Supplementary Materials: Raman Investigations to Identify Corallium Rubrum in Jewelry and Ornaments

Sebastian Fürst, Katharina Müller, Liliana Gianni, Céline Paris, Ludovic Bellot-Gurlet, Christopher F.E. Pare and Ina Reiche

Table S1. List of objects from archaeological contexts that have been analyzed by Raman spectroscopy. The bold entries (25) indicate changes or at least clarification of the originally proposed material.

Object Inventory Number Museum Origin Laser (nm) Analyzed Substance Gold and coral RGZM 1 532; 638; 758; 1064 (all Diode); - Agris (département Charente/F) Corallium ornamented helmet /Angoulême 487.9 (Ar+); 632.8 (He-Ne) Pieces of red 12199 MAN 2 Algère (?) 532 (Diode) Enamel material Collier of longitudinally Allensbach-Kaltbrunn (Landkreis drilled coral C 2826 BLM 3 632.8 (He-Ne) Corallium and ivory Konstanz), from branches together with ivory spacers Altheim-Heiligkreuztal (Landkreis Ring-shaped coral HMI 354E Kar. II LMW 4 ), tumulus “Hohmichele”, 632.8 (He-Ne) Corallium pieces grave VI Asperg (Landkreis ), tumulus Bronze V 68, 34 LMW 632.8 (He-Ne) Corallium “Grafenbühl”, grave 25 Asperg (Landkreis Ludwigsburg), tumulus Bronze fibula V 64, 22 LMW 632.8 (He-Ne) Corallium “Grafenbühl”, grave 3 Chape of a dagger 20,391 MAN Auves (département /F), grave 1 532 (Diode) Corallium Bussy-le-Château (département Marne/F) Bronze neck ring 23039 MAN 785 (Diode, HE) Corallium and enamel “”, grave 24 Bussy-le-Château (département Marne/F), No specification, Nail cutter 4749 MAN 532 (Diode) without context possibly bone Bussy-le-Château (département Marne/F), Part of a belt chain 20933.001 MAN 532 (Diode) Corallium without context Bussy-le-Château (département Marne/F), Part of a belt chain 20933.002 MAN 532 (Diode) Corallium without context

Minerals 2016, 6, 56 S2 of S7

Table S1. Cont.

Object Inventory Number Museum Origin Laser (nm) Analyzed Substance Shield boss, ornamented with Châlons-sur-Marne (département Marne/F), 13672 MAN 532 (Diode) Corallium bright small Camp de Châlons segments Châlons-sur-Marne (département Marne/F), Fragment of a shell 13661.002 MAN 785 (Diode, HE) Shell without context Bronze fibula 67911 MAN Charmont (département Marne/F), grave 28 532 (Diode) Corallium Piece of unknown Cierges-Caranda (département Aisne/F), bright substance on a 39412.001 MAN 785 (Diode, HE) No specification grave 84 bronze wire Eberdingen-Hochdorf (Landkreis Bronze fibula A 3273 LMW Ludwigsburg), from tumulus of 632.8 (He-Ne) Corallium “Pfaffenwäldle” cemetery Écury-sur-Coole (département Marne/F), Nail cutter 77050L MAN 532 (Diode) Corallium “Les Côtes en Marne”, wagon grave 11 Necklace with large Nr. H1-10 Esslingen 5 Esslingen-Sirnau, grave 1 632.8 (He-Ne) Corallium coral beads Bracelet of coral Nr. H1-10 Esslingen Esslingen-Sirnau, grave 1 632.8 (He-Ne) Corallium beads Iron fibula 12830.002 MAN , origin unknown 785 (Diode, HE) Bone or dentine Small bronze disc with two bright inlays, almost 13153 MAN France, origin unknown 532 & 785 (Diode, HE) Corallium and Metaloxid completely covered by corrosion layer Iron fibula 13377.001 MAN France, origin unknown 785 (Diode, HE) Corallium Fragment of unknown bright 27846.001 MAN France, origin unknown 532 (Diode) Bone or dentine substance Friedingen-Langenenslingen (Landkreis Bronze fibula A 3341 LMW 632.8 (He-Ne) Corallium Biberach), grave FIBULA with (now) white coral inlay Gäufelden-Nebringen (Landkreis Corallium (proof of red - LMW 632.8 (He-Ne) and red enamel Böblingen), grave 17 pigments in coral) button

Minerals 2016, 6, 56 S3 of S7

Table S1. Cont.

