Voltammetric identification of lead(II) and (IV) in mediaeval glazes in abrasion-modified carbon paste and polymer film electrodes. Application to the study of alterations in archaeological ceramic

摘要

Direct identification of lead(II) and (IV) in glazed ceramics by cyclic voltammetry and differential pulse voltammetry is described. Characteristic cathodic and anodic profiles are obtained for microsample coatings in Paraloid B72-film electrodes immersed in NaCl and HAc/NaAc media. The electrochemical response of PbO, PbO2 and Pb3O4 and a series of test specimens of glaze is compared with that of microsamples extracted from the glaze of blue and white decorated ceramic produced in Manises (Spain) in the 15th century which have been buried in a damp place. Under abrasive conditions, striping peaks at -0.12 and -0.25 V (vs. SCE) appear for Pb(IV) centers and, at -0.55 and -0.75 V, for Pb(II) centers. The weathering process is accompanied by a significant decrease of the total lead content and an enhancement of the Pb(IV)/Pb(II) ratio suggesting that a significant fraction of Pb(II) ions is released. Electrochemical data are compared with those obtained from SEM/EDX. [References: 41]