ORIGINAL SCIENTIFIC PAPER Croat. Chem. Acta 2015, 88(4), 421–425 Published online: January 15, 2016 DOI: 10.5562/cca2747 Investigations of Ancient Terra-cotta Sarcophagi, Excavated in Enez (Ainos) Turkey, by Instrumental Neutron Activation Analysis Sevim Akyuz,1,* Tanil Akyuz,1 Nuranya M. Mukhamedshina,2 Kubilay Balci,3 A. Adiba Mirsagatova,2 Gulnur Kurap,4 Sait Basaran5 1 Physics Department, Science and Letters Faculty, Istanbul Kultur University, Atakoy Campus, Bakirkoy 34156, Istanbul, Turkey 2 Institute of Nuclear Physics, Uzbek Academy of Sciences, 702132, Ulugbek, Tashkent, Uzbekistan 3 Physics Department, Science Faculty, Istanbul University, 34134 Vezneciler, Istanbul, Turkey 4 Restoration and Conservation of Artefacts Department, Fine Arts Faculty, Mimar Sinan Fine Arts University, Istanbul, Turkey 5 Restoration and Conservation of Movable Cultural Assets Department, Letters Faculty, Istanbul University, Vezneciler, Istanbul, Turkey * Corresponding author’s e-mail address: [email protected] RECEIVED: September 29, 2015 REVISED: November 26, 2015 ACCEPTED: November 26, 2015 THIS PAPER IS DEDICATED TO DR. SVETOZAR MUSIĆ ON THE OCCASION OF HIS 70TH BIRTHDAY Abstract: Ten terra-cotta sarcophagi, together with a terra-cotta aryballos (perfume jar), excavated in Su Terazisi necropolis of Enez-Turkey (Ancient Ainos), were investigated by Instrumental Neutron Activation Analysis (INAA), to determine the concentration of thirty two chemical elements: Na, K, Ca, Fe, Sc, Cr, Mn, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Sb, Cs, Ba, La, Ce, Nd, Sm, Eu, Tb, Dy, Yb, Lu, Hf, Ta, Th and U. The dataset was submitted to multivariate statistical analysis. The classification was done by cluster analysis. The results demonstrated the occurrence of two different groups of terra-cotta samples. Group I contains nine sarcophagi and terra-cotta aryballos whereas group II contains only one sample (E09-ST5-M26). High correlations between La and Ce (r2 = 0.92), and U and Th (r2 = 0.91) indicated that local clay was used for manu- facturing the terra-cotta sarcophagi and aryballos but probably the claybed used for E09-ST5-M26 was different from that of others. Keywords: ancient terra-cotta sarcophagi, archaeometry, Instrumental neutron activation analysis. INTRODUCTION the sea. The archaeological excavations in Enez have been going on for the last 45 years in a number of areas at this NEZ is a spectacular coastal town with its historical, ar- site.[2] During the excavations, some cemeteries were also E chaeological and natural values, at the Aegean Sea unearthed. The Su Terazisi Necropolis, named for an Otto- coast of Edirne. It is known as Ainos in antique periods and man water level in this area, is just to the east of the bridge is located on the southwest part of Edirne with the Aegean at the entrance to the city, contains tombs dating from the Sea on the west and Greece on the north. The center of the 6th and 5th centuries BC. At this necropolis, cremation and town was built in the ancient times as a Greek colony.[1] The inhumation burials in various types of tombs have been name of Enez comes from a Greek princess called Eneyaz.[1] found. The town was under the sovereignty of the Roman Empire, In our previous studies some ancient terra-cotta sar- Byzantium, republic of Genoa, Ottoman Empire, Russia and cophagi excavated in Enez in 2005 and 2008 were investi- Greece, in order.[1] The town was included in the Turkish gated by FTIR and XRF techniques.[3–4] In continuation of our Republic borders after the 1922. Enez (Ancient Ainos) is one studies on terra-cotta sarcophagi unearthed in the excava- of the most important archaeological sites in Turkey.[2] The tions of ancient Ainos, in this study, ten rectangular terra- excavation center is at the northern coast of the Aegean cotta sarcophagi, together with a terra-cotta aryballos (per- Sea, at the place of where Antic Hebros (Meric) river meets fume jar), belonging to 6th and 5th centuries BC and found 422 SEVIM AKYUZ et al.: Investigations of Ancient Terra-cotta Sarcophagi, Excavated in Enez … in the fourth, fifth or sixth zones of Su Terazisi necropolis in the half-life time of the elements.[9] For measurement and the 2009 excavations, were investigated by Instrumental treatment of the sample spectrum, gamma-spectrometer Neutron Activation Analysis (INAA). INAA is a very accurate was used with HPGe coaxial gamma-ray detector (the reso- and highly sensitive method for multi-elemental analysis, lution 1.8 keV at 1332.5 keV, relative efficiency 15 %), which has been extensively applied to provenance stud- charge sensitive preamplifier and multichannel analyzer ies.