Object Inventory Number Museum Origin Laser (nm) Analyzed Substance Gerabronn (Landkreis Schwäbisch Hall), Bronze fibula A 3359 LMW 632.8 (He-Ne) Corallium tumulus Bronze birds Goethite (oxidation - Glauberg 6 Glauberg, tumulus 1, elite 1 532 & 785 (Diode, HE) head fibula layer) Goethite (oxidation Bronze birds head - Glauberg Glauberg, tumulus 1, elite burial 1 532 & 785 (Diode, HE) layer) + CaCO3 + fibula N° 2 pigments Zoomorphic fibula - Glauberg Glauberg, tumulus 1, elite burial 1 532 & 785 (Diode, HE) Goethite + coral Goethite (oxidation chape - Glauberg Glauberg, tumulus 1, elite burial 1 532 & 785 (Diode, HE) layer) + CaCO3 + pigments Zoomorphic fibula - Glauberg Glauberg, tumulus 1, elite burial 2 532 & 785 (Diode, HE) Pigments Sword chape - Glauberg Glauberg, tumulus 1, elite burial 2 532 & 785 (Diode, HE) No pigments, but calcite Only organic Iron fibula with gold - Glauberg Glauberg, tumulus 2, elite burial 1 532 & 785 (Diode, HE) compounds of sheet decoration conservation treatment Anthropo- - Glauberg Glauberg, tumulus 2, elite burial 1 532 & 785 (Diode, HE) Pigments /zoomorphic fibula Hahnheim (Landkreis -Bingen), Im Bronze fibula V 246 LM Mainz 7 632.8 (He-Ne) Corallium Letten, tumulus - (Landkreis Bronze fibula - LMW 632.8 (He-Ne) Corallium Sigmaringen), Gießübel, tumulus 1, grave 2 Pin with large round Herbertingen-Hundersingen (Landkreis head made of amber Corallium (instead of - LMW Sigmaringen), Gießübel, tumulus 1, 632.8 (He-Ne) with small inlays of “white paste”) grave 4 bright substance Herbertingen-Hundersingen (Landkreis Bronze fibula T210 LMW 632.8 (He-Ne) White calcite Sigmaringen), Herbertingen-Hundersingen (Landkreis Scabbard of a dagger - LMW 632.8 (He-Ne) Corallium Sigmaringen), Talhau, tumulus 4, grave 14 Small tubular object Herbertingen-Hundersingen(Landkreis - LMW 632.8 (He-Ne) No specification as part of an amulet Sigmaringen), Gießübel, tumulus 1, grave 2 Bronze knob of a Heutrégiville (département Marne/F), Le 80129.003 MAN 532 (Diode) No specification phalera Mont Sapinois, without context

Minerals 2016, 6, 56 S4 of S7

Table S1. Cont.

Object Inventory Number Museum Origin Laser (nm) Analyzed Substance Ilvesheim (Rhein-Neckar-Kreis) Corallium & dentine or Iron fibula BW2006-09-33-08 REM 8 458 (Ar+); 532 (Diode) “Weingärten”, grave 1 bone Ilvesheim (Rhein-Neckar-Kreis) Part of a bronze fibula REM50883 REM 785 (Diode, HE) Corallium “Weingärten”, grave of 1954 Ivory (département Jura/F), Les Moidons, Bronze fibula - MAN 532 (Diode) Corallium Tumulus de Champ Peupin, grave D Laval (département Marne/F), without Bronze fibula 13026.001 MAN 532 (Diode) Corallium context Bronze neck ring with (Landkreis ), 30179 bzw. Speyer650 MAN 532 (Diode) Corallium gold sheet grave Bronze fibula BW1974-A5381 REM Mannheim-Vogelstang, from grave (?) 514 (Ar+) Corallium Mannheim-Wallstatdt, aus Siedlung “Hinter Bronze fibula REM12887 REM 458 (Ar+) Corallium der Nachtweide” Corallium rubrum 24228-1 MAN Marsal (département Moselle), aus Siedlung 532 (Diode) Corallium rubrum branch, (bright color) Monsheim (Landkreis Alzey-Worms), Bronze fibula BE 283d Worms 9 632.8 (He-Ne) Corallium aus Flachgrave Monsheim (Landkreis Alzey-Worms), Bronze fibula V 657 LM Mainz 632.8 (He-Ne) Corallium without context Small bronze bracelet V 69, 39 LMW Mühlacker (Enzkreis), tumulus 10, grave 1 632.8 (He-Ne) Corallium Bronze fibula V 69, 39 LMW Mühlacker (Enzkreis), tumulus 10, grave 1 632.8 (He-Ne) Corallium Small bronze ring V 69, 39 LMW Mühlacker (Enzkreis), tumulus 10, grave 1 632.8 (He-Ne) Corallium Zoomorphic fibula V 69, 15 LMW Mühlacker (Enzkreis), tumulus 4, grave 5 632.8 (He-Ne) Corallium Private Buddhist prayer beads - Nepal 632.8 (He-Ne) Corallium collection Nierstein, OT Schwabsburg (Landkreis Birds head fibula V1111 LM Mainz 632.8 (He-Ne) Corallium Mainz-Bingen) Osthofen (Landkreis Alzey-Worms), Bronze fibula BE 339 Worms 632.8 (He-Ne) Enamel Rheinchaussee, without context (département Marne/F), Le Terrage, Bronze fibula 33331.001 MAN 532 (Diode) Corallium grave B Chape of a sword - LMW Renningen “Lauerhalde”, Siedlung 632.8 (He-Ne) Corallium scabbard

