No R T (min) Chemical Compound Chemical formula B35-I B35-II B35-IIa B35-III B43a-I B37-I 1 1,205 Ethanethioamide C 2 H 5 NS + 2 1,209 Benzenepropanoic acid, tetr-butyldimethylsilylester* C 15 H 24 O 2 Si + 3 1,274 Disiloxane, hexamethyl * C 6 H 18 OSi 2 + 4 1,282 Disiloxane, hexamethyl * C 6 H 18 OSi 2 + 5 1,422 2,4-Hexadiyne C 6 H 6 + 6 1,827 2,4,6,8-tetramethyl-1-undecene C 15 H 30 + 7 1,841 Caprolactam C 6 H 11 NO + 8 2,587 Pentane,2,3-dimethyl C 7 H 16 + 9 3,136 Napthalene-1-isocyano C 11 H 7 N + 10 3,151 1-Octanol,2-butyl- C 12 H 26 O 11 3,939 Propanoic acid,2-methyl-,butylester C 8 H 16 O 2 + 12 5,848 Pentanoic acid C 19 H 30 O 3 + 13 7,267 Didodecyl phthalate C 32 H 54 O 4 + 14 7,926 1,3- Dioxolane-2-propanoic acid,2-methyl-,ethyl… C 9 H 16 O 4 + 15 8,349 Cyclooctasiloxane, hexadecamethyl * C 16 H 48 O 8 Si 8 + 16 8,855 Hexane, 3,3-dimethyl C 8 H 18 + 17 10,333 Nonadecane C 19 H 40 + 18 10,925 2,5,8,-Triphenylbenzotristriazole C 24 H 15 N 9 + 19 10,932 8-Benzylquinoline C 16 H 13 N + 20 10,962 Benzimidazo[2,1-a]isoquinoline C 15 H 10 N 2 + 21 11,105 Butane, 1-chloro-3,3-dimethyl C 6 H 13 Cl + + 22 11,249 1,2-Benzenedicarboxylic acid,bis[2-methylpropyl]… C 16 H 22 O 4 23 11,284 Phthalic acid, 6-ethyl-3-octylisobutylester C 22 H 34 O 4 + 24 11,313 1,2-Benzenedicarboxylic acid,bis[2-methylpropyl]… C 16 H 22 O 4 + 25 11,569 6-Undecylamine C 11 H 25 N + 26 11,935 1,4-Oxathiin,2.3-dihydro-6-methyl C 5 H 8O S + 27 11,979 Formic acid, ethoxymethylene hydrazide C 4 H 8 N 2 O 2 + 28 12,509 Dibutylphthalate C 16 H 22 O 4 + + 29 12,515 Dibutylphthalate C 16 H 22 O 4 30 12,520 1,4-Benzenedicarboxylic acid,bis(2-methyl… C 16 H 22 O 4 + 31 12,586 Dibutylphthalate C 16 H 22 O 4 + 32 13,007 Sulfurous acid, butyldecylester C 14 H 30 O 3 S + 33 13,047 Nonadecane, 2-methyl- C 20 H 42 + 34 14,166 Morpholineethanamine C 6 H 14 N 2 O + 35 14,203 Thiophene3-(1,1-dimethylethoxy) C 8 H 12 OS + 36 14,956 p-Terphenyl C 18 H 14 + 37 15,417 2-Piperidinecarboxylic acid, methylester, PFP C 10 H 12 F 5 NO 3 + 38 16,485 1-(Prop-2-ynyl)-3,3-bis(trifluoromethyl)diaziridine C 6 H 4 F 6 N 2 + 39 17,487 Fenoterol-N-trifluoroacetyl-o,o,o,o-tetrakis… * C 31 H 52 F 3 NO 5 Si 4 + 40 24,458 Boron, bis[μ]-(3,5-bis(1,1-dimethylethyl)-1 H-… C 26 H 50 B 2 N 4 + 41 24,487 Tricosanoic acid,tert-butyldimethylsilylester * C 29 H 60 O 2 Si + 42 25,072 10-Ethyl-3-chloro-7-(N-p--nitrobenzyldeneamino)-… C 21 H 16 ClN 3 O 2 S + 43 25,840 1,8-Dihydroxy-3-methylanthraquinone,O,O'-… * C 21 H 26 O 4 Si 2 + + 44 26,337 Hexadecanoic acid, 1-[[(trimethylsilyl)oxyl]methyl…* C 38 H 76 O 5 Si + 45 27,215 Yohimban-16-carboxylic acid, 17-hydroxy-10-… C 22 H 28 N 2 O 4 + 46 27,655 Tetracosamethyl-cyclododecasiloxane * C 24 H 72 O 12 Si 12 + 47 27,661 Tetracosamethyl-cyclododecasiloxane * C 24 H 72 O 12 Si 12 + 48 28,978 Hexadecanoic acid, 2-hydroxy-1,3-propanedi… C 35 H 68 O 5 + 49 30,384 9-Octadecanoic acid (Z)-2 hydroxy-1,3-… C 39 H 72 O 5 + 50 33,404 1-Hydroxy-3-(hydroxymethyl)anthraquinone,… * C 21 H 26 O 4 Si 2 + 51 33,989 n-Hexadecanoic acid, dimethyl… * C 22 H 48 O 2 Si 2 + 52 35,899 1,3-Dipalmitin trimethylsilylether * C 38 H 76 O 5 Si + 53 38,123 9-Octadecanoic acid (Z)-2 hydroxy-3-... C 37 H 70 O 5 + METAL CONTAINERS OF THE 4 TH CENTURY B.C. ANALYSIS