Berliner Beiträge zur Archäomet:rie Seite 217-236 1998

Chemical profile of medieval grafitto ceramic finds. V. Investigation of archaelogogical finds from Nessebar and ()

L. KULEFF, R. DHNGOVA

Abstract Using instrumental neutron activation analysis the chemical composition of33 archaeological finds of sgraffito pottery excavated in Nessebar and Sozopol (Southeastern Bulgaria) has been determined. The analytical data, which are presented in the paper and include the concentration of Al, As, Au, Ba, Br, Ce, Co, Cr, Cs, Dy, Eu, Fe, Hf, K, La, Lu, Mg, Mn, Na, Nd, Rb, Sb, Sc, Si, Sm, Ta, Tb, Ti, U, V and Yb were interpreted by duster analysis. On the basis of similarity in the chemical composition the investigated 33 samples are grouped in 5 clusters. The chemical profile of the sgraffito pot:tery production from Nessebar and Sozopol during 12-th - 14-th century AD has been established. The analytical data for pot:tery, which does not belang to the local production, are compared with analytical data taken from the literature, with the aim to determine its provenance.

Zusammenfassung Durch instrumentellen Neutronenaktivierungsanalyse wurde die chemische Zusammensetzung archäologischen Sgraffitokeramikfunde aus Nessebar und Sozopol Südost Bulgarien) be­ stimmt. Die analytische Daten für Al, As, Au, Ba, Br, Ce, Co, Cr, Cs, Dy, Eu, Fe, Hf, K, La, Lu, Mg, Mn, Na, Nd, Rb, Sb, Sc, Si, Sm, Ta, Tb, Ti, U, V und Yb sind dargestellt und durch Clusteranalyse bearbeitet. Auf Grund ihrer Ähnlichkeit in der chemischen Zusammensetzung wurden die untersuchten 33 Funden in 5 Gruppen geteilt und der chemische Profil der in Nessebar und Sozopol während 12.-14.Jh. hergestellten Sgraffitokeramik bestimmt. Durch Vergleich mit der analytischen Daten, die von Literatur bekannt sind, wurde es auch versucht, die nicht zu der Ortsproduktion gehörten Keramikfunde, zu lokalisieren. lntroduction The medieva1 Sozopol has been situated on the same place as Apolonia- the ancient colony of the Greek town Mi letus and the present Sozopol (Fig.l ). The town has played significant roJe in the Bulgarian-Byzantine relations. In the period 12th-15th century the historical fate of Sozopol is extremely variable since the town periodically changed the Bulgarian or Byzantinian rule. During 13th-14th century Sozopol was established as one of the significant religious and cultural centers along the (e.g. Dimitrov, 1981 ), although it has been periodically plundered by the crusaders and the Genuese. The hi story of the small town Nessebar. situated to the north side of the Bourgas bay (see Fig. 1). is not much different. The medieva1 town is the inheritor of the Greek colony- Mesambria and sirnilary to Sozopol developed as an important administrative and cultural center, periodically changing from Bulgarian to Byzantine rule during 12th-14th century (e.g. Guezelev, 1981).

217 The archaeological excavations revealed a Iot of sgraffito ceramic fragments in both towns and among them there are big number of finds. decorated with monograms from the types shown in Fig.2. A pottery kiln has been excavated in Sozopol as weil as a number of wasters and unfinished sgraffito vessels have been discovered in both towns (Drajeva, 1985). This is an objective indication that sgraffitoceramies has been produced in Nessebar and Sozopol. Having in mind the strong Byzantine influence on the life style ofboth towns it is an interesting question whether pottery. decorated with monograms has been produced there and ifthe answer is positive then what exactly types of monograms. The present study has been devoted to looking for an answer to the above question and it represents a continuation of our systematic investigations of sgraffitoceramies discovered on the territory of Bulgaria (Kuleff et al., 1991; 1993; 1994; 1995). The already existing data permit the comparison of the chemical composition of the present finds to archaeological sgraffito pottery, produced in the Black Sea towns - Varna (Kuleff et al., 1994 ), , and (Kuleff et al. , 1995), in the interior towns- (Ku1eff et al., 1991) and Veliko Tirnovo (Ku1eff et al., 1993), as well as to finds from Greece (Megaw&Jones, 1985) and Turkey (Waksman, 1995). This comparison permits to Iook for objective exidence for possible trade contacts between these countries and towns by pottery exchange.

Experimental 1. Materials. Thirty three sgraffito ceramic finds have been investigated. They have been excavated in Nessebar (14) andin Sozopol (19). situated on the Bulgarian Black Sea coast (see Fig.l). The bigger part of the investigated finds are fragments of bowls, plates, jags etc. but there are several totally preserved finds. Nine ofthe finds have been discovered in the pottery workshops. excavated in Nessebar and Sozopol (Drajeva, J985), 13 finds are decorated with monograms (see Fig.2 and Fig.3 (Talbot-Rice, 1930; Kuzev, 1975) and the rest- with diffe­ rent geometric and stylized plant motives. The description of the finds is presented in Table 1 and part of the finds are illustrated in Fig.2. 2. Method of analysis. The investigated samples were subjected to instrumental neutron activation analysis (INAA), using the the scheme for INAA of pottery, proposed in Kuleff et al., (1986); Kuleff&Djingova (1990) which permited the determination ofthe concentration of 31 elements: Al, As, Au, Ba, Br, Ce, Co, Cr, Cs, Dy, Eu, Fe, Hf, K, La, Lu, Mg, Mn, Na, Nd, Rb, Sb, Sc, Si, Sm, Ta, Tb, Ti, U, V and Yb. The analytical data have been interpreted using the program package of the Brookhaven National Labaratory (Sayre, 1988) for multivariate analysis.

