Nvtl, v wt t u, mu wkma t b d dtyg t vat umb mat-al ud by tmpay ad md att ad dv-lpg a btt udtadg t ppt tmatal. Aamty ad Cvat a playa gat l t t. T a w a umb t aalytal tqu, u a t abvmt-d, t ad ad dty att matal ad tqu

ad altug mt w d ad dvlpd t tudywk at mad wt m tadtal matal, ty aal b appld t 20t tuy atwk ad t mat-al.

Idtat t matal ad t ppt tmpay bjt ad w dvlpmt bg pu-ud at val maj ttut. Tma La, atGally, Ld, dvlpd a tqu t dty mdpat mda ug pyly ga matgapy- maptmty. Paul Wtm, Cag Mll RaIttut, dvlpd a dv ag, a mp-zd pt, t lgtat tmpay lat aly

a bjt l. Stt at t Caada CvatIttut tutd a taptabl FIR ptmttat a b ud t dtat tadtal matal ua Japa laqu m mtat mad m aw l alkyd.

T applat t aalytal tqu ttmpay wk at a ad udtadg att matal ad tqu (pgmt, bdg mda,atual agg matal). Plazd lgt mpy, XRF,

XRD, GC, LC, MS, FIR w appld t t patg t 20t-tuy U.S. att Wllm d Kg ad

Jab Law dutd t labat t GttyCvat Ittut ad t Natal Gally At(Sllg et al., 2002). T a llutatd w md a val w gt abut tmpay wk at, w ultmatly a ad t vat t

wk (D et al., 1989; Bw et al., 1994)A tgatd llabatv pjt tatd 2002 by at,

Ld, t Natal Gally At (NGA), Wagt,D.C., ad t Gtty Cvat Ittut (GCI) gavaw t m t may qut gadg t a-


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at md pat matal, ug t lag md patg, mal aaly, ad pyal aat-zat (La et al., 2002. I 2000, 11 Eupa muum,datd by t ICN ad at Md, tabld t

Itatal Ntwk t Cvat CtmpayAt (INCAA) (, www.a.g).

3. HIstorIcalandarcHItecturalcontext

I d t appat t mpat Papaluka Gkaly 20t tuy patg mvmt, m ba atuallmt maj att mvmt, t -pa-lt, a ay. H wa b 1892 at Da, a vllagl t t aalgal t Dlp. T vmtalladap ad t aalgal t Dlp w t tmp ad lat pat dptd a lag pat

wk ludg t datv ad guatv patg t t wall ad lg t Ama Catdal.

I G, Byzat at wa add t gd ul. Itwa a Cta at ddatd t t v t Cutlld at a maj pat by t Cu. I tat ptay attmpt vlut ad vat wa t apta-bl. Papaluka vlutay appa, altug appa-td at a aly tag by t lal mmuty, t wa dd upa a tl atttud agat m, ggd by t lgy.

4. orIgInaltecHnIques used Bypapaloukas

T t ta vual ad map bvatmad in situ by E. Plyadu, jut wtdata avalabl m t pt aaly. T patg wad ut a gl lay lm mta appld dtlyt t wall, tat , a secco. T pgmt w appld tt dy gud mxd wt lm a, gg, amal glu,ld l vgtabl gum. T att d t tu t gu by a abtay tk l w a a vtal qua-lty ad appl amut pgmt patula aa mpt t av dttv vual t.

Papaluka ppad v 320 p-dawg (anthivolo-aa t t quvalt Gk) 4 pptv mp-t (Fg 1, 4) t Ama Catdal.

4. T mual patg w xutd m a ppaaty dawg pap anthivolo, Gk xptal att qualty. T talmpt w daw by pl aal ad tad t t wall.T u pkld at ad at a at tqu ta dg. T a 340 anthivola t Ama Catdal, w ma uqu llt ppaaty lgu dawg.

T anthivolo (Fg. 2) wa appld t llutat t Aagl t a t aw upp a at tgt al.

Fgu 2:Anthivolo: T Aagl (Mupalty Ama llt). Sz: 3.30 x 0.85 m.Figure 2 :Atvl: lArchange (collection de la muni-cipalit dAmssa). Dimensions : 3,30 x 0,85 cm.


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H tad t p- dawg t wall by pg a mall l wt a ptd tumt, atually t ud at t tm by d mak, tat t dawg

wuld b pdud by dabbg t t bak d wt a

gauz at lld wt aal pwd.T anthivola, ppty Spy Papaluka daugt,tad t w a wk at, vd a-tv tugt p ad tal vtuty a apat. M Ma Papaluka d tm t t AmaMupalty a t ma ubjt t Spy PapalukaGally Ama.