[5−7] Moreover, INAA, a technique that gives qualitative DSA-1000 with software Genie-2000 (Canberra industries). and quantitative information about rare-earth elements Uncertainties of the impurity content determination were and represents the preferred analytical technique to ad- estimated by the relative standard deviation (Sr), which was dress questions such as composition of ancient materials calculated from the results of 5 multiple (independent) and their provenance. The classification of the archaeologi- measurements. It was found to be in the range of 0.07−0.1. cal findings was done by multivariate statistical analysis. Cluster analysis was performed on INAA results using The Unscrambler CAMO software.[10] EXPERIMENTAL RESULTS AND DISCUSSION In this study body samples of ten terra-cotta sarcophagi (E09-ST4-M6; E09-ST4-M9; E09-ST4-M10; E09-ST4-M11; Concentrations of the 32 elements of the sarcophagi and E09-ST6-M13; E09-ST4-M16; E09-ST4-M17; E09-ST4-M19; the aryballos fragments were determined by the use of E09-ST5-M25; E09-ST5-M26) along with a terra-cotta INAA. The analytical results of Na, K, Ca, Fe, Sc, Cr, Mn, Co, aryballos fragment (perfume jar) (E09-ST5), that were un- Ni, Cu, Zn, As, Se, Br, Rb, Sr, Sb, Cs, Ba, La, Ce, Nd, Sm, Eu, Tb, earthed in the fourth, fifth or sixth zones of the excavation Dy, Yb, Lu, Hf, Ta, Th and U elements are given in Table 1. area of the Su-Terazisi (ST) necropolis (abbreviated as ST4, The relative abundance of rare-earths elements ST5 or ST6, respectively) in 2009, were investigated. All in- (REEs) is peculiar of the geological history of a material and vestigated sarcophagi are known as Clazomenian type[8] represents the fingerprint of an archeological material.[11,12] and have been discovered fragmented in the excavations It is often used as provenance indicator. The REEs, Hf, Ta, U (see Figure 1). Some of them have egg-frieze decorations at and Th elements distributions of the investigated samples the rim. The photographs of some terra-cotta sarcophagi are shown in Figure 2. Analysis of the graph of Figure 2 and the aryballos fragment are shown in Figure 1. shows that all the samples (except E09-ST5-M26) are fea- The terra-cotta fragments were analyzed using in- tured by a very similar pattern concerning REEs, Hf, Ta, U strumental neutron activation analysis. The samples were and Th elements, suggesting that the common geological irradiated simultaneously with reference materials from source of local clay was used for manufacturing the terra- IAEA (SL-1, Soil-7) for 70 hours, at thermal neutron flux den- cotta sarcophagi and aryballos, but may be two different sity of 6.5 1010 cm−2 s−1, in the nuclear reactor of Institute of clay sources were used. Figure 3 shows the scatterplots of Nuclear Physics, Tashkent, Uzbekistan. Conditions of cool- all samples projected on axes of mg/kg U and Th, and on ing and measuring were chosen by taking into account of Figure 2. Concentrations of REE, Hf, Ta, Th and U in terracotta sarcophagi and aryballos fragment. M9 = E09- ST4-M9; ARY = aryballos fragment; M6 = E09-ST4-M6; M10 Figure 1. Photographs of some investigated sarcophagi = E09-ST4-M10; M11 = E09-ST4-M11; M16 = E09-ST4-M16; (E09-ST4-M6, E09-ST4-M17, E09-ST5-M26) and terra-cotta M17 = E09-ST4-M17; M13 = E09-ST6-M13;M19 = E09-ST4- aryballos. M19; M25 = E09-ST5-M25; M26 = E09-ST5-M26. Croat. Chem. Acta 2015, 88(4), 421–425 DOI: 10.5562/cca2747 DOI: Table 1. INAA Analysis results (mg/kg unless where indicated) 10.5562/cca No Element ST4-M9 ARY ST4-M6 ST4-M10 ST4-M11 ST4-M16 ST4-M17 ST6-M13 ST4-M19 ST5-M25 ST5-M26 1 Na (%) 0.7±0.1 1.6±0.1 1.6±0.1 1.6±0.1 1.7±0.1 1.6±0.1 1.3±0.1 1.4±0.1 1.7±0.1 1.6±0.1 1.7±0.1 2 K (%) 3.3±0.1 1.0±0.1 2.8±0.1 3.2±0.1 2.6±0.1 2.8±0.1 2.5±0.1 2.7±0.1 3.9±0.1 2.7±0.1 4.8±0.1 2747 3 Ca (%) 5.8±0.3 13.0±1.0 7.0±0.3 5.0±0.3 4.0±0.3 3.0±0.2 5.0±0.3 2.7±0.2 4.1±0.2 3.6±0.2 3.4±0.2 4 Sc 24±1 23±1 5.8±0.5 8.3±0.5 13.0±0.9 9.8±0.9 9.0±0.9 9.4±0.9 12.0±0.9 12.0±0.9 11.0±0.9 5 Cr 430±20 220±10 29±2 51±3 78±3 71±3 42±3 59±3 60±3 52±1 28±2 AKYUZ SEVIM 6 Mn 760±30 820±40 380±17 490±22 570±27 540±22 650±30 520±20 720±32 820±38 1200±65 7 Fe (%) 6.1±0.3 5.9±0.3 1.6±0.1 2.1±0.1 3.2±0.1 2.8±0.1 2.3±0.1 2.5±0.1 3.2±0.1 3.6±0.1 6.3±0.3 8 Co 40±2 31±2 7.2±0.6 8.0±0.6 14.5±1.0 9.8±0.9 8.9±0.9 9.7±0.9 12±0.9 13±0.9 12±0.9 9 Ni 390±20 210±20 nd nd 28±2 52±2 nd nd 52±2 46±2 nd et al.