Results and discussion The analytica1 data are presented in Table 2. Each result is a mean of three parallel determinations and is characterized by the respective standard deviation. The analytical data were subjected to cluster analysis and the results are presented in Table 3, where the formation of 5 clusters (and 4 outliers) may be seen. The composition of the clusters (Table 3), as weil as the description of the samples (Tab1e 1) indicate that the members of two of the clusters (cluster 1 and cluster 4) are local production. The reason for this statement is the fact among the members of the two clusters are samples found in the pottery kilns near Sozopol (26l.SOZ, 262.SOZ, 263.SOZ, 264.SOZ, 265.SOZ,

218 266.SOZ) and Nessebar (294.NES and 295.NES). The fact that the local Nessebar and Sozopol production is mixed in the clusters is quite interesting. This mean that the medieval potters from the two towns have used simultaneously two clay beds. The archaeological evidences about the finds from the kilns of the towns exclude the possibility for a single production center. The fact that the potters from one town use two clay beds is not an unusal practice in medieval Bulgaria (see Kuleff et al. , 1991; 1993; 1994; 1995). It is also not suprising that the potters from near-by towns (50 km away- see Fig. 1) use the same clay bed. Such practice has been established for Roman ceramies (2nd-4th century AD), produced in the region of Nicopolis ad Istrum (Kuleff&Djingova, 1996 a). The establishment ofthese facts however reveals some interesting sides of the organization of pottery production in Nessebar and Sozopol. Only one find (282.SOZ), decorated with a monogram "K" is a member of the local cluster. The style ofincising the Ietter "K" on this find is not unusual (see Talbot-Rice, 1930; Kuzev, 1975; Fig.3). Similar style is known for a find , local production in Varna (Kuleff et al. , 1994). (In Varna both types of writing the monogram "K" (see Fig.3) have been established as Iocal production.) In dusters 3 and 5 only monograms are participating inclusive "Dimitrios". "K" . "A". and "Paleologos" (duster 3) and "Dimitrios" . "Mikhail" and "Paleologos" (cluster 5). The distribution of the vessels with monograms among two clusters and the outliers indicates that the significant part of these vessels have been imported in the two towns. Simultaneously as in our previous investigations (Kuleff et al., 1986; 1989; 1991; 1993; 1994; 1995) mono­ gram vessels of lokal (Bulgarian) origin have been estalished. This confirms once more the fact that sgraffito vessels, decorated with monograms from some of the types in Fig.3, have been produced in the setlements along the Black Sea coast. Up till now the investigations (Kuleff et al. , 1986; 1989; 1991; 1993; 1994; 1995) proved that an object of Iocal production in Varna and Kaliakra have been vessels, decorated with monograms, deciphered as "Dimitrios", "Mikhail", "Andronikos" and "K" as weil as such decorated with signs of unknown meaning (see Fig.2; Fig.3; Talbot-Rice, I 930; Kuzev, 1975). Such a diversity in the production in Nessebar and Sozopol has not been established. Untill present we do not have evidences that such monograms have been produced in the interior towns (Shumen, Tcherven, Veliko Tirnovo- see Fig 1) . Most probably this is due to the stronger Byzantine influence in the Black Sea towns. Untill now however Iocal Bulgarian production of a monogram. deciphered as "Pafeologos" (Talbot-Rice, 1930; Kuzev, 1975; see Fig.2; Fig.3) has not been established. The mean concentrations for the determined elements for the clusters with local origin are presented in Table 4. These results represent the chemical profile ofthe Iocal pottery production in Nessebar and Sozopol (12th-14th century). The data in Table 4 demonstrate the high statistical significance of the formation of the clusters. The relative standard deviation (RSD) for most ofthe elements are in the range 5-30 %. High er variationwas established for elements. already discussed in details in (Kuleff et al. , 1986; 1987; Kuleff&Djingova, 1990; 1996; Djingova&Kuleff, 1991): As (65 %, 75 %); Sb (42 %, 83 %); Ba (43 % in cluster 1) and Tb (41 % in duster 4). Therefore these elements have not been used in duster analysis. The mean chemical composition of the dusters with unknown origin is presented in Table 5. Except for As, Sb and Tb unusually high variation is established in the case o[ Ce ( 43 %) and Co (49 %) in cluster 5. where only 3 finds are included. At present we cannot give an explanation of this fact. The analytical data presented in Table 2 and the results from the cluster analysis (Table 3) permit a comparison to finds from other Black Sea towns (Kuleff et al., I 994; 1995) as weil

219 as to finds from Shumen and Tsherven (Kuleff et al. , 1991). Veliko Tirnovo (Kuleff et al., 1993). investigated earlier.

The cross exmination ofthe outliers from Nessebar and Sozopol to the loca1 groups from Varna, Ka1iakra, Baltchik, Kavarna, Shumen, Tcherven and Veliko Tirnovo and of their outliers to the Jocal Nessebar and SozopoJ groups proved that neither of the outliers has been an object of exchange between these centres.

The sametestwas performed for the three clusters (clusters 2 and 3 and 5 in Table 3) with unknown origin and it proved that neither of them originates from North Bulgaria.

Using the same procedure (pro gram ADSEARCH- Sayre, 1988) test of the similarity has been performed between the investigated finds from Nessebar and Sozopol to sgraffito ceramic finds from Greece. described in (Megaw&Jones, 1985) and analyzed by us using INAA. The result proved that the investigated finds have not been produced in Thessaloniki. Lemba (Cyprus) or Didymoteichon.

Hoping to discover the probable origin of the sgraffito ceramic finds from Nessebar and Sozopol a comparison was also performed to finds from (Waksman, 1995). In order to exclude any difference due to analytical procedures and methods, used in (Kuleff et al., 1986) and Strasbourg (Waksman, 1995), a concentration correction factor was introduced. calculated after comparison ofthe analytical data obtained in Sofia (Djingova et al., 1990) and Strasbourg (Waksman, 1995) by analysis of the "Lefkandi brick" standard of Dr.R.E.Jones (I 991 ). The comparison proved that the fi nds from Nessebar and Sozopol are not produced from Pergarnon clays.

Conclusion

The analytical data presented in this paper (Table 2) represent the chemical characterization the sgraffito ceramics. excavated in Nessebar and Sozopol. They can be used for further investigations and comparison with analytical data for sgraffito pottery, excavated in different places of the Balkan peninsula, Asia Minor and Near East. The statistical interpretation of the analytical data (cluster analysis) permited to distinguish the local production from imported ceramies and thus to establish of the chemical profile of the locally produced sgraffito ceramics. The formation of two statistically significant local groups is an indication that the potters in Nessebar and Sozopol have used two common clay beds.

