Synthetic sodium bimessite, having a cation-exchange capacity (CEC) of 240 meq/100 g (cmol/kg) was transformed into Li, K, Mg, Ca, Sr, Ni, and Mn2+ cationic forms by ion exchange in an aqueous medium. Competitive adsorption studies of Ni and Ba vs. Mg showed a strong preference for Ni and Ba by bimessite. The product of Mg2+-exchange was buserite, which showed a basal spacing of 9.6 Å (22°C, relative humidity (RH) = 54%), which on drying at 105°C under vacuum collapsed to 7 Å. Of the cation- saturated bimessites with 7-Å basal spacing, only Li-, Na-, Mg-, and Ca-bimessites showed cation exchange.

Heating bimessite saturated with cations other than K produced a disordered phase between 200° and 400°C, which transformed to well-crystallized phases at 600°C. K-exchanged bimessite did not transform to a disordered phase; rather a topotactic transformation to cryptomelane was observed. Generally the larger cations, K, Ba, and Sr, gave rise to hollandite-type structures. Mn- and Ni-bimessite transformed to bixbyite-type products, and Mg-bimessite (buserite) transformed to a hausmannite-type product. Li-bimessite transformed to cryptomelane and at higher temperature converted to hausmannite. The hollandite-type products retained the morphology of the parent bimessite. The mineralogy of final products were controlled by the saturating cation. Products obtained by heating natural bimessite were similar to those obtained by heating bimessite saturated with transition elements.

The diagenetic to very low-grade metamorphic manganese ores of the Postmasburg manganese field provide a unique example of oxide-facies manganese ores in a Palaeoproterozoic palaeokarst setting. The ores are composed mainly of braunite group minerals, including braunite, partridgeite and bixbyite, with rare braunite II and Ca-poor, silica-depleted braunite. Iron-poor partridgeite is distinguished from Fe-rich bixbyite and the occurrence of Ca-poor, silica-depleted braunite is reported for the first time. Braunite and partridgeite formed during early diagenesis but remained stable under greenschist facies metamorphic conditions. In contrast, bixbyite is apparently a product of metasomatic remobilisation under peak metamorphic conditions. It is suggested that local variations of the metamorphic mineral association reflect variations of the host rock composition and that they are not related to changing P-T conditions of metamorphic alteration, a model promoted by previous authors. The phase chemistry of braunite, braunite II and bixbyite is explained by the existing polysomatic stacking model for the braunite group. However, the chemical composition of partridgeite and Ca-poor, silica-depleted braunite can only be explained by introducing a distinct module layer, with partridgeite composition, to the existing polysomatic stacking model.