White lead or basic lead carbonate, 2PbCO3·Pb(OH)2, the synthetic analogue of hydrocerussite Pb3(OH)2(CO3)2, has been known since antiquity as the most frequently used white paint. A number of different minerals and synthetic materials compositionally and structurally related to hydrocerussite have been described within the last two decades. Herein, a review is given of general structural principles, chemical variations and IR spectra of the rapidly growing family of hydrocerussite-related minerals and synthetic materials. Only structures containing a hydroxo- and/or oxo-component, i.e. which are compositionally directly related with hydrocerussite and `white lead', are reviewed in detail. An essential structural feature of all the considered phases is the presence of electroneutral [PbCO3]0 cerussite-type layers or sheets. Various interleaved sheets can be incorporated between the cerussite-type sheets. Different sheets are stacked into two-dimensional blocks separated by the stereochemically active 6s2 lone electron pairs on Pb2+ cations. Minerals and synthetic materials described herein, together with a number of still hypothetical members, constitute a family of modular structures. Hydrocerussite, abellaite and grootfonteinite can be considered to constitute a merotype family of structures. The remaining hydrocerussite-related structures discussed are built on similar principles, but are more complex. Structural architectures of somersetite and slag phase from Lavrion, Attica, Greece, are unique for oxysalt mineral structures in general. Thus, the whole family of hydrocerussite-related phases can be denoted as a plesiotype family of modular structures. The crystal structures of hydrocerussite from Merehead quarry, Somerset, England, and of its synthetic analogue, both determined from single crystals, are reported here for the first time. The results of the infrared (IR) spectroscopy show that this method is useful for distinguishing several different minerals related to hydrocerussite and their synthetic analogues.
Keywords: basic lead carbonates; hydrocerussite; infrared spectroscopy; layered structure; lone electron pair; modern white lead; modular structure; white lead.