The comparison of the samples with unknown origin excavated in Nessebar and Sozopol to finds. produced in North Bulgaria. Greece. Cyprus and Turkey. proved that they were not produced in any of the investigated centres. The Iack of analytical data for sgraffito pottery from lstambul (Constantinopole) hinders the testing with the mostprobable producing center.

Aknowlegelment. The authors are thankful to Dr.J.Cimbuleva (Archaeological Museum Nessebar) and Dr.Z.Drajeva (Archaeological Museum Bourgas) for providing of pottery samples for investigation.

220 References

DnviiTROV, B., 1981. Sozopol.- In: Bulgarski srednovekovni gradove i kreposti (Bulgarian medieval towns and fortresses). Eds. A. Kuzev and V.Guezelev, G.Bakalov, Varna, 1981, (in Bulg.), pp.388-407. DliNGOVA, R, KuLEFF, 1., 1991. Provenance study of pottery and glass:- In: Neutron Activation and Plasma Emission Spectromctric Analysis in Archacology: Eds.M.Hughes, M.Cowell, D,Hook, British Museum Occasional Paper 82; British Museum, London, 1991, pp. 121-141. DnNGOVA, R., KuLEFF, 1., PENEV, 1., 1990. INAA of reference materials for archaeometric investigation of pottery.- J.Radioanai.Nuci.Chem., 144. 397-406. DnNGOVA, R., KuLEFF, 1., PENEV, 1., 1995. Himiceski profil na nahodki ot srednovekovna sgrafito keramika. II.Izsledvane na arheologiceski nahodki ot Kaliakra, Baltchik I Kavarna. (Chemical profile of mediieval sgraffito ceramic finds. II.Investigation of archaeological finds from Kaliakra, Kavarna, and Baltshik). (in Bulg.).- Izv.National Hist. Museum Vama. (in press). DRAJEVA , Z., 1985. Masterskaiapo proizvodsvu sgrafito keramiki iz Sozopo1ia. (Workshop for production of sgraffito pottery in Sozopol). -In: Bulgaria Pontika Medii Aevi III. (in Russian). Sozopol. 1985. (in press). GuEZELEV, V., 1981. . - In: Bulgarski srednovekovni gradove i kreposti (Bulgarian medieval towns and fortresses). Eds. A. Kuzev and V.Guezelev, G.Bakalov, Varna, 1981, (in Bulg.), (in Bulg.). pp.325-355. JoNES, R., 1991. Current trends and issues in Mediterranean ceremic studies. -In: Proc. European Workshop on Archaeometric Research andArchaeometrical Studies of Ancient Ceramics. Rome. 1991. pp. 13-21. KuLEFF, I., DnNGOVA, R., 1990. Activation analysis in archaeology.- In: Activation Analysis. Ed. Z.Alfassi, CRC-Press, Boca Raton. Florida, 1990, vol.2, pp 427-489. KuLEFF, 1., DJJNGOVA, R., 1996. Provenance study of pottery:Choice of elementstobe determined. - Revue d' Archeometrie, 20, 57-67. KuLEFF, 1., DliNGOVA, R., 1996 a. Chemical profile of the pottery production in the ceramic centyre near Nicopolis ad Istrum. - Analyt.Lab., 5. 238-244. KuLEFF, I., DnNGOVA, R., DJINGOV, G., 1986. Provenance study ofpottery by INAA.- In: Proc.7- th Int.Conf. Modern Trends in Acti vation Analysis. Copenhagen, 1986. vol.2, pp. 787-791. KULEFF, 1., DnNGOVA, R., DJINGOV, G., 1989. Provenance study of sgraffitoceramies (13-th -14-th century) from Shumen and Tcherven. -In: Proc.25-th Int. Symp. Archaeometry, 1987. Archaeometry, Ed. Y.Maniatis.Elsevier, Amsterdam, Oxford, 1989, pp. 533-542. KuLEFF, 1., DJJNGOVA, R., DJJNGOV, G., PENEV, 1., 1994. Himiceski profil na nahodki ot sredno­ vekovna sgrafito keramika. I.Izsledvane na arheologiceski nahodki ot Varna. (Chemical profile of mediieval sgraffito ceramic finds. I.Investigation of archaeological finds from Varna), (in Bulg.). - Ann.Univ. de Sofia. Fac.Chim., 81. 63-78. KuLEFF, I., DHNGOVA, R., PENEV, I., 1986. INAA of pottery for provenance study.­ J.Radioanai.Nucl.Chem., 99. 345-358. KuLEFF, I., DliNGOVA, R., PENEV, I., 1991. Himiceski profil na nahodki ot srednovekovna sgrafito keramika. III.Izsledvane na arheologiceski nahodki ot Sumen i Cerven. (Chemical profile of mediieval sgraffito ceramic finds. III.Investigation of archaeologica1 finds from Sumen and Cerven). (in Bulg.). - Jahrbuch der Museen in Nordbu1garien, XVII, 289-311. KULEFF, I.,DJTNGOVA, R., PENEV, I., 1993. Himiceski profil na nahodki ot srednovekovna sgrafito keramika. IV.Izsledvane na arheo1ogiceski nahodki ot Veliko Tirnovo. (Chemical profile of mediieva1 sgraffito ceramic finds. IV.Investigation of archaeo1ogical finds from Veliko Tirnovo), (in Bulg.).- Jahrbuch der Museen in Nordbulgarien, XIX, 131-158.

221 KuzEv, A., 1975. Srednovekovna sgrafito keramika s monogrami ot Varna (Medievav sgraffito pottery with monograms from Varna). (in Bulg.)- Izv.National Hist.Museum Varna, X (XXV), 155-165. MEGAW, A., JoNES, R., 1985. Byzantine and allied pottery: A contribution by chemical analysis to problems of origin and distribution.- Ann.British School of Archaeol. at Athens, 78, 225- 231 SAYRE, E., 1988. Comments of Brookhaven data handling program, Brookhaven National Laboratory, New York, 1988. TALBOT-RICE, D., 1930. Byzantine Glazed Pottery, Oxford, Clarendon Press. Waksman, S.Y., 1995. Les ceramiques byzantines des fouilles de Pergame. Caracterisation des productions locales et importees par analyse elementaire par !es methodes PIXE et INAA et par petrographie.These CNR 95-40 No. 1979. Universire Louis Pasteur, Strasbourg, 1995.

