A thorough assessment of the secondary minerals on 796 Chinese Pb-Cu-Sn-Zn bronze coins from ∼1100 BC to AD 1911 has been made. Malachite is found on more than 80% of the coins irrespective of their dynasties, but a botryoidal texture is only observed on the coins of the Song dynasty or older. Azurite, however, is seen in microscopic quantities on a single coin of ∼AD 1800, but is clearly visible on the Ming dynasty or older coins. Cerussite is a common secondary mineral of the Qin dynasty and older coins, though it has not been found on the Qing dynasty or younger coins. Cuprite is observed on the Song dynasty and older coins.

New stability constant data are presented for the minerals blixite, mendipite and the compound Pb7O6Cl2.2H2O at 298.2 K and P = 105 Pa. Mendipite is in fact a metastable phase at this temperature, being thermodynamically stable under the appropriate conditions at temperatures above about 29°C Kinetic influences are of some significance with respect to the sequence of formation of solid phases in the PbO-HCl-HH2O system, and these have been elucidated for some important reactions. Penfieldite and fiedlerite appear to be metastable phases at all temperatures at 105 Pa. The results have been used to reassess the conditions of formation of the lead(II) oxy- and hydroxychloride phases that are known to form as minerals and as corrosion products of lead-containing artefacts. The effect of CO2 on the system is also described.

Solution studies have been carried out on natural and synthetic arsenate minerals, which are often found in the oxide zones of base metal orebodies. Solubility products and free energy of formation data have been derived for the minerals olivenite, cornubite, clinoclase, adamite, legrandite, euchroite, duftite, conichalcite, austinite, bayldonite, and schultenite at 298.2 K (25 °C). The data have been used in turn to construct stability field diagrams illustrating the chemical conditions under which the various species may crystallize from aqueous solution. This equilibrium model is then compared with several natural occurrences of the arsenate suites and it is demonstrated that it can be used to explain a number of observed paragenetic sequences. Descriptions of solution conditions which describe the stabilities of the arsenate minerals with respect to more commonly found secondary minerals of Pb(II), Cu(II), and Zn(II) involve more complex calculations and estimates of the likely levels of various dissolved species, but it is shown how these may be taken into account in the development of a more complex equilibrium model.

An unusually diverse array of 25 secondary Te oxysalt minerals has been documented from Otto Mountain, California, and 18 of these from the Bird Nest drift sublocality. A paragenetic sequence for these minerals is proposed, using observed overgrowth relationships plus spatial association data and data from other localities. Apart from Te and O, the components Pb, Cu and H are essential in the majority of the minerals. The atomic Cu/Te ratio decreases through the paragenetic sequence. This, and the occurrence of minerals with additional components such as Cl–, CO32–, SO42– and Fe3+ at an intermediate stage, suggests nonmonotonic evolution of the parent fluids, reflecting differing access to or spatial distribution of various components. For the minerals with known crystal structures, two alternative 'structural units' were identified, one consisting only of the Te4+ or Te6+ oxyanion, while the other also included small, strongly-bound cations such as Cu2+. The degree of polymerization for the Te oxyanion correlated with the paragenetic sequence: the monomeric tellurate anions of early minerals were replaced progressively by dimers, chains and sheet structures, which may relate to a decreasing abundance of the 'network modifying' Cu2+ cation, analogous to Bowen's discontinuous reaction series in igneous rock-forming silicates. No relationship was seen between paragenetic order and the larger type of structural unit, or structural complexity as defined by information content. This contrasts with results in the literature for evaporite sulfates and pegmatite phosphates. While structure–paragenesis relationships may be widespread, the exact nature of such relationships may be different for different chemical systems and different paragenetic environments.