XRF analysis of the Serra d’Alto figuline pottery (Matera, Italy) Lucia Angeli (1) , Cristina Fabbri (1) , Emanuela Grifoni (2,3) , Stefano Legnaioli (2,3) , Giulia Lorenzetti (2,3) , Vincenzo Palleschi (2,3) , Giovanna Radi (1) (1) Department Civilizations and Forms of Knowledge, University of Pisa, Via dei Mille, 19 - 56126 Pisa (ITALY) (2) Applied and Laser Spectroscopy Laboratory, Institute of Chemistry of Organometallic Compounds, CNR, Via G. Moruzzi, 1 -56124 Pisa (ITALY) (3) National Interuniversity Consortium of Materials Science and Technology (INSTM) Geographical area of study (Abruzzo region in green and Basilicata region in yellow) and Neolithic sites of Matera’s area: Setteponti, Serra d’Alto, Murgia Timone, Trasano, Tirlecchia, Pipistrelli’s Cave and Funeraria cave. sampling Serra d’Alto Trasano Tirlecchia Setteponti Grotte Pipistrelli Grotte Funeraria figulina Serra d’Alto 59 23 3 10 6 1 References Angeli L. et al., 2007, Analisi archeometriche applicate allo studio delle ceramiche dipinte del Neolitico dell’Italia centro meridionale , Atti IV Convegno Nazionale AIAr (Pisa, 1-3 febbraio 2006), Pisa, pp. 425-433. Muntoni I. M., Eramo G., Laviano R., 2009, Production of mid-late Neolithic “Serra d’Alto” ware in the Bradanic trough (South Eastern Italy) , in Vessels: inside and outside. Proceedings of the Conference Emac 2007, 9th European meeting on ancient ceramics (Budapest, 24-27 october 2007), Budapest, pp. 53-62. Introduction This study is part of a wider research project about the Neolithic painted pottery in the Adriatic side of the Italian peninsula, which aims to define the organic or inorganic nature of pigments employed in the painted decoration of pottery productions between the Early and Middle Neolithic. The research here reported focuses on the study of the Middle Neolithic painted pottery dated between 5000-4500 cal. BC and referred to the Serra d’Alto Culture. This archeological facies was widespread in southern Italy, with a particular concentration in the trenched villages located in Matera’s area and also in the Apulia region (Tavoliere and Murge). It is largely documented even in central Italy and also in funeral-cultual contexts in northern Italy. Serra d’Alto figuline pottery with zoomorphic plastic application and black painted decoration from different sites of Matera (photo by Museum Domenico Ridola - Polo Museale Regionale della Basilicata) Mn-based black pigment It is worth to mention that in all samples the painting layer shows a concentration of Mn considerably higher than the clay body, also considering the variability above calculated. In all the samples analyzed, the intense spectral Raman line at 620 cm-1 associate to the symmetric stretching vibration of the Mn-O bond from the iron manganese spinel jacobsite (610-625 cm-1) was evident. In some cases, also a spectral band around 660 cm-1 have been detected, probably associated to the presence of hausmannite. We have to consider that, besides jacobsite, intermediate members between jacobsite ((Mn 2+ ,Fe 2+ ,Mg)(Fe 3+ ,Mn 3+ ) 2 O 4 ) and hausmannite (Mn 2 +Mn 3 + 2 O 4 ) are certainly also part of the composition of the black pigment. C39 pottery paste C39 black decoration C4 pottery paste C4 black decoration XRF spectrum sample C39 - Serra d’Alto village XRF spectrum sample C4 - Trasano village The sampling was carried out in the Matera’s area where Domenico Ridola identified for first time the Serra d’Alto ware production in the eponymous hill and in other villages. A total of 102 samples of figuline pottery with black painted decoration have been analyzed. Methodes and materials All the compositional measurements have been performed with the Energy Dispersive X-Ray Fluorescence (ED-XRF) technique at the Museum of Domenico Ridola (Polo Museale Regionale della Basilicata) in Matera. For all the analysis hereby reported we used an energy-dispersive (ED-XRF) spectrometer produced by XGLab (Milan, Italy). The X-ray tube has an Rh anode and can deliver X-rays up to the energy of 50 keV; the measurements area is about 1 mm2. The X-ray spectrometer has a large area (25 mm 2 ) silicon drift detector, having a resolution of 130 eV at the Mn Kα line. For each sample, both the pottery paste (bulk) and the black decoration (dec.) have been analyzed employing an acquisition time of 90s, with the energy of the X-ray tube set at 40 keV and the current at 30 μ A. To better understand the nature of the black Mn-based pigment used for the decoration, we performed a μ - Raman spectroscopy analysis on some of the samples that it was possible to analyse outside the Museum, at the ALS laboratory in Pisa. In particular, three fragments from Serra d’Alto villages and Trasano. Discussion On the basis of the extensive sampling and the data emerged from this study, it is important to note that we were able to determine the peculiar use of Mn-based black pigments in all the Serra d’Alto figuline pottery samples in the Matera’s area. The presence of jacobsite in the black pigments indicates a relatively high firing temperature (about 1000°C) and our data confirms a firing temperature of the Serra d’Alto figuline pottery in the range of 800- 1000°C, in an oxidizing atmosphere, as reported in the literature. At the present state of the research the Serra d’Alto figuline pottery is considered to be an exceptional pottery manufacturing characterized by a very particular ceramic class. The technological progress is proven from the selection and control of raw materials to the technologically advanced firing system. In this regard, the choice of a manganese pigments is a peculiarity of Serra d’Alto potters, during the first half of the 5th millennium cal. BC in the Middle Neolithic.