5. currentcondItIonandprevIousInterventIons

T u dt t tal tutu t buldg,

t lw qualty matal pvdd by lal p, txpmtal tqu t att appld t av dt-tv vual t, t put a wat m t , addtv vat tatmt ad vau tvtbtw 1970-1994 tbutd mmly t t l amaj pat t gal patg tably w aaat t lg t dm, t ap ad t lg tgyaum (t apatmt vd wm at t upplvl t u) at t gt ad lt av (Fg. 3). Tpat lay wa a utabl ad dtatd dt,

may aa w uly attad, akg ad xtmlyabl ad ty ttd t att v w lgtly tu-d.

Futm, t m atvty t g wa t

ma au t mv tutual matal ultda xbt umu ak ad dtat mtajt

T vat tatmt ad val tvtud dug 1970-1994 w amd at t tablzat t tutual lmt t buldg ad t mualpatg. T wa xtv u mt t -mt tutual lmt, jt vtal wall adplamt wd tutu u a t wd ta-a at t lt d t av ladg t t upp .Cmt wa al ud a a gdt t mta t llt l t pat. Bd, tutual wk t t Catdal qud patal mval t tld ad

plamt wt w tl wt mt dg (Fg. 3).L wakg t pat lay ad akg

w maly tatd wt Pmal AC-33, Plyvyl AtatEmul ad Ca a, t latt a t ytully latd. But u a tatmt t xt tag t pjt w byd u pm p t pt

wk (Bauma et al., 1998).

6. tHeconservatIonproject

Lgty du ad t bvu d tat

t Ama Catdal t mual patg ld t tapptmt a vat tam ad vat -tt t udtak t plmay tudy b t atualvat pdu. T vat pjt tatd May 2001 ud t aup t may Ama,t daugt t att ad t gal dt, GalDtat Cultual Dvlpmt, Hll Mty Cultu.

7. saMplIng

Samplg lat agd m t lg t gudlvl ad vau datv mt ad mpt.Oly mut ampl (mllmt al) w pmttdt bta. Ay pptbl vav amplg wa avdd.N-dtutv EDXRF maumt w pmd aggap ptat t pulpt, t wm gal-ly, ad t lt al. I all 26 ampl (mut amplg)

w aalyd ad 114 maumt (mut amplg& 10 -dtutvly) wt all mtd w mad; 64

Fgu 3: T gyaum (wm gally) at t lt al. Majl patg bvd t lg. Pgmt ad ubtatm pt lat t pat ad mla m t pat t u w ampld ad pd t lab aalyzdin situ.Figure 3 : Le Gynce (galerie des emmes) dans laile gauche.Principales pertes de peinture observes sur le plaond. Des pigmentset substrats provenant de points localiss de cette partie et de pointssimilaires dautre parties de lglise ont t chantillonns et traits aulaboratoire ou analyss tu.


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Rama, 14 FIR, 27 EDXRF (10 t patg), 7 GC-MS ad 2 IRPAS.

8. MetHodologyT llwg tqu w appld: FIR (Fu

am Iad), IR-PAS (Iad PtautSptpy), RAMAN, EDXRF (Egy Dpv X-ay Flu), ptal mpy ( t vbl adUV g) ad GC-MS (Ga Cmatgapy by MaSptmty) w mbd, a a tgal pat tpt aamtal xamat 5 (.g. Kakul, 2002)(abl 1-4).

XRF (X-Ray Flourescence)

I tu XRF maumt, a wll a m labatymaumt, w pmd a m-quattatv -gt pgmt, m maj ad m lmt p-. T EDXRF ld ptabl aalyz Spta 9000N wa ud wt a mu dd (HgI

2) dtt, w

a a ptal lut abut 260 V FWHM at 5.9kV, ad t xtat u adtp wtt pb ut Amum Am-241 (26.4 KV K-l ad59.6 KV L-lV) maug Ag, Cd, S, Ba, Sb; CadmumCd-109 (22.1 K-l, 87.9 K- & L-l KV) maug C,M, F, C, N, Cu, Z, A, S, S, Z, M, Hg, Pb, Rb, T,U; ad I F-55 (5.9 KV K-l) maug K, Ca, ,

C. T wd ag xtat x-ay g ttallya mau all mal lmt m ulu t uaum.Hwv, lmtat at pdu a lw tld dtt, ad pat 26 multau lmt la maud, ua up t a dpt a w mllmt(tk dpd t atm umb t lmtmaud ad ampl dty). T mmum dttlmt maud lmt w bud by t ta, add by EPA, a) t tm t tadad dvat takm a blak ampl, b) a tattally gat umb maumt a tak t dtm t atual ta-dad dvat w t multpld by t, ad ) t