Table 1. Description of the investigated archaeological finds of sgraffito pottery from Nessebar and Sozopol.

Lab. Description of the finds index 26l.SOZ Fragment without glaze. Kiln No. I (excavation Z.Drajeva, 1985) 262.SOZ Fragment. Wall of vessel. Fireplace of the kiln No.l, Drajeva, 1985 263 .SOZ Fragment. Wall of vessel. Fireplace of the kiln No.!, Drajeva, 1985 264.SOZ Fragment of vessel. Yellow glaze with brown lines. Kiln No.2, Drajeva, 1985 265.SOZ Bottom of vessel. Yellow glaze with brownish lines. Kiln No.2, Drajeva, 1985 266.SOZ Fcogmont. W•ll of ve3'el. Yellow gl"e. Kiln No.2, Dmjen, 1985 m 267.NES Fragment. Bottom of vessel. Beige brownish body. Traces of colourless glaze Monogram "L1IMITPIOl:". Arch.No.625 268.NES FragmentBottom of vessel. Cream-coloured body. Whiteengobe. Colourless glaze. Monogram "MMITPIOl:". Arch.No.628 269.NES Fragment. Bottom of vessel. Cream-coloured body. Colourless glaze. Monogram "L1IMITPIOl:". Arch.No.633 ..~ 270.NES Fragment of cup with handle. Cream-coloured body. White engobe. Colourless glaze. Monogram "MIXAHA". Arch.No.622 )it 271 .NES Fragment of bottom of cup. Beige brownish body. •" White engobe. Yellowish glaze. Darkgreen line. Monogram "MIXAHA". Arch.No.639 it 272.NES Fragment of bottom of cup. Cream-coloured body. White engobe. Yelowish glaze. Monogram "MIXAHA". 1)11 Arch.No.670

222 Lab. Description of the finds index 273.NES Fragment. Bottom of vessel. Cream-coloured body. Yellowish glaze with brownish lines. Monogram "K". Arch.No.1826 ® 274.NES Fragment. Body of vessel. Cream-coloured body. Yelloish glaze with brown lines. Monogram "K". 275.NES Fragment. Bottom of vessel. Beige brownish body. ® White engobe. Lightgreen glaze. ~ Monogram " AN~PONIKOI: " (?). Arch.No.62J 276.NES Fragment. Bottom of vessel. Cream-coloured body. White engobe. Lightgreen glaze. Monogram @) " AN~PONIKOI: " (?). Arch.No.623 277.NES Fcagment. Bottom ond woll of bowl. Ughtbmwn hody. 'ffic White engobe. Lightgreen glaze with brown lines. Monogram " OAAAIOAOrOI:". Arch.No.592 278.NES Fragment. Bottom of vessel. Cream-coloured body. fflr White engobe. Light yelloish glaze. Monogram "OAAAIOAOfOI:". Arch.No.640 279.SOZ Fragment of cup. Cream-coloured body. Yelloish glaze. Outside-green and greenbrownish glaze. Darkbrown lines. Rosette. Arch.No.533 280.SOZ Bowl. Lightbrown body. Yellow-brown glaze. Brown lines. Geometrie motive. Arch.No.525 28l.SOZ Bowl. Cream-coloured body. Yellow glaze with brown line. Outside - yellow brown glaze with brown spot. Geometrie motive. Arch.No.517 282.SOZ Fragment. Bottom of vessel. Cream-coloured body. Light yellow glaze with green spot. Brown line. ~ Monogram "K". Arch.No.524 283.SOZ Fragment. Wall of cup. Red body. White engobe.

Light yellow glaze. Outside- green glaze. Rosette. Arch.No.522 284.SOZ Fragment of bowl. Cream-coloured body.

Light yellow glaze. Brown line. Stylized bird. Arch.No.644 285.SOZ Fragment of bowl. Light brown body. White engobe. Colourless glaze with brown lines. Arch.No.643

223 Lab. Description of the finds index 286.SOZ Fragment. Cream-coloured body. Yellow glaze. Brown line. Bird (?). Arch.No.Sll 287.SOZ Fragment. Cream-coloured body. White engobe. Yellow glaze with brown line. Bird (?). Arch.No.509 288.SOZ Fragment. Cream-coloured body. Brown glaze with darkbrown line. Outside - trace of white engobe. Arch.No.504 289.SOZ Jar. Cream-coloured body. Trace of white engobe. Light yellow glaze with green spot. Plant motive. Arch.No.l700 290.SOZ Fragment of jar. Light brown body. Yellow brown glaze with brown line. Arch.No.506 29l.SOZ Fragment without glaze. Kiln No.l (excavation Z.Drajeva, 1985) 294.NES Amphore(?). Kiln. dated 14'h century. Arch.No.2344 295.NES Amphore(?). Kiln. dated 14'h century. Arch.No.l920

