The pigment lead white ((PbCO3)2·Pb(OH)2) was analyzed by LDI-MS/MS and LDI-Orbitrap-MS/MS for the first time. The elucidation of formulae from a suite of isotopically complex cluster ions was obtained from low- and high-resolution full- and tandem-mass spectra in concert with both deductive and inductive reasoning. The unique isotopic pattern of lead was used both to delineate the full-scan spectrum into superclusters and to identify the monoisotopic mass of each cluster, from which a lead-limited, accurate formula could be derived. Chemical formulae for the clusters of lead white followed the form PbxOyHz. Also, the in situ detection of lead white by LDI-MS was achieved for cross sections of painted works of art.
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