5. Fgu 4, 5B, 6, 8 ad ptv maumt abl 1-4 wtRama, FIR, GC ad dgtal pt, w xutd at t OmylaDagt Ct At Objt, At, G, v, (/ D C.Adkpul ad D akal); Fg. 7B ad Rama maumt abl 1-3 by av Tmp, DltaNu (USA); Fg.9 ad FIR/ IRPASmaumt abl 3 by D C Stv at Vga, Dpt. Htal Ru, USA; ad a w XRD by u llabat P. V.Pdkat, al Uvty Ct. Mp xamat byPLM ad dgtal pt w tak m ampl t Labaty Aamty, Uvty t Aga, Rd, G.

mmum dtt lmt wll da a maumt tma (4 x utg tm appx.= dtt lmt).P t ay u maumt lablty tt wappld t au t tumtal tablty t aalyz

(ga ad gy dt, albat gy ax), tugt tumt ad a autmat ga mpat). Ttumt pwdd by agabl batt wav a ld dua 4-5 . Small atat a aalyzdby plag tm v t 25 mm damt aalyz w-dw. W a aaly qu tatd, a u xpd autmatally tu bd t aalyz wdwt xt t 25 mm damt aa t ua t am-pl. Cut tm dvdual adtp u mayb ptmzd adg t t applat, but ttal uttm ltd t wk w l ta 10 m. At td a aaly qu, pta m a u advlutd by t data pg twa t dtm

u tt a p-ltd ag lmt.T tty data a t quatd autmatally uga udamtal paamt t pdu, pa-tg ampl matx t, bad at tat a p-pgammd t apppat applat ( t a,lat k). Rult w vwd t tgal dplay ad a td ubqut dw-ladg t a PCad pt tug a RS232 pt. T pma tptabl XRF tumtat t labaty a aladyb ptd (Ltz, 2007; Matzua & Ltz,2006), wl t t pt t pt vtgatmay b appld t ay avalabl ptabl XRF tumt

tat qu a adatd aa ta a pt u. H, awd ag lat k matal w aalyzda pwd pllt t valuat auay, p ad dt-t lmt. R ampl ludd (ylt, mtal,lay, l, lw adatvty ampl). T tudywd t apablty t tumt t dtm majad m lmt (K, F, Ca, M, ) ad ltd talmt (S, Z, Ba, Rb, Pb, M) typal lat (yl-t) k. Ot ta lmt w t maud baut lw utg tvt ma tat t ta-t w a t blw dtt lmt. Sampl mau-d t labaty w dd vgt t v at 75 Cp t ay maumt.

T -dtutv tqu wa ud a amplg wattd vw t valu ad t dt t wallpatg. Patulaly t t Nativity tgt bal-vaultd am t , ad t anthivolappaaty dawg pap (, tt 4).

Hwv, lmtat du t x-ay attuat by abp-t mak t tqu dal mt ua aaly.Ca tak t avd ay ua day pdut m


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watg / t, wl vy t lay, ua t patd lay, t btad data pvd m-qua-ttatv ult, wl a mult-layd mpt,t dd pta a mpt m all lay wtut

paat. It wa al appld m mut ampl mmall l agmt dtatd aa t wall, butmaly t atual patg by plag t pb tat

wt t pt tt, a -dtutv ma (Tpt XRF a b appld xtvly aalgalmatal, .g. Ltz et al., 2002; Matzua ad Ltz,2006; Papaggu ad Ltz, 2007; Ltz, 2007, ad mual patg, .g. Agl et al., 2007; Capta-Vallvyetal., 1994). T, t pt aaly pt a aa t mual patg vd by t damt t utg

wdw aud 25 mm ad a vaabl dpt mmllmt w aut ay m lmt dttd,byd t ptg t pgmt mal. Smulat

xpmt ad umal alulat av w t ult(Ltz, 2007).

FTIR (Fast Fourier Inrared Transorm)

FIR (Lw ad Ba, 1977) ad a t u IadPtaut Sptpy (IR-PAS) w ud t day ga (laqu u a bd, va), ad -ga pgmt. T ty ampl bm a t t lta 1 mm tk ytal ty bm mpd pwd m 1% dlutd KB d ppaat, adt IR bam pa tug. H, ampl w mutd

, ut wt damd aw ad gdd by ma u-vly gad abav. T way upmpdpatd lay (m-tatgapy) w pbl t b m CCD dgtal mag t mp ud vbl UV lgt (, d blw). FIR ampl z 50-100 m tk w ut, mpd a damd mpdll ad pta w btad. T FIR ud wa tat Bad (FS-45A upld wt mp UMA500). Ival a IR ud t dty wat atual gla,gypum amb. Hydat ud agg xpmtad may ad auttty m bjt ad pgmt adv t datg (Stv et al., 2002; Gdall et al.,2004; Lw ad Ba, 1977).