224 Table 2. Chemical content of the investigated finds of sgraffito pottery from Nessebar and Sozopol [)lg/g]. Eie- 26l.SOZ 262.SOZ 263.SOZ 264.SOZ 265.SOZ ment Al(%) 9.45±0.36 98 .59±0.38 9.R8±0.38 9.95±0.20 9.69±0.12 As 6.9±1.1 5.7±0.9 6.7±0.9 18.7±3.1 11.4±1.5 Au 0.0 15±0.004 <0.002 0.004±0.002 0.019±0.004 <0.002 Ba 654±70 576±65 500±70 750±100 420±50 Br 1.3±0.3 0.5±0.3 0.6±0.3 7.9±0.3 2.7±0.3 Ce 162.0±17.0 152.2±15.1 153.0±14.0 87.3±9.4 131.3±13.7 Co 19 .3±1.1 19.8±0.6 16.1±1.0 24.0±0.8 19.4±0.8 Cr 120±10 81±8 85±5 175±10 155±5 Cs 7.8±0.8 7.1±0.7 6.5±0.7 10.2±1.2 8.5±0.9 Dy 7.1±0.3 6.1±0.3 6.7±0.3 5.8±0.3 6.2±0.2 . Eu 1.14±0.10 1.47±0.13 1.53±0.14 1.34±0.12 1.35±0.12 Fe(%) 4.67±0.02 3.73±0.03 3.75±0.07 4.82±0.05 4.00±0.04 Hf 4.6±0.4 7.5±0.6 7.8±0.7 4.9±0.4 5.4±0.4 K (%) 1.91±0.08 2.46±0.10 2.53±0.12 2.55±0.21 2.72±0.12 La 46.4±1.9 56.6±2.4 48.0±1.9 47.2±2.3 44.6±2.2 Lu 0.75±0.07 0.49±0.05 0.60±0.07 0.53±0.06 0.57±0.07 Mg(%) 1.09±0.12 0.77±0.07 0.75±0.07 1.63±0.15 1.41±0.14 Mn 806±32 ] 100±50 1030±30 867±35 820±40 Na(%) 1.41±0.14 1.79±0.19 1.56±0.16 1.10±0.10 1.21±0.13 Nd 48±5 54±6 40±5 37±4 33±4 Rb 110±14 115±15 85±11 126±16 73±9 Sb 1.3±0.2 1.5±0.2 2.1±0.3 0.4±0.1 4.3±0.4 Sc 16.0±0.8 12.2±0.7 12.2±0.8 19.7±1.0 16.9±0.9 Si (%) 29.46±2.16 31.28±2.17 29.95±2.33 25 .35±1.77 24.40±2.34 Sm 8.9±0.6 8.2±0.6 8.5±0.6 7.5±0.6 6.9±0.7 Ta 1.1±0.1 1.5±0.2 1.1±0.1 1.2±0.2 1.3±0.1 Tb 1.30±0.13 1.00±0.11 1.23±0.12 1.11±0.12 1.12±0.12 Th 12.6±1.8 17.8±1.8 18.0±1.8 14.0±1.4 12.8±1.0 Ti 7480±600 6795±575 6185±550 6260±380 6500±520 u 3.7±0.3 4.5±0.3 4.5±0.3 2.5±0.2 2.5±0.2 V 127±7 110±8 117±7 130±10 123±8 Yb 3.4±0.3 1.9±0.2 3.7±0.4 2.3±0.3 2.7±0.3

225 Table 2. (continuation)

Ele- 266.SOZ 267.NES 268.NES 269.NES 270.NES ment Al(%) 7.39±0.22 10.35±0.62 9.90±0.30 10.26±0.25 12.15±0.37 As 2.9±0.3 8.4±0.8 6.4±0.7 8.7±0.9 9.2±1.1 Au 0.012±0.002 0.007±0.002 0.0 11±0.002 0.011±0.003 0.015±0.002 Ba 475±80 300±70 375±50 450±80 190±30 Br <0.3 9.6±1.4 2.5±0.4 <0.3 3.2±0.5 Ce 111±5 108±4 82±3 103±5 117±5 Co 17 .8±0.8 9.3±0.6 18.5±0.5 23.0±0.3 16.1±0.8 Cr 103±10 176±15 132±14 137±15 57±6 Cs 7.8±0.9 5.7±0.7 5.2±0.8 6.7±0.7 2.5±0.3 Dy 5.9±0.3 6.1±0.4 5.8±0.3 6.7±0.4 15.5±0.7 Eu 1.60±0.15 1.70±0.17 1.21±0.12 1.34±0.14 3.52±0.35 Fe(%) 3.89±0.16 6.34±0.26 3.11±0.12 3.67±0.12 6.49±0.25 Hf 9.0±0.7 6.6±0.6 5.5±0.5 6.7±0.6 5.1±0.4 K (%) 1.80±0.07 1.41±0.06 0.89±0.04 1.22±0.06 1.08±0.05 La 39.9±1.6 42.:1±1.7 30.8±1.2 35.6±1.3 52.5±2.1 Lu 0.66±0.06 0.46±0.04 0.49±0.04 0.51±0.04 1.19±0.09 Mg(%) 0.99±0.08 0.79±0.08 0.36±0.04 0.94±0.09 1.37±0.11 Mn 720±30 150±6 880±35 1030±40 190±8 Na(%) 1.26±0.08 0.56±0.04 1.01±0.06 0.92±0.06 0.90±0.06 Nd 51±6 52±6 26±3 42±5 79±8 Rb 107±9 60±8 37±5 73±8 63±8 Sb ] .4±0.1 21.0±1.6 3.2±0.2 1.3±0.1 3.8±0.3 Sc 13.9±0.4 24.8±0.8 16.7±0.4 18 .9±0.6 23.0±0.8 Si (%) 25.61±1.82 21.38±1.54 27.33±1.95 28.88±1.96 14.04±0.98 Sm 8.0±0.5 8.2±0.5 6.4±0.4 6.9±0.5 15 .2±0.9 Ta 1.4±0.2 2.5±0.3 1.2±0.2 1.3±0.2 1.4±0.2 Tb 1.2±0.1 0.9±0.1 0.9±0.1 0.7±0.1 1.9±0.2 Th 15 .0±0.5 12.5±0.5 9.9±0.5 12.3±0.5 7.5±0.4 Ti 5820±700 6600±850 7800±860 9450±950 9570±900 u 3.4±0.2 3.3±0.2 3.8±0.2 4.0±0.3 4.4±0.3 V 98±5 174±7 109±6 116±6 197±8 Yb 2.9±0.3 2.9±0.3 2.3±0.2 2.6±0.3 6.5±0.6