OF THEIR COMPOSITION AND CONTENTS Christos Katsifas A , Despoina Ignatiadou B , Nikolaos Kantiranis C , George A. Zachariadis D* A Archaeometry Laboratory, Archaeological Museum of Thessaloniki, 54013 Thessaloniki, Greece, chkatsifas@culture.gr B Department of Metalwork, Archaeological Museum of Thessaloniki, 54013 Thessaloniki, Greece, dignatiadou@culture.gr C Department of Mineralogy, Petrology and Economic Geology, School of Geology, Aristotle University, 54124 Thessaloniki, Greece, kantira@geo.auth.gr D Lab. of Analytical Chemistry, Dept. of Chemistry, Aristotle University, 54124 Thessaloniki, Greece * zacharia@chem.auth.gr 1 . Introduction The Derveni tombs were accidentally revealed in 1962, 10 km NW of Thessaloniki. The six cist graves and one Macedonian tomb that were excavated then had not been looted and contained rich offerings, mainly dated to the 4 th century BC (1). The deceased were members of a rich and important Thessalian family that probably lived in the nearby ancient city Lete. In tomb A was found the so-called Derveni papyrus; fragments of a papyrus roll with a most important Orphic religious text of the 4 th century BC, preserving also excerpts of an earlier poem. The biggest and richest grave was tomb B. It contained the cremated remains of a man and his female consort, which had been placed in an elaborate bronze vessel, today known as the famous Derveni krater. That male individual was an important member of the elite, probably a royal companion who died when he was approximately 35-50 years old. In addition to the bronze krater, the burial contained a gold wreath and other gold jewelry, twenty silver vessels, many bronze vessels, stone alabastra, glass vessels and pottery vases, the iron weapons of the dead, a folding board gaming set with glass gaming counters, pieces of a leather cuirass, bronze greaves and a gold coin of King Philip II. Among the numerous grave goods (Fig. 1-4), was a lidded box (B35), preserving its content which was macroscopically identified to be of cosmetic nature. It is a half-cylindrical case divided in three compartments. Each is filled with a mass possibly of clay; one is still preserving the finger impressions of its user, another is additionally preserving remains of a fibrous nature. The case has a hinged lid that protects the contents. Recent study of the case associates it with three miniature vessels also found in the same context: two bronze bowls (B43a, B43b) and a pyxis (B37), all preserving their original content. In the two bowls is preserved a thin dark-colored cake. The pyxis is a small cylindrical box still filled with a red powder. B35 B35-I B35-II B35-III B35-IIa Fig.1 Fig.2 Fig.3 Fig.4 B37 B43a B43b B43a-I B43b-I Sample Quartz Plagioclase Mica Chlorite Dolomite Amorphοus K-feldspar Calcite Amphibole Cristobalite Gypsum Graphite Hydrozincite Hematite Magnetite Bassanite Inderite Β35-I 41 29 15 8 6 1 Β35-II 43 8 9 5 18 7 7 3 B35-IIa 42 9 8 7 3 31 Β35-III 44 13 6 4 16 8 6 3 Β43a-I 7 1 1 1 78 6 5 1 Β43b-I 11 1 1 65 2 12 5 1 2 Β37-I 9 74 10 6 1 Description Cu (%) Sn (%) Pb (%) Fe (%) As (?) (%) Ag (%) Au (%) B35 lid 88.1 11.6 0.12 0.08 0.04 detected - B35 lid’s ring 93.0 6.6 0.23 0.13 0.03 - detected B35 nail 99.3 0.19 0.45 0.19 - - - B35-encircling band 83.2 15.8 0.70 0.04 - - detected B37 lid 85.2 13.1 0.80 Detected - - detected B43a 99.2 0.06 0.40 0.20 - - detected B43b 99.1 0.06 0.50 0.20 - - detected Sample Major detected elements Minor detected elements B35-Ι Al, Si, K, Ca, Ti, Fe, Cu, Sr, Mn Pb, Rb B35-ΙΙ Si, K, Ca, Ti, Mn, Fe, Cu, Sr Br, Rb, Bb B35-ΙΙa Al, Si, K, Ca, Ti, Mn, Fe, Cu, Br Ni, Sr, Pb B35-III Si, K, Ca, Ti, Mn, Fe, Cu, Pb Ni, Sr, Pb B37-I Ca, Fe, Cu, Zn Sr, Pb B43a-I Si, K, Ca, Ti, Fe, Ni, Cu, Pb Sr B43b-I Si, K, Ca, Ti, Fe, Cu, Pb Ni, Sr Operating conditions Value GC model Agilent 6873K gas chromatograph (Electron Ionization mode) Column DB-5MS (capillary) 30 m x 0.25 mm x 0.10 μm Injector port temperature 200 o C (SPME fiber was remained there for 6 min) Carrier gas, Flow-rate Helium, 2.0 mL/min (constant pressure at 29.8 psi) Oven temperature program 60 o C (3 min) to 270 o C, 10 o C/min ramp time Transfer line temperature 250 o C MS model Agilent 5973 quadrupole mass detector (Scan mode) Total time of chromatographic analysis 40 min 5 10 15 - keV - 0 2 4 6 x 1E3 Pulses Cu Fe Br Br Ca Ti Mn Ni K Si Al 2. Methodology & instrumentation Since there was no possibility for sampling, the metal containers were analyzed by a non invasive & non destructive technique such as XRF. Measurements were taken from every different part of the containers in order to determine their chemical composition and to study the manufacturing technology. To characterize the components of the three cakes (B35a, B35b, B35c) that are preserved in the lidded box B35, as well as the two from the bronze bowls (B43a, B43b) and the red powder from the pyxis (B37), a physico-chemical analysis was undertaken in combination with mineralogical examination. After the preliminary morphological examination by stereomicroscopy, XRF spectroscopy was carried out for the analysis of the inorganic components. Small fragments were sampled from the cakes and XRD spectrometry was implemented in order to determine their mineralogical composition. Specifically from the cake B35b an extra sample was taken from a red lump, since its colour and texture differs from the rest of the material. In order to study the organic constituents, the samples were pre-treated with the HS-SPME technique and the absorbed volatiles were analyzed by GC-MS. 2.1 X-Ray Fluorescence spectroscopy For the implementation of the X-ray Fluorescence technique was used the Energy Dispersive ARTAX 400. It’s measuring head comprising of: a metal ceramic, air-cooled, Mo tube, a Silicon Drift - peltier cooled - Detector & a CCD camera. The X-ray beam is restricted by a collimator (200-1500 μm). At the present study was used the 650 μm collimator. The measuring head is placed on a x,y,z – motor driven positioning stage. For the determination of elements with lower atomic number, helium (He) gas purging system is available in order to improve excitation conditions (2). 