IR-PAS (Photoacoustic Inrared Spectroscopy)

T dtmat t bd ad pgmt ta-t lvl wt a patd lay a al b btad wt aad ptaut ay. I t tqu, a ampll ta 10 mm damt plad a lum-lldamb quppd wt a g tvty mp. T

pm abb t ad adat ad udg allaty atg ad bm a u tmal wav.T wav wt t bulk ampl ppagat t t uaad t t lum atmp. T ptaut gal

gatd at t ua ad aud by t tmal xpa- t ga (MClllad et al., 1993; Nwma et al.,1986).

T magtud t gal va ppt t ttat t ad p. T abba valua alulatd m tgatd pak aa. Ea abbavalu pt a avagd mau t t ua t ampl xpd t t 5 mm damt ad bam.

IR-PAS ud t mau t tat vaup t patd ua lay a MEC 300 pt-aut ll ay a Bmm MB-120 ptmt.Ea ampl wll b u at a lut 8 wav umb 256 a. Cab blak, uppld by t mauatu-

, ud t tabl t bakgud dt ttumt. Sval abpt pta w btad tadad pgmt w vd a a data bak, ad tdtat pgmt ad bdg mda a uk-w mpt ptum wa avd wt apppatptum tadadzat ad multvaat aaly (Ltzet al., 2008a) (Fg. 9). T ult aalyd ampl ad t abl 3, 4.

H, t IR ad XRF tqu w ud t gza) pgmt, b) laqu, ) l (Gtt ad Stut,1966; D, 1984; Wt, 1981).

GC-MS (Gas Chromatography with MassSpectrometry)

A Fga Ga Cmatgapy wt Ma Sptmty(GC-MS) wa ud dtat t ga p-t (amad t), llwg tadad pdu (Wt,1978; Kt et al., 1996)

Raman

Rama ptpy t gt patula l- attbutabl t ta pgmt mal mpudtug mpa wt avalabl data bak pta (p-al data ba twa at dvlpd a d ba m-pl) (.g. Clak, 2007). Equpmt ud a: a) 1000Rama, Raw, wt a H-N la lgt u (632.8m), ad u x50 ad x100 bjtv l Olympu,t ug aud 1 mW pw la bam wa mad gl pt a -td ampl, ad t u-a, wt a ptal lut 4 m-1, b) ExamR HgPma Mp Sytm DltaNu, 785 m la


9/17



bam, BX51 Olympu ama, lut ~ 4 m-1, damtpt z ~1 m, ad ) t RkHud Rama Sytm DltaNu wt Nup, 785 m la bam FSX tlgy,lut ~ 8 m-1 ad damt pt z ~35 m (Ltz

t al., 2007; Guau, 1989; Cupy ad Laut, 2001). Im ampl wt tamatd ua t ama ptaw maly m u. I t a la bamptd t mv t day pdut ad du g-atly u, ad mau t ama ptum t atual udlyg patd lay. All Rama pta abal td a btt vualzat t ult.T typ Rama tumt w ud. I t tta (a) wa ud a tal pa t pjt, ad(b, ) w appld a lat pa t pjt pptg ta mal pt am ad w ampl, ad vtgatg t fy t ptabl RkHud tu llt pta a dtutv ma.

Imaging

Ptgap dg a p-qut tp p t ayut aaly. Pt ampl ua ad d t d-ty m-tatgapy w mad ug ptal mptmulatd by wt plazd lgt ad UV (Hg u),

wt bjtv l x10, x20 ad x50. T pt wbtad va a 3CCD ama (Gwg, 1999). T UV ad m a lat ga mpud m tut m, a wll a t bdg mda m-pud wt tg u (.g. va, laqu,

t). By t way ay patd lay a wll a t aw dtd, ut dtald maaly.

X Ray Difraction (XRD)

T XRD Pwd Datmt wa a Sm D500,Cu-ub, Gapt Mmat, 2-tta ag 4-70gad, tp 0.02 gad, m/Stp 3 .

T mal gt wa mad by twa DaPlu,Fma Buk ad t PDF-data Ba (Pwd Dat Fl).

M aalytal wk X-ay dat maldtat plat ubtat ad Sag EltMpb aaly pt mal aaly ad bvat mult-layd pat ud tudy (Ltz et al., 2008b).