Minerals 2016, 6, 56 S5 of S7

Table S1. Cont.

Object Inventory Number Museum Origin Laser (nm) Analyzed Substance Pearl on a bronze wire, Saint Etienne-au-Temple (département 80133.001 MAN 532 (Diode) Corallium possibly earring Marne/F), Mont de la Tonnelle, grave 119 Pendant with several Saint-Etienne-au-Temple (département 12718.001 MAN 532 (Diode) Amber or glass pearls Marne/F), from grave Saint-Etienne-au-Temple (département Bronze fibula 12828.001 MAN 785 (Diode, HE) Enamel Marne/F), from grave Saint-Etienne-au-Temple (département Bronze fibula 12828.005 MAN 532 (Diode) Enamel Marne/F), from grave Saint-Etienne-au-Temple (département Large bright pearl 3105.001 MAN 532 (Diode) Bone or dentine Marne/F), without context Saint-Etienne-au-Temple (département Pendant 12730 MAN 532 (Diode) No specification Marne/F), without context Bracelet with several Saint-Etienne-au-Temple (département 12729.001 MAN 532 (Diode) No specification pearls and pendants Marne/F), without context Saint-Hilaire-au-Temple (département 3 coral branches 27849 MAN 532 (Diode) Corallium rubrum Marne/F), from grave Saint-Hilaire-le-Grand (département Boar tusk 27622.002 MAN 785 (Diode, HE) Dentine Marne/F) ,without context Saint-Hilaire-le-Grand (département Boar tusk (?) 33943.001 MAN 785 (Diode, HE) Bone or dentine Marne/F), without context Saint-Hilaire-le-Grand (département Boar tusk 27622.003 MAN 785 (Diode, HE) Dentine Marne/F), without context Saint-Rémy-sur-Bussy (département Bronze fibula 4831.001 MAN 532 (Diode) Corallium Marne/F), unspecified grave Saint-Rémy-sur-Bussy (département Bronze fibula 4838.001 MAN 532 (Diode) Corallium Marne/F), unspecified grave Salins-les-Bains (département Jura), Camp Bronze fibula 50883 MAN 532 (Diode) Corallium du Château, western rampart, layer C Salins-les-Bains (département Jura), Camp Bronze fibula 50884 MAN 532 (Diode) Corallium du Château, western rampart, layer C Bronze fibula 79409 MAN Saône valley, without context 532 (Diode) Corallium Iron fibula with gold Schwieberdingen (Landkreis Ludwigsburg) Corallium & white A 35/34 LMW 632.8 (He-Ne) sheet decoration “Wartbiegel”, grave calcite

Minerals 2016, 6, 56 S6 of S7

Table S1. Cont.

