Manganiferous karst bauxites are rare on a worldwide scale. One such body, recently mined at Kincsesbánya, Hungary, has been studied by chemical, petrographic, X-ray powder diffraction, scanning electron microscopic, and energy dispersive X-ray analytical techniques. The bauxite deposits of Kinesesbánya are of Paleocene to Lower Eocene age; however, the enrichment of manganese in them was a much later, epigenetic process. Lithiophorite is the main Mn mineral in this bauxite and occurs chiefly in dusters of < 1-μm size crystallites. Well-developed crystallites, however, 5–10 μm in size, line the walls of many microfissures and voids.

The oxidation of pyritic bauxite and lignitic clays in the overlying beds apparently mobilized finely disseminated Mn and Fe. Downward-migrating acidic solutions were gradually neutralized, and Mn and Fe minerals precipitated. The manganiferous bauxite was found only along the eastern rim of heavily eroded Middle Eocene sedimentary rocks. Here, epigenetic oxidation and mobilization were optimum. Farther to the east, pyrite-rich overburden and bauxite were apparently eroded away before Fe and Mn could be mobilized.

Lithiophorite is a naturally occurring Mn oxide mineral commonly found in soils and sediments. The usual method of synthesizing lithiophorite is via a hydrothermal process in an autoclave at relatively high temperature and pressure. In the present study, an alternative, reflux method, at atmospheric pressure, for synthesis of lithiophorite was developed successfully. The influence of reaction duration, temperature, type of precursor birnessite (H-birnessite, Na-birnessite, aged Na-birnessite), and pH on the formation of lithiophorite were investigated by reflux treatment of lithium-aluminum hydroxide complex ion ()-exchanged birnessite. The results show that the degree of conversion of lithiophorite decreases with decreasing reaction temperature. Lithiophorite can be obtained at pH values from 5.0 to 9.0, but a circumneutral pH is more favorable for formation at atmospheric pressure. Conversion of Na-birnessite (Bir-OH) to lithiophorite is more favored than aged Na-birnessite (Bir-OH-A). Lithiophorite was not obtained by