9. results

T ult a ptd abl 1-4 a utld blw.1) T pat ud a wd paltta. Amgt t vau

pgmt a: ultramarine, (Na8-10

Al6S

6O

24)S

2-4), carbon black,

hematite or red ochre(F2O

3),yellow ochre(F

2O

3*H

2O) (though

the principal matter is goethite, alpha-FeOOH) but kaolinite too,Prussian blue(F

4(F(CN)

6)

3), lead white(PbCO

3*Pb(OH)

2),

ud m at tm tll tday, lead chromate sulate (mem-

ber o the generic name chrome yellow) (2PbSO4*PbCO4). Hal ud baum abat a wt but al t dlut dakpgmt. I a mta t ag pt wa dtdby Rama a a typ ut (CaF

2) w kw t av

a xtm vaablty l.2) Sta mla pgmt w ud t anthivolon

(abl 1, Fg. 4). I patula, vau aa w aalyzdby EDXRF ad Rama t pap uppt, d ad blakta. T blak ta ta mtly pbably a uk-w d pat pud adtally t tampg (tam-p) lay t pkld pap w tad a,m yllw, wt ttaum, ad t. T d tata mu m dtd a xd (a).

T t t pap ta at yllw, ta a,m yllw ad lad xd (tmb mat).

I patula, tw p w aalyzd (AMF-A1 26x56.5-59 m, ad AMF-A2 18x85 m). Cl wa bv-uly dppd m t att bu wl patg tmual (Fg. 4).Anthivolo umb AMF-A1 ad

AMF-A2 m pat la dg a datv mtv. IAMFA2 val ly ta w bvd. Ptabl EDXRFpb wa ud patula ta t ua. FRama ptpy al -dtutv aaly w p-md ag t ua ad ug la bam HN(632.8 m) vually dtd pgmt mal ga.

Pap ampl z 50-100 m w ut, mpd a da-md mpd ll ad FIR pta w btad. Papad a ly ta w al md wt FIR.

3) Sampl AMF29 6, AMF13 (Fg. 6 ad abl 2), AMF2 Fg.5 t v pat lay, yllw (gtt),alum abat wt, d (aydu xd), ab blak ad ultama.

4) I AMF13 (mta bag patd lay, Fg. 6, 7,9), t llwg pgmt w gzd tug IR-PAS, FIR, Rama tqu: a) yllw (pblygtt) b) alum abat t wt, ) d d) blak ab, ) ultama, ) Pua blu ad g)ut (~1880 m-1). Rama maumt w patdby tw dt tumt, ad a xampl w Fg. 7, wa t dtat bad t pak udbtw 230 ad 660 m-1. Nvtl, t ptat ptal g t 2000 m-1 wa al mplyd.

5) F AMF29 t uv lay B, C, D tamaly ultama ad Pua blu. Ty a gzd

6. AMF 17 : AMFISSA +umbg amplg.


10/17



a dtt du t dt tt t tw pgmt.I lay E t xt tg mxg d ad blu pg-mt, but Pua blu a b ud. T p ga ubta g dttd but uld t bdtd a t kw pgmt. Pap t dvm lat tvt t atwk. Smlaly t dakpgmt lay A uld t b dtd.

6) I AMF17 (3)7 d m t lg, pgmt adubtat, gypum wa gzd wt, Ultama blu, d tgt wt a laqu. T wa ud

m magyg pt ampl pl --td m, wt ad UV lgt upld wt Ramaptum. T ppaaty lay a wll a t ly d lay

wa .7) Fut X-Ray Dat wa ud a w a

ty ampl. T pta av w Gypum ubtatum

7. 3 : wm gally ( gyaum) Rgt al, 3 3d ap.

(CaSO4*2H

2O) wt quatz (AMF27), wl at a

(AMF28) a vaty ld ga blu, bw adwt w latd. T blu w du t lap lazul(dalt, NaS(AlSO

4)

6(ClO

4)

2), t bw w du

t matt dlutd wt bat (Ltz et al., 2008b).8) T t AMF2 av w tw patdlay. Fg. 5 (AMF2) w typal Rama ptum -ptvly, ad abl 3 w all aalyzd ampl. Pgmt(AMF18-26) m a lal p w aalyzd bau t watugt t av b ud by Papaluka, a t wa a tad-tal p t day Papaluka, gtt m

Fgu 4: AMFA1 Dgtal pt anthivolo (ppaaty dawg pap), ud t al gmt mt llutat tap t wm gall at t upp pat t gt ad ltal t vbl ptum, ad a la dawg kt blw(26 x 56.5-59 m).Figure 4 : Photo numrique datvl (dessin prparatoire sur

papier), utilis pour les illustrations du moti gomtrique oral dansles absides des galeries des emmes dans les parties suprieures des ailesdroites et gauches, dans le spectre visible, et ci-dessous un dessin sch-

matique au trait (26 x 56,5 x 59 cm).

