The electrocatalytic effect exerted by hematite, a ubiquitous component of clay bodies, on the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) can be used to acquire information on archaeological ceramics. The solid-state voltammetric response of different hematite and ochre specimens, accompanied by SECM analysis in contact with 0.10 M HCl aqueous solution, is described. In air-saturated solutions, catalytic effects on the ORR and OER are accompanied by Fe(III)/Fe(II) and Fe(IV)/Fe(III) redox reactions. Such processes are conditioned by a variety of factors, the hydroxylation degree of the mineral surfaces being particularly influential, and exhibit significant variations upon heating the specimens between 300 and 900 °C. Voltammetric measurements carried out on a set of archaeological samples of Apulian red-figured pottery dated back within 5 th and 4 th centuries BCE permit to obtain sitecharacteristic voltammetric profiles.

Electrochemical impedance spectroscopy (EIS) was applied to a set of microsamples of Apulian red-figured pottery coming from the archaeological sites of Altamura, Arpi, Conversano, Monte Sannace, Taranto, and Pella. EIS data using Fe (CN) 6 3À /Fe (CN) 6 4À as a redox probe yields information on the roughness, porosity, shape, and size distribution of inclusions in the clay body. Impedance parameters after equivalent circuit modeling permit the discrimination of manufacturing in Apulian and Attic modes as well as the characterization of the different archaeological sites.

Voltammetry of immobilized particles (VIMP) and scanning electrochemical microscopy techniques are combined to study nanosamples from 60 Apulian redfigured pottery objects from six Apulian archaeological sites (Altamura, Arpi, Conversano, Egnazia, Monte Sannace, Taranto) and three Attic samples from Pella. The VIMP signatures corresponding to the electrocatalytic effect of microparticulate deposits of the clay body and the black gloss on the oxygen evolution reaction and the oxygen reduction reaction are obtained. These signatures provide information on the reducing/oxidizing conditions of firing. The combination of the above voltammetric data permits us to distinguish between Apulian production and Attic importations as well as to discriminate the productions from different archaeological sites or even within different technologies in samples from the same site.

The electrocatalytic effect exerted by hematite, a ubiquitous component of clay bodies, on the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) can be used to acquire information on archaeological ceramics. The solid-state voltammetric response of different hematite and ochre specimens, accompanied by SECM analysis in contact with 0.10 M HCl aqueous solution, is described. In air-saturated solutions, catalytic effects on the ORR and OER are accompanied by Fe(III)/Fe(II) and Fe(IV)/Fe(III) redox reactions. Such processes are conditioned by a variety of factors, the hydroxylation degree of the mineral surfaces being particularly influential, and exhibit significant variations upon heating the specimens between 300 and 900 °C. Voltammetric measurements carried out on a set of archaeological samples of Apulian red-figured pottery dated back within 5 th and 4 th centuries BCE permit to obtain sitecharacteristic voltammetric profiles.