226 Table 2. (continuation) Eie- 27l.SOZ 272.NES 273 .NES 274.NES 275.NES ment Al(%) 14.19±0.56 11 .95±0.36 9.51±0.29 10.76±0.33 9.98±0.25 As <0.1 11.8±1.2 8.2±0.8 16.0±1.7 7.5±0.8 Au 0.016±0.003 0.009±0.002 0.016±0.003 <0.002 <0.003 Ba 430±60 382±52 560±70 540±70 376±50 Br 1.1±0.2 2.1±0.3 1.3±0.2 1.0±0.2 4.8±0.7 Ce <1 57.0±2.4 104.0±4.8 104.0±4.5 92.0±4.0 Co 7.0±0.3 9.4±0.4 22.1±0.9 24.5±1.1 15.3±0.6 Cr 193±20 176±18 129±13 143±15 132±14 Cs 4.2±0.5 3.9±0.4 6.3±0.7 6.1±0.6 3.7±0.4 Dy 7.6±0.4 6.2±0.3 6.1±0.3 6.2±0.3 5.9±0.3 Eu 2.40±0.24 1.00±0.10 1.45±0.15 1.68±0.17 1.07±0.11 Fe(%) 5.78±0.23 7.78±0.31 3.62±0.15 4.62±0.21 2.93±0.13 Hf 8.5±0.6 8.0±0.6 8.2±0.6 9.3±0.8 6.9±0.5 K (%) 0.75±0.04 I .04±0.05 1.71±0.10 1.73±0.10 1.38±0.6 La 58.0±1.8 27.1±0.8 35 .8±1.1 41.7±1 .4 31 .2±0.9 Lu 0.52±0.04 0.70±0.06 0.58±0.06 0.28±0.03 0.40±0.03 Mg(%) 0.19±0.02 0.86±0.07 0.60±0.05 0.95±0.08 0.77±0.07 Mn 140±5 220±7 940±40 1040±40 547±17 Na(%) 0.20±0.02 0.39±0.02 1.05±0.05 1.02±0.05 1.16±0.05 Nd 37±4 63±6 50±5 67±7 34±4 Rb 139±15 56±7 72±10 119±15 67±9 Sb <0.1 2.0±0.2 6.4±0.5 2.7±0.2 1.0±0.1 Sc 27.3±1.1 30.3±1 .2 21.1 ±0.8 25.8±1.0 18 .9±0.8 Si (%) 24.49±1.56 22.72±1.38 28.28±1.68 27.64±1.68 24.49±1.50 Sm 11.0±0.7 3.8±0.2 6.9±0.4 8.4±0.5 6.0±0.4 Ta 1.4±0.1 1.6±0.1 1.7±0.1 1.4±0.1 2.0±0.1 Tb 5.2±0.5 3.5±0.4 3.4±0.4 1.8±0.2 1.0±0.1 Th 10.5±0.4 9.2±0.4 12.7±0.5 15.6±0.6 11.6±0.5 Ti 8750±450 11300±570 9070±450 8520±450 10250±520 u 5.2±0.3 4.3±0.2 4.1±0.2 3.8±0.2 4.2±0.2 V 93±4 175±7 109±5 122±5 131±6 Yb 3.6±0.4 3.8±0.4 2.7±0.3 3.6±0.4 3.0±0.3

227 Table 2. ( continuation)

Eie- 276.NES 277.NES 278.NES 279.SOZ 280.SOS ment Al(%) 9.05±0.3 6 13.68±0.56 10.13±0.40 12.30±0.48 8.80±0.35 As 6.6±0.7 21.3±2.1 9.3±0.9 <0.1 <0.1 Au 0.017±0.003 0.030±0.005 0.024±0.004 0. 127±0.019 0.016±0.002 Ba 470±70 315±35 790±120 1660±250 500±75 Br

228 Table 2. (continuation) Eie- 28l.SOZ 282.SOZ 283.SOZ 284.SOZ 285.SOZ ment Al(%) 10.07±0.40 8.99±0.36 8.34±0.33 10.97±0.44 10.13±0.40 As <0.1 24.1±2.4 24.2±2.5 20.6±2.1 25.6±2.6 Au 0.038±0.006 0.010±0.002 0.007±0.001 0.027±0.005 0.039±0.006 Ba 720±100 462±60 690±90 630±90 530±75 Br 13 .1±1.4 <0.7 13.6±1.4 10.7±1.1 <1 Ce 124.0±5.0 130.0±6.5 102.0±5.2 <1 62.0±3.1 Co 9.3±0.5 19.8±1.0 24.8±1.2 17.5±0.9 2l.l±l.l Cr 145±15 122±12 150±15 218±21 120±12 Cs 4.1±0.4 7.5±0.7 13 .6±1.4 18.1±1.8 10.4±1.1 Dy 8.2±0.5 6.0±0.3 5.4±0.3 5.2±0.3 6.7±0.4 Eu 1.44±0.15 1.29±0.13 1.32±0.13 1.08±0.11 1.28±0.13 Fe(%) 6.69±0.27 3.77±0.15 5.35±0.22 6.82±0.27 4.25±0.17 Hf 8.6±0.6 7.4±0.6 4.6±0.4 <1 5.5±0.5 K (%) 1.96±0.10 1.53±0.08 2.24±0.11 3.00±0.15 3.23±0.16 La 39.5±1.2 38 .6±1.4 35 .5±1.8 41.3±2.1 43.6±2.1 Lu 0.65±0.06 0.47±0.04 0.43±0.04 0.47±0.04 0.46±0.04 Mg(%) 1.27±0.11 1.42±0.13 0.18±0.02 1.90±0.15 1.33±0.11 Mn 1090±40 840±30 1350±55 950±40 900±30 Na(%) 1.18±0.07 1.06±0.07 1.01±0.06 1.52±0.08 1.31±0.07 Nd 70±7 68±7 47±5 73±7 72±7 Rb 187±25 118±16 222±26 375±45 190±25 Sb <0.1 1.9±0.2 2.9±0.3 4.5±0.4 2.8±0.3 Sc 26.7±1.1 21.3±0.9 21.9±0.9 21.5±0.8 17 .8±0.7 Si (%) 29.75±1.80 29.21±1.75 29.39±1.75 27.34±1.53 28.93±1.73 Sm 9.7±0.6 7.5±0.8 6.3±0.5 8.0±0.5 8.4±0.5 Ta 1.1±0.1 1.2±0.1 0.8±0.1 5.9±0.1 1.1±0.1 Tb 0.6±0. 1 1.9±0.2 1.3±0.1 9.2±0.9 1.9±0.2 Th 12.0±0.5 13 .0±0.4 15.6±0.6 24.0±1 .0 13.9±0.5 Ti 10500±500 9250±450 7580±350 6850±350 5900±300 u 3.1±0.2 4.0±0.3 3.0±0.2 2.6±0.3 2.2±0.2 V 158±7 127±6 109±5 132±6 109±5 Yb 4.6±0.5 3.0±0.3 4.1±0.4 2.7±0.3 3.1±0.3