Fgu 5: Ama Catdal, wm gally, ampl AMF2wg tw patd lay. H Rama ptum lw yl-lw lay (gat ta 600 mmt), val mum yllwad yllw .Figure 5 : Cathdrale dAmssa, galerie des emmes, chantillon

AMF2 montrant 2 couches peintes. Ici le spectre Raman de la couchejaune inrieure (dpassant 600 micromtres) rvle du jaune chromet de locre jaune.

Fgu 6: Pt wt ptal mp AMF13 (3), pla-t wt lu m t wdw, wm gally, gt al, 3dap wt v lay. T (a) lt, tak wt wt lgt ad t(b) gt, by UV lgt.Figure 6 : Photos au microscope optique sur AMF13, pltre avec cou-leur provenant de la entre, galerie des emmes, aile droite, 3eabsideavec 5 couches. La photo (a) gauche est prise en lumire blanche etcelle (b) de droite en lumire UV.


11/17



ld bx tugt t b a ld a 70 ya. N w udby Papaluka.

9) Ga matgapy wa mplyd t dty tmpa(gg bd) ad amal glu. Ppal mpt (PCA)lut aaly t GC-MS ampl wa appld t d-

ty bdg mda mpa wt avalabl data bak.PCA mplyd t bplt t t tw mpt (, Matzua & Ltz, 2006; Baxt, 1994). Amalglu wa ud, a ad gg, a bdg ubta tppaat gud ad patd lay. I patu-la, AMF5, AMF6, AMF16 wa t gg, AMF8,

AMF10 wa amal glu, ad AMF15 a t lut a. (abl 4, Fg. 8). T g tt glu blakakd ampl AMF15 au t ampl t utd tmlk lut. T ampl wa aalyzd mblgally adxgu at at .g. b-dtat at wdttd8. T gdt ad ppt t glu m

t av attatd mgam. N ut xplaata b gv at t mmt t latp btwg glu tt ad p mb, ad t ud ut vtgat T GC aaly pvdd t

8. Mblgal aaly t ampl (AMF27, 30, 31) a dt-td, batal p, ugal p wt dak mylum ad p Apgllu (kdly mad by D Alxad B, PuStat Uvty, Rua).

am ad tt a t ampl a wll a atgam ptag tt am ad.

10. conclusIonsT applat aamtal tqu ad

udtadg t att matal ad wkg mtd,tby ag vatt ablty t pv tpatg. All t abv mtd aaly mplmta t, lablty, ad lay t tqu xut u a mptat wk at wt mut -dtutv amplg.

T pat dd t llw t uual a secco pat,tad mbd val patg tqu (pgmtmxd wt lm, tmpa ad l) t p up w aa atv pblt ad matd t atual aatt

t pgmt by t qualty butk ad tpatula mdum dg gl.

T att utlzd uvtal matal t avdd vual ad txtual t. Hwv, xpmtaltqu ad lw qualty matal ad a gatv t t lg tm tablty mual patg, ad pmaj pblm t vat. It dpabl t dt tabl w vat tqu t mv pvuvat matal ad apply apppat matal ttablz t patg ua.

AcknowledgementsT aut w t wamly tak lat M Ma Papaluka

ad M May Maldu t uagmt tpjt, t Ama w Mupalty ad t May

Ama t ad ad aal uppt. W a gatult M Val Taak, M Ia Ml, tCultual Fudat t Alpa Bak, G, ad tSlv ad Bayt O Mg C. S. A, aal up-pt. W xtd u tak t M Iaa Ktadupat, pap vat adv ad mmt adM. Alxad Plyad tug uppt.

W appat M Sbyl Ng, P. Lug D , DavdPak, D. Mal Staagg t tu mmt aduggt, ad t Gk Mty Cultu, Dtat Cvat At ad Ctmpay Mumt, gatg pm t amplg.

Tak t M Ela Magaa tal atat adt dt FOKIS wpap pmttg a tav.

Fgu 7: RAMAN ptum (tty/wavlgt) AMF13lay b (t d amgt v lay) d mal tak byExamR. T Blu pt Ultama, tak m lay b, pt5 (lay tk 90-100 m). T tw pgmt dtd tba tw pta ( Fg. 6 ad 9). Blu l (upp) ludu ad d l (lw) bal td.

Figure 7 : Spectre Raman (intensit / longueur donde) de AMF13 cou-che b (la seconde parmi les 5 couches), minral rouge pris par ExamineR.Le point bleu est lultramarine, pris de la couche b, point 5 (paisseurde la couche : 90-100 m). Les deux pigments sont identis partirde deux spectres (voir gure 6 et 9). La ligne bleue (en haut) inclut la

uorescence et la ligne rouge (en bas) est la ligne de base corrige.