2.2 X-Ray Diffraction spectroscopy The samples were studied in their bulk form, ground in an agate mortar and homogenized. Powder X-ray diffraction (PXRD) analysis on random oriented samples was used to identify the mineralogical composition of the studied samples. A Phillips (PW1710) diffractometer was used and the samples were scanned over the 3-63 ο 2θ interval at a scanning speed of 1.2 ο /min 2.3 HS – SPME / GC– MS The pre-treatment of the samples was done by the HS-SPME technique, using a PDMS coated fiber (100 μm film) in the head space above the heated samples. GC-MS analysis of the absorbed volatiles from the samples was carried out and finally the identification of the compounds was succeeded by using NIST library. The GC-MS operating conditions are listed in Table 1. Table 1: GC-MS operating conditions Table 5: Chemical constituents of samples as determined by HS-SPME/GS-MS method. Compounds marked with a star either are not constituents or they are derivatives). 3. Results – discussion Table 2: Chemical composition of metal containers ( XRF method) Table 3: Results of qualitative analysis by XRF technique Table 4: Results of mineralogical analysis by the XRD technique (% m/m) Fig.5: Detection of Br (XRF spectrum – B35-IIa sample). For the bronzes analysis, measurements were taken from pre- cleaned spots. Especially the pyxis B37 suffers from thick corrosion layers in combination with extensive conservation treatment. These facts make the archaeometric interpretation unreliable. According to the XRF results (table 2) parts of the object B35, like a nail or the lid’s ring present high Cu content and low Sn. The detection of Au could be attributed to the excavation’s golden co-findings (1). The presence of As is unusual for Greek bronzes of this era (4) but its detection is problematic because of the co-existence with the Pb (overlapping of the peaks). The presence of Br, in the cake’s analysis, is an indicator for the possible presence of organic pigment “porphyra” (Fig.5). Fig.6: GC-MS chromatogram of volatile constituents of the sample B35-IIa. 4. Conclusions  The low content of foreign impurities is an indication that copper was of Cypriot origin (5).  Parts of the metal container B35 (i.e. nails and ring) present high copper content.  The presence of low traces of As requires further investigation with more sensitive and selective analytical techniques.  The main constituent of pyxis B37 is the red inorganic pigment hematite.  The observation of a purple color in combination with the detection of Br (B35-IIa) is indicative for the possible existence of the pigment porphyra. In almost all the contents, traces of organic fatty acids were determined. 5. References 1. Themelis P.G., Touratsoglou Y.P., The Derveni tombs, Athens 1997 (in Greek, English summary) 2. Bronk H., Rohrs S., Bjeoumikhov A., Langhoff N., Schmalz J., Wedell R., Gorny H.-E., Herold A., Waldschlager U., Artax – a new mobile spectrometer for EDXRF spectrometry on art & archaeological objects, Freseniu’s J. Anal Chem 371: 307-316, 2001. 3. Giachi G., P. Pallecchi, A. Romualdi, E. Ribechini, J.J. Lucejko, M.P. Colombini, M. M. Lippi, Ingredients of a 2000-y-old medicine revealed by chemical, mineralogical and botanical investigations, PNAS 110, 4, 1193-1196, 2013. 4. Cesareo R., S. Sciuti, M. Marabelli, Non-destructive analysis of ancient bronzes, Studies in conservation, 18, 64-80, 1973. 5. Varoufakis G.J., Chemical polishing of ancient bronzes, Archaeometry 19, 219-221, 1977. Figures 1-4: Examined metal containers and their content material.