Old Masters' lead white pigments: investigations of paintings from the 16th to the 17th century using high precision lead isotope abundance ratios

Abstract

White lead (2PbCO₃·Pb(OH)₂), a common component in 17c. artists' painting materials, was singled out to investigate the potential of lead isotope abundance ratios in the field of authentication and origin assignment. Paintings by Peter Paul Rubens, Anthony van Dyck and other Old Masters of the Northern and Southern schools were chosen for this study. An interdisciplinary approach was chosen using both analytical instrumental methods, art technological and art historical knowledge. Minute samples taken from paintings from selected art collections worldwide were investigated using mass spectrometry, scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). The high precision lead isotope abundance ratios were measured by multiple collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The determination of the calcium matrix influence with respect to possible bias effects to the isotope ratios gave clear decision support, to whether a result lies within the stated combined measurement uncertainty of the result, to eliminate time-consuming matrix separations. The scatter plots of the measured isotope abundance ratios for the painting pigments from P. P. Rubens, A. van Dyck and other Flemish painters exhibit a very narrow distribution forming a cluster. The range of the measured ratio ²⁰⁶Pb/²⁰⁴Pb amounts to 0.55% and for the ratio ²⁰⁷Pb/²⁰⁴Pb to 0.2%. The comparison of the data to cis-alpine (Italian) sample pigments from paintings from the same time period reveals a clear distinction between the two fields. With respect to the lead isotope data originating from the ores it is assumed that the pigment isotope ratio distribution can be explained by very distinct origin of raw materials. Presumably, no mixing of different lead ores from Europe took place. The comparison of the measured white lead isotope ratio values (Flemish paintings) and the data from ore samples led to the unexpected conclusion that local ores were not used for the pigment production but British or German sources.