12/17



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abl 1: N-dtutv aaly pgmt dtat lu tw p atvl, by Rama ad EDXRFmtd. Nt tat EDXRF gv ly mal lmt -tat, wl Rama ptpy gv mat abut ttutu.

ableau 1 : Analyse non destructive pour lidentication de couleurde pigments sur deux pices danthivolo, par les mthodes Raman etEDXRF. Notons que lEDXRF donne uniquement les concentrationschimiques lmentaires, tandis que la spectroscopie Raman donne desinormations sur la structure.

ANHIVOLOSAMPLE REF.

COLOUR PIGMEN MEHOD

AMFA-1(26x56,5-59 m)

Yllw Lad mat ulatRama,EDXRF

BlakBlak ta

CabCta (a)

RamaEDXRF

Rd taI Oxd (a)I Oxd + taumdxd wt (O

2)

Rama

EDXRF

Blu Ultama Rama

Rd I Oxd (a) Rama

AMFA-2(18x85 m)

Rd I Oxd (a) Rama

Blu Ultama Rama

Dak blu Pua blu Rama

Blak Cab Rama

Wt O2

Rama

Yllw Lad mat ulat Rama

abl 2: Rama maumt pgmt dtat -td ampl AMF29, AMF13 ad AMF2, dvd mwm gally, gt al 3 d ap ad ppad a matx(, Fg. 6). Lttg (A, B, ) pd t aalyd ad-wd lay, ad t umb t t patula pt wt

t lay wt bvu lu.(AMF: AMFISSA + umbg amplg, 3: wm gally (gyaum), gtal, 3 3d ap). Spt lu aalyd lud d, g,blak, yllw, blu, ag, wt. [NOE t ukw,udld t g latv tty. Rama Wavlgt(m-1). * A4: 233.8, 311.4, 675.2; ** A7 (at m ga ub-ta) 292.2, 332.4, 510.7, 546.9, 644.7, 686.3, 707.7, 741.2,777.4, 819, 958.4, 979.8, 1083, 1213, 1281.4, 1377.7, 1392.7,1444.3, 1481.1, 1537.4, 1596.4, 2822, 2873.8, 3074.9. *** D6:414.2, 493.3, 546.9, 622, 671.6, 1008, 1099.1, 1306.9, 3404,3490].ableau 2 : Mesures Raman pour lidentication de pigments sur dessections des chantillons AMF29, AMF13 et AMF2 de la galerie des

emmes, aile droite 3e abside, et prpars dans une matrice de rsine(voir g. 6). Les lettres (A, B) correspondent aux couches analyses,et les numros ont rrence aux points particuliers dans la coucheayant une couleur vidente (AMF : AMFISSA + numrotation delchantillonnage, 3: pour galerie des emmes (gynce), pouraile droite, 3 pour 3e abside). Les point colors analyss incluent lerouge, le vert, le noir, le jaune, le bleu, lorange, le blanc. [note pourles indtermins : les longueurs donde Raman des intensits relati-ves les plus leves sont soulignes : * A4: 233,8, 311,4, 675,2 ; **

A7 (plutt une substance organique) 292,2, 332,4, 510,7, 546,9,644,7, 686,3, 707,7, 741,2, 777,4, 819, 958,4, 979,8, 1083,1213, 1281,4, 1377.7, 1392.7, 1444,3, 1481,1, 1537,4, 1596,4,

2822, 2873,8, 3074,9. *** D6: 414,2, 493.3, 546,9, 622, 671,6,1008, 1099,1, 1306,9, 3404, 3490].

Sampl . Lay Aalyd

Pt

Clu Pgmt

AMF293, lw pat .

A 1 Rd Hamatt

2 Yllw Rd & Yllw O

3 Rd Rd&Yllw & SO

2

4 Blak Ukw*

6 Blak Cab

7 G Ukw**Oga

8 Blu Ultama

B 1 Blu Ultama

2 Blu Ultama &Pua blu

C 7 Blu Ultama

D 3 Rd Rd &Pua Blu

4 Blu Ultama

5 Blu Ultama &Pua blu


16/17



6 G UkwOga***

E 1 Blu Ultama &Gypum

2 Blu Ultama &

Gypum3 G Ukw

Oga a D6

4 Rd Rd &Ultama

5 Blu Ultama &Gypum

6 Blu Gypum &Ultama

AMF13,3 plat(Mta) wtlu m twdw t t 3d

ap

A 1 Yllw Oag

Cm yllwFlut

2 Yllw Yllw

3 Wt Calumabat

B, 90-100 um

4 Rd Rd

5 Blu Ultama

6 Wt

7 blak Cab

C, 60-70 um

8 yllw Cm yllw

9 d

10 blu Ultama

11 wt

12 laqu

13 yllw

14 blak Cab

D, 200um

15 wt Calumabat

16 yllw Cm Yllw

17 bw Rd

18 g Pua blu

E, abut30 um

19 yllw Yllw

AMF2Yllw

pgmt ak.Vault

A, >600um

1 yllw Cm yllw +Yllw

B,abut50 um

2 d Rd

3 yllw Cm Yllw (FIR: kalt)