229 Table 2. ( continuation) Ele- 286.SOZ 287.SOZ 288.SOZ 289.SOZ 290.SOZ ment Al(%) 9.04±0.27 9.64±0.32 9.89±0.36 8.59±0.32 8.65±0.26 As 4.4±0.4 13.9±1.4 5.2±0.6 11.3±1.1 <0.1 Au 0.032±0.005 0.038±0.005 0.020±0.004 0.026±0.003 0.013±0.002 Ba 760±80 1000±110 780±80 218±1 2 775±80 Br <0.4 <0.8 2.2±0.3 1.3±0.2 4.9±0.6 Ce 108.0±4.1 114.0±5.0 62.0±7.2 109.0±4.3 119.0±5.1 Co 16.6±0.7 18.7±0.7 16.0±0.6 18.7±0.7 7.7±0.4 Cr 82±8 94±10 80±8 109±10 167±17 Cs 9.0±0.9 14.1 ±1 .4 9.2±0.9 14.1±1.4 4.6±0.5 Dy 6.9±0.4 6.6±0.4 5.6±0.3 7.70.4 6.6±0.4 Eu 1.57±0.16 1.70±0.17 1.33±0.13 1.60±0.16 1.62±0.16 Fe(%) 4.20±0.17 5.03±0.20 4.39±0.18 4.42±0.18 5.39±0.21 Hf 8. 1±0.7 9.7±0.9 5.4±0.5 9.6±0.9 14.3±1.2 K (%) 2.28±0.09 2.51±0.10 2.80±0.12 2.11±0.09 3.03±0.13 La 48.6±1.5 52.5±1.6 33.8±1.0 50.2±1.6 43.8±1.4 Lu 0.53±0.04 0.53±0.04 0.38±0.04 0.60±0.05 0.55±0.04 Mg(%) - 0.83±0.07 1.04±0.08 1.22±0.09 1.00±0.08 Mn 895±30 785±25 926±30 923±30 909±30 Na(%) 1.40±0.08 1.48±0.08 1.49±0.09 0.87±0.04 1.22±0.07 Nd 56±6 112±11 41±4 72±7 44±5 Rb 170±18 210±22 126±13 190±20 286±30 Sb 3.0±0.3 1.9±0.2 1.4±0.2 2.6±0.3 <0. 1 Sc 15.0±0.5 17 .2±0.5 16.4±0.5 16.2±0.5 19.2±0.6 Si (%) 33.41±2.00 27.48±1.68 30.39±1.86 33.90±2.02 30.70±1.90 Sm 9.3±0.6 10.1±0.6 6.7±0.6 9.9±0.6 7.9±0.5 Ta 1.0±0.1 1.7±0.2 1.1±0.1 1.4±0.1 1.6±0.2 Tb 2.0±0.2 1.9±0.2 1.8±0.2 2.2±0.2 <0.3 Th 15.8±0.7 28.0±1.2 12.1±0.6 17.2±0.7 18 .5±0.7 Ti 7520±480 6525±400 6740±420 7770±500 6400±400 u 4.4±0.4 3.9±0.4 3.1±0.3 3.2±0.3 4.0±0.3 V 110±4 117±5 118±6 115±5 120±6 Yb 3.9±0.4 3.7±0.4 3.1±0.3 3.9±0.4 4.0±0.3

230 Table 2. ( continuation) Eie- 29l .SOZ 294.NES 295 .NES ment Al(%) 9.88±0.30 9.55±0.30 9.18±0.25 As 2.2±0.3 15 .1±1.5 8.7±0.9 Au 0.007±0.002 0.041±0.004 0.023±0.003 Ba 480±50 338±35 425±45 Br 5. 3±0.6 2.9±0.4 4.3±0.5 Ce 120.0±5.0 57.2±2.4 87.0±0.4.0 Co 15.7±0.6 13 .0±0.4 16.9±0.5 Cr 87±8 70±7 91±9 Cs 8.5±0.9 4.6±0.5 5.9±0.6 Dy 8.3 ±0.4 9.0±0.4 6.9±0.3 Eu 1.72±0.18 1.08±0.11 1.45±0.15 Fe(%) 4.16±0.17 3.64±0.14 4.44±0.17 Hf 8.9±0.7 5.2±0.4 8.6±0.7 K (%) 2.29±0.09 3.04±0.12 2.41 ±0.09 La 46.3±1.4 30.1 ±1.2 45.3±1.4 Lu 0.58±0.05 0.33±0.03 0.50±0.04 Mg(%) 0.89±0.09 1.47±0.12 0.91 ±0.09 Mn 850±30 835 ±30 900±30 Na(%) 1.47±0.08 1.37±0.07 1.48±0.08 Nd 63±6 26±3 40±4 Rb 197±22 116±16 162±17 Sb 0.6±0.1 0.9±0.1 1.1 ±0.1 Sc 14.6±0.6 11.7±0.5 13 .7±0.6 Si (%) 27.95±1.70 27 .68±1.80 30.00±1 .90 Sm 9.3±0.8 5.0±0.4 8.5±0.6 Ta 1.2±0.1 0.9±0. L 1.4±0.1 Tb 2.1 ±0.2 0.6±0.1 1.0±0.2 Th 18.3±0.7 10.3±0.5 15 .3±0.6 Ti 7870±320 7025±330 6930±280 u 3.8±0.3 2.6±0.3 3.0±0.3 V 132±5 125±5 114±5 Yb 4.3±0.4 2.6±0.3 3.9±0.4

231 Table 3. Membership in the clusters. Cluster Membership 1 262.SOZ, 263.SOZ, 266.SOZ, 286.SOZ, 287.SOZ, 289.SOZ, 291.SOZ, 295 .NES . 2 281.SOZ, 290.SOZ 3 268.NES, 269.NES, 273.NES, 274.NES, 275.NES, 276.NES, 2n.NES , 4 26l.SOZ, 264.SOZ, 265.SOZ, 280.SOZ, 282.SOZ, 285.SOZ, 288.SOZ, 294.NES. 5 267.NES, 270.NES, 272.NES, 277.NES. outlier 27l.NES, 279.SOZ, 283.SOZ, 284.SOZ

Table 4. Chemical profile of sgraffito pottery [mg/g] produced in Nessebar and Sozopol during 12'h-14'h century.

