                   E. Cantisani 1 , M. Cavalieri 2 , C. Lofrumento 3 , E. Pecchioni 4 , M. Ricci 5 1 CNRICVBC Institute for Conservation and Enhancement of Cultural Heritage  Via Madonna del Piano 10, Sesto Fiorentino –Florence (Italy), e.cantisani@icvbc.cnr.it. 2 Department of Archaeology and History Art, Institute for Civilizations, Arts and Literature Université catholique de Louvain (UCL) Place B. Pascal, 1 Collège Erasme 1348 LouvainlaNeuve (Belgium). 3 Department of Chemistry  University of Florence, Via Della Lastruccia, 3 –Sesto Fiorentino  Florence (Italy). 4 Department of Earth Sciences – University of Florence, Via G. La Pira, 4  Florence (Italy). 5 Department of Construction and Restoration –University of Florence, Via Micheli, 8  Florence (Italy).     Red covered ceramics represents an imitation, often on a regional basis, of the late African Red Slip ware, already starting from the 2 nd 4 th century A.D. until the 7 th century A.D. In particular, from the 7 th century A.D. the typologies produced in Tuscany start a process of transformation that will give, after a progressive diversification from the typologies attested in other parts of Italy, specific and autonomous characters during the 7 th century A.D.. 400 500 600 700 800 900 1000 1100 1200 1300 0,00 0,05 0,10 0,15 0,20 0,25 0,30 Absorbance [a.u.] wavenumber [cm-1] 400 500 600 700 800 900 1000 1100 1200 1300 -0,05 0,00 0,05 0,10 0,15 0,20 0,25 M Ms M M M M Al C Al Al Q Q Q δ 2 A/δω 2 wavenumber [cm-1] Q H H Al C M Ms 0,25 0,30 0,35 0,15 0,20 0,25 In the archaeological site of AianoTorraccia di Chiusi (SienaItaly) the remains of a Roman Villa, dated from the beginning of 4 th century to the end of the 5 th century or the beginning of the 6t h A.D., were discovered. The complex, abandoned in the 6 th century A.D. was occupied by a group of barbaric artisans (Lombards or Ostrogoths) in the period between the 6 th and the 7 th century A.D. Numerous ceramic findings (simil africane, ingobbiate, acrome grezze) dated back to 5 7 th century were discovered in the archaeological site. These findings were analyzed using different analytical methodologies (OM, XRD, XRF, SEM EDS, ATR FTIR and microRaman) in order to characterize the paste and the cover of the ingobbiate (INGR) and simil africane (TCC), the paste and the tempera of the acrome grezze (AG) and to determine the compositional relationship among different kinds of ceramics. For the characterization of red covered ceramics the use of chemical or mineralogical techniques for the bulk are not very useful, because the data obtained on the powders show the mean composition of the samples, without any difference between paste and covering. The micro chemical and mineralogical analyses, such as FTIR, SEMEDS and micro Raman performed on small samples’ fragments allow to discriminate the composition and texture of paste and covering. The red covered ceramics are clearly subdivided in two groups:   were fired at a temperature >900°C , probably imported. The temper, observed with OM and SEMEDS, is constituted by sorted Aerial photography of the valley of Torrente Foci placed in the border among Poggibonsi, Colle di Val d’Elsa and San Gimignano (Siena). Aerial photography of the Roman Villa (summer 2009). a) Thin section (nicols //, 5 X) and b) SEM image of INGR 27 sample. Infrared spectra of the ceramic paste of 3 samples of INGR. a) absorption spectrum; b) second derivative profile . Al, albite; C, calcite; H, hematite; M, microcline; Q, quartz; Ms, muscovite.   400 500 600 700 800 900 1000 1100 1200 1300 -0,05 0,00 0,05 0,10 0,15 0,20 Absorbance [a.u.] wavenumber [cm-1] 400 500 600 700 800 900 1000 1100 1200 1300 -0,05 0,00 0,05 0,10 Ms Al Al Al H C M M M M Q Q Q δ 2 A/δω 2 wavenumber [cm-1] Q M C H Al Ms 200 300 400 500 600 700 800 H H H H H H H H H Intensity (a.u.) Wavenumbers (cm -1 ) H Q A The temper, observed with OM and SEMEDS, is constituted by sorted and rounded quartz fragments (frequently found in African territory), besides the covering is characterized by a significant Feenrichment.   that do not show clear chemical and mineralogical difference between ingobbio and paste (comparing SEM EDS and ATR FTIR data), while the most relevant difference is linked to the grain size, that is small in the covering with respect to the paste. The covering seems to be obtained using well sorted clayey raw material. This ceramic has been produced using low firing temperatures. The ingobbio of the INGR samples contains the same constituents of the ceramic paste, with a small difference in the intensity of the peak of hematite (FTIR analyses).    This kind of ceramic findings shows a complete summary of typologies, with a dowry constituted by olle, bowllids, casseroles, lids, jugs, small jugs, dated back to the second half of the 5 th  end of the 6 th century A.D. The acrome grezze were analyzed through XRD, OM, performed on the bulk and SEMEDS on the temper and paste. These ceramics were realized re employing the material coming from the mosaic tesserae of the Roman Villa ( white and yellow marbles, Lapis Laecedaemonius, Lapis porphyrites, Portasanta, Greco scritto).      !    ""   The comparison among the analyses of red covered ceramic’s paste has been performed with the areal data (investigated area 20X30 micron) obtained by SEMEDS. A statistical approach was tried in order to emphasize the difference among the pastes. The PC1 and PC2 supply the 94% of information of the samples variability. The graph of scores, compared to the loadings ones represents the variables in the new space formed by the principal component and reveals that samples’ grouping along the first principal component is mainly due to the relative content in SiO 2 , Al 2 O 3 , TiO 2 ,K 2 O, while the second one is characterized by the Na 2 O and SiO 2 content. From this comparison it’s clear that the TCC ceramic findings are obtained using different raw material with respect to AG and INGR samples. Otherwise at the present moment it’s not evident an unmistakable differentiation between AG and INGR samples. Infrared spectra of the ceramic paste of 3 samples of INGR. a) absorption spectrum; b) second derivative profile . Al, albite; C, calcite; H, hematite; M, microcline; Q, quartz; Ms, muscovite. Raman spectra of four different points on the red covering of sample INGR 27 H = hematite, ε = εFe2O3, γ = γFe2O3, Q = quartz, I = illite Raman spectra of four different points on the red covering of sample TCC 2136 H = hematite, ε = εFe2O3, γ = γFe2O3, A = AlforFe substituted hematite, Q = quartz Na2O MgO Al2O3 SiO2 K2O CaO TiO2 FeO INGR 14 ingobbio 0.6±0.1 3.0±0.4 22.5±1.7 55.2±2.4 3.2±0.8 5.0±1.2 1.6±0.2 8.8±1.2 INGR 14 paste 0,6±0.2 2.8±0.3 21.9±2.0 57.2±1.7 3.8±0.7 5.3±1.3 1.3±0.2 7.1±0.7 INGR 28 ingobbio 0,6±0.1 2.3±0.3 15.8±1.4 65.0±1.3 2.8±0.2 6.9±0.7 0.6±0.3 5.9±1.2 INGR 28 paste 0,8±0.1 2.6±0.2 16.3±1.2 58.6±2.7 3.1±0.3 11.3±2.1 0.9±0.2 6.4±1.4 INGR 4 Ingobbio 0,9±0.3 3.0±0.4 15.7±0.6 63.4±2.3 2.1±0.5 7.3±0.6 0.9±0.1 6.8±1.1 INGR 4 paste 1,2±0.3 2.9±0.4 17.0±1.8 58.9±1.8 2.7±0.6 9.6±0.9 0.9±0.1 6.7±1.0 TCC 2136 ingobbio bdl 1.9±0.4 23.1±2.0 57.9±3.5 2.2±0.3 1.4±0.7 1.3±0.2 12.3±1.5 TCC 2136 paste 0.4±0.1 1.9±0.2 21.2±2.3 66.5±3.7 3.1±1.0 0.6±0.2 1.1±0.2 5.4±0.2 TCC 2157 ingobbio 0.7±0.0 1.7±0.0 26.3±0.7 56.7±0.2 2.1±0.4 1.0±0.2 1.2±0.1 10.7±1.5 TCC 2157 paste 0.64±0.3 1.7±0.2 26.3±1.9 61.1±2.8 2.9±0.1 0.7±0.0 1.3±0.1 5.3±0.5 Microchemical analyses (SEM EDS) of the covering (ingobbio) and ceramic pastes. The measures are obtained as mean of 3 measured areas. a) Thin section (nicols //, 5 X) and b) SEM image of TCC2136 sample. #$% &’$(% $) %$&( ⊥* (a) sample AG 4 realized with temper constituted only by calcite with a tipical bimodal grain size distribution (5X); (b) sample AG 4 realized with temper constituted by marble fragments, pyroxenes and plagioclases (2.5X); (c) sample AG 34 realized with temper constituted by pyroxenes, plagioclases and micas (2.5X).  $)* (d) sample AG 23: particular of an altered albitic plagioclase (e) sample AG7: particular of a marble fragment and of a pyroxene. a b c d e   200 300 400 500 600 700 800 200 300 400 500 600 700 800 200 300 400 500 600 700 800 200 300 400 500 600 700 800 γ γ γ γ Intensity (a.u.) I H H Q ε H H H γ Wavenumbers (cm-1)