4 blu Ultama

abl 3: Sampl lat, l, mtd ud ad pgmt d-tat by dt mtd l mut amplm vau pt t wall patg (g baum tta BaCO3 wt a pt at wgt a ad tug t). Ptabl EDXRF aaly t a dtu-

tv ma gt a lag aa t ua mual patg.Cmal lmt a ptd w t kw mpud.I tat t t ty ampl dtad ad aalyzd by Ramaad FIR. T mpud a gzd m a data bakptal lbay. Maga ad xd () ad mw ud at tm.ableau 3 : Localisation de lchantillon, couleur, mthode utilise etidentication du pigment par difrentes mthodes de couleurs sur deminuscules chantillons provenant de difrents endroits de la peinturemurale (de ortes teneurs en barium blanc BaCO

3sont prsentes plutt

pour un accroissement de poids, et ainsi pour un cot plus lev). Lesanalyses EDXRF in situ se rrent une approche non destructive surune plus grande surace de la peinture murale. Les lments chimi-ques retent des composs connus. Par contraste avec les chantillonsminuscules dtachs et analyss par Raman et FIR. Les composs icisont reconnus partir dune banque de donnes spectrale. Les oxydesde manganse et de er (ocres) et leurs drivs taient utiliss dans lestemps anciens.

Sampl

.

Dpt Cl Pgmt Mtd

AMF2 3, wm

gally, gt al 3d

ap, yllw

akd pgmt

Yllw I 4 uv

patd lay:

Cm yllw+

Yllw +

Ultama+

Rd

(yllw

=kalt by

FIR)

Hg tt:

Pb ad F

(maly yllw m

mla pgmt a

abv)

Rama, FIR

EDXRF

AMF3 2, wm gally

Rgt al, 2d ap.

Rd

Flakd pgmt

Rd I Oxd

+ Ca + S.

Rd

EDXRF

AMF4 Pulpt, d dat Rd Hg F, Ca,

S, Ba.

Rd

EDXRF

AMF5 Lt al

Ital d

lum

Blu Hg F,

Ba, CaCO3,

K, Pua Blu

EDXRF,

FIR, IRPAS,

AMF12 3 Wm

gally, gt al, 3d

ap )

Blu Hg F

ad CaCO3.

Rd

EDXRF

AMF13 3, Wm

gally, gt

al, wdw

t t

3d ap

5 lay Cm yl lw,

Rd ,

Ultama,

Cab ,

t (dtal

abl 2)

Rama,

FIR, IRPAS


17/17



AMF14 Pulpt

Pat ua

Flaky pgmt

pap wt lttg

Yllw Yllw Pb-S

+ PbO, K, F

(a upg ult

w a t at

pt b jutd)

EDXRF

AMF15 Pulpt

Pap wt ltt

Blak FIR, IRPAS

AMF16 2, wm

gally gt al,

2d ap.

Bw Rd Rama,

AMF17 3, wm

gally gt al,

3d ap d m

t vault

Rd Rd laqu +

Rd .

I xd +

MO2+

Clay. Rd

Rama

EDXRF

AMF18-

AMF26

Lal p

.

Vau

lu

(md

pgmt)

Gypum, mum,

Oxd

maga

ad ,

g baum

EDXRF

abl 4: Ga matgapy-ma ptmty (ptag amad pt ad mpa wt a data bak va ppalmpt aaly plt) ad FIR ad IR-PAS g(pta mpad wt data bak) dtt ga ampl m vau pat t wall patg.

ableau 4 : Spectromtrie de masse en phase gazeuse (pourcentagedacides amins prsents et comparaison avec la banque de donnes viaun diagramme danalyse en composantes principales), et ltrage FIRet IR-PAS pour dtection dlments organiques sur des chantillons dedifrentes parties du mur peint.

SAMPLE REF. BINDING MEDIA

AMF-5, AMF-6, AMF-16 Egg (ma ttg qu: 463,530, 618, 794, 926, 1009, 1097, 1359,1577, 3325, 3500, 3587 m-1)

AMF-8, AMF10 Amal glu

AMF-15 Na Ca lut

AMFA-1 (Atvl) Pap / l, Abba : 897, 1061, 1161,

1267, 1317, 1373, 1427, 1508, 1653, 2905,3353 m-1.

!! archaeometric analysis of papaloukas mural paintings in amfissa cathedrale

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