Eie- Cl.l RSD Cl.4 RSD ment (n=7) [%] (n=7) [%] Al(%) 9.18±0.93 10.1 9.55±0.50 5.3 As 6.7±4.4 65.7 13.2±9.9 75 .0 Ba 573±247 43.1 585±143 24.4 Ce 123.7±19.7 15.9 103.7±39.8 38.3 Co 17.6±1.7 9.7 18.4±4.8 26.0 Cr 91.6±10.9 11.9 133.0±32.5 24.5 Cs 9.6±3.2 33.3 9.0±1.1 12.4 Dy 6.9±0.9 13.0 6.3±0.5 8.4 Eu 1.61±0.09 5.7 1.24±0.14 11.5 Fe(%) 4.17±0.46 11.0 4.45±0.50 11.2 Hf 8.7±0.9 10.3 5.4±1.0 18.8 K (%) 2.32±0.28 12.2 2.37±0.61 26.0 La 48.9±5.2 10.6 39.5±9.0 8.4 Lu 0.57±0.06 10.5 0.51±0.12 23.5 Mg(%) 0.91±0.18 19.7 1.47±0.46 30.9 Mn 900±133 14.8 835±78 9.4 Na(%) 1.40±0.29 20.7 1.26±0.16 12.4 Nd 62±19 30.6 51±15 29.9 Rb 153±50 32.7 124±35 27.9 Sb 1.9±0.8 42.1 1.7±1.4 82.8 Sc 14.5±1.9 13 .1 19.0±2.4 12.6 Si (%) 30.00±3.12 10.4 27.68±2.27 8.2 Sm 9.0±0.8 8.9 7.2±1.5 20.2 Ta 1.33±0.24 18.3 1.09±0.23 20.9 Tb 1.65±0.50 30.0 1.36±0.55 40.8

232 E1e- Cl.l RSD Cl.4 RSD ment (n=7) [%] (n=7) [%] Th 18.6±4.3 23.2 12.8±1.0 8.1 Ti 6926±807 11.7 7023±1217 17.3 u 4.0±0.5 12.5 2.9±0.7 24.1 V 114.1 ±10.3 9.0 124.9±9.7 7.8 Yb 3.5±0.8 22.9 3.4±1.3 36.8

Table 5. Chemical profile of sgraffito pottery [mg/g] imported in Nessebar during 12'h -14'h century from other pottery centres. E1e- Cl. 3 RSD Cl.5 RSD ment (n=7) [%] (n=3) [%]

Al(%) 9.94±0.55 5.5 12.01±1.67 13 .9 As 9.0±3.3 36.6 13.8±6.7 48 .3 Ba 509±143 28.2 332±44 24.4 Ce 99.4±10.6 10.6 103 .7±44.7 43 .1 Co 21.2±3.3 15.4 13.0±6.4 49.0 Cr 134.4±6.5 4.8 186.3±15.4 8.3 Cs 6.2±1.8 28.2 5.6±2.0 36.6 Dy 6.0±0.4 6.6 6.5±0.6 8.5 Eu 1.39±0.20 14.5 1.45±0.39 26.8 Fe(%) 3.77±0.68 18.1 6.99±0.73 10.5 Hf 7.8±1.4 18.6 7.1±0.8 1.1.0 K (%) 1.42±0.29 20.7 1.15±0.22 19.2 La 36.9±4.9 13.3 36.2±8.0 22.2 Lu 0.45±0.10 22.0 0.56±0.12 21.9 Mg(%) 0.71±0.22 30.4 0.91±0.15 16.6 Mn 866±1 83 21.2 214±61 28.6 Na(%) 1.00±0.09 9.8 0.41±0.13 31.0 Nd 50±19 37.8 58±6 10.3 Rb 93±32 34.8 69±19 36.2 Sb 3.0±2.0 66.7 8.6±1 0.7 124.2 Sc 21.3±3.4 15 .8 30.2±5.4 17.9 Si (%) 27.17±1.44 5.3 22.34±1.05 4.7 Sm 7.3±1.0 13 .5 6.6±2.4 36.7 Ta 1.46±0.29 19.8 1.87±0.55 29.5 Tb 1.77±0.98 55 .2 2.00±1.35 67.3 Th 13.0±2.3 17.7 11.1±1.7 15.4 Ti 8860±730 8.2 8870±1960 22.1 u 4.0±0.2 4.7 4.4±1 .1 25.2 V 116.1±7 .9 6.8 185.3±18.8 10.1 Yb 2.8±0.4 14.7 3.3±0.5 15.2

233 N VJ .jO.

) J ( ·- · -·"·~.,...... ,~"\ ( a Baltchtk \ l b Kavarna ·~·-·-· \ \ c Kaliakra ..... "" \ \ .. 0 I Shumen I varna. r· 0 ...... ·..., V.Tirnovo \ < Nassebar w i 0 cn \ Sofia ) 'C .;.' (.) Sozopol < \ ...J ·, ,....,"..., Ul '-· BULGARIA ( -:-- ·- ,.,· ' ) \ ( .-· ) ., . . \.. -· . .-·" \ -L-.._.,..r·-·J'"..,..J' . -· '...... ) -...... ,... • ..",. • ...".• ..J

Fig. 1. Map of Bulgaria. Fig. 2. Some of the analyzed samples of sgraffito pottery.

235 1 2 3 4 5 6 7

8 9 10 11 12 13 14 15

16 17 18 19 20

Fig. 3. Some types of monograms. I +5 = Dimitrios 6, 7, 20 = Palaiologos 8-10 = K 11 = Ioanis; 12, 13 = Andronikos 14, 15 = no decipherment can be attempted; 16-19 = Michail

236