As a part of a systematic study aimed at assessing the chemical composition of ancient pigments as well as at collecting information useful for the understanding of the technical aspects related to pottery preservation and decoration, the results of analysis performed on red, brown and black pigments decorating pre-Roman pottery excavated in thirteen different tombs unearthed in the archaeological zone of Canosa (Puglia, Italy) are presented. Both surface (XPS) and bulk (ET-IR) spectroscopies were used which gave complementary information and XRD was used in some cases to further support the spectral assignments. Results suggested that the shards characterized by "nominally" the same color could be differentiated by the chemical composition of the pigmented layers; in particular, the shards exhibiting the red pigment could be divided into three groups containing, respectively, either hematite or ochre plus other substances not related to the color but of great concern for the understanding of ancient techniques used for color preparation. Manganese oxides were found to be the basis of the brown pigments, which could be divided into three groups on the basis of Mn and Fe contents. Either magnetite or carbon of vegetable origin was found in the black-pigmented layers. Furthermore, an attempt was made to find a possible correlation between this classification and the results of a provenance study carried out on the same pool of shards analyzed in the present investigation.
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