Object Inventory Number Museum Origin Laser (nm) Analyzed Substance Sept-Saulx (département Marne/F), from Bronze fibula 80111.001 MAN 532 (Diode) Corallium grave Somme-Tourbe (département Marne/F), La Shoe knob 33299.003 MAN 532 (Diode) Corallium Bouvandeau, wagon grave Somme-Tourbe (département Marne/F), La Shoe knob 33299.004 MAN 532 (Diode) Corallium Bouvandeau, wagon grave Scabbard of a dagger A29/140 LMW -Weilimdorf, tumulus 7 632.8 (He-Ne) Corallium (département Marne/F), “Le Rond Bronze fibula 33275 MAN 532 (Diode) Corallium Bois”, from grave Val-de-Vesle, Thuisy (département Boar tusk 27662.001 MAN 785 (Diode, HE) Dentine Marne/F), from grave Viernheim (Landkreis Bergstraße), Bronze fibula BE 308b Worms 632.8 (He-Ne) Enamel without context Necklace with Villingen-Schwenningen (Schwarzwald- 487.9 (Ar+); 632.8 (He-Ne); almost unprocessed Vi 73/512 ALM 10 Baar-Kreis), tumulus “Magdalenenberg”, Corallium rubrum 830 (Diode) coral branches grave 122 Bronze fibula with Worms “Rädergewann”, from gold sheet BE 822 Worms 632.8 (He-Ne) Corallium grave 23.10.1935 decoration Roman fibula with REM14028 REM Worms, no further information 458 (Ar+) Goethite yellow inlay Worms-Abenheim, Rautwiesen, Bronze fibula BE 1070c Worms 632.8 (He-Ne) Corallium grave 2 Bronze fibula BE 1064 Worms Worms-Herrnsheim, grave von 1969 632.8 (He-Ne) Corallium Imitation of deer St 147 k Worms Worms-Rheindürkheim 632.8 (He-Ne) Spondylus spec. teeth Zwiefalten-Mörsingen (Landkreis Bronze fibula 11159 LMW Reutlingen), “Gassenäcker”, tumulus 2, 632.8 (He-Ne) Corallium grave 5 1 RGZM = Römisch-Germanisches Zentralmuseum, Mainz (); 2 MAN = Musée d’archéologie nationale, Saint-Germain-en-Laye (France); 3 BLM = Badisches Landesmuseum, (Germany); 4 LMW = Landesmuseum Württemberg, Stuttgart (Germany); 5 Esslingen = Stadtmuseum im Gelben Haus, Esslingen (Germany); 6 Glauberg = Keltenwelt am Glauberg, Glauburg (Germany); 7 LM Mainz = Landesmuseum Mainz (Germany); 8 REM = Reiss-Engelhorn-Museen, Mannheim (Germany); 9 Worms = Museum der Stadt Worms im Andreasstift, Worms (Germany); 10 ALM = Archäologisches Landesmuseum Baden-Württemberg, Zentrales Fundarchiv, Rastatt (Germany).

Minerals 2016, 6, 56 S7 of S7

Table S2. List of used Raman spectrometers with their settings and the amount of measurements.

Grating Power (mW or % of Raman Spectroscope Objective Laser (nm) Measurements (L/mm) Full Power) LabRAM HR800 (Jobin-Yvon-Horiba) 100× 458 (Ar+) 600 0.1 7 LabRAM HR800 (Jobin-Yvon-Horiba) 100× 458 (Ar+) 600 0.8–0.9 9 LabRAM HR800 (Jobin-Yvon-Horiba) - 487.9 (Ar+) 1800 - 7 LabRAM HR800 (Jobin-Yvon-Horiba) - 487.9 (Ar+) 900 10 37 LabRAM HR800 (Jobin-Yvon-Horiba) 100× LWD 514 (Ar+) 600 0.8–0.9 32 LabRAM HR800 (Jobin-Yvon-Horiba) 100× LWD 514 (Ar+) 600 0.11 16 XploRA (Horiba) 100× LWD 532 (Diode) 1200 10% 9 XploRA (Horiba) 100× LWD 532 (Diode) 2400 10% 1 Portable HE 532 (Jobin-Yvon-Horiba) 50× LWD 532 (Diode) 920 0.1 191 LabRAM HR800 (Jobin-Yvon-Horiba) 50× 532 (Diode) - - 47 LabRAM HR800 (Jobin-Yvon-Horiba) - 632.8 (He-Ne) 900 10 149 LabRAM HR800 (Jobin-Yvon-Horiba) - 632.8 (He-Ne) 1800 10 2 XploRA (Horiba) 100× LWD 638 (Diode) 1200 100% 1 XploRA (Horiba) 50× LWD 638 (Diode) 1200 100% 1 XploRA (Horiba) 100× LWD 785 (Diode) 1200 100% 1 XploRA (Horiba) 100× LWD 785 (Diode) 600 100% 1 XploRA (Horiba) 50× LWD 785 (Diode) 1200 100% 2 Portable HE 785 (Jobin-Yvon-Horiba) 40× IR LWD 785 (Diode) 685 0.4 103 LabRAM HR800 (Jobin-Yvon-Horiba) - 830 (Diode) - - 1 LabRAM HR800 (Jobin-Yvon-Horiba) - 1064 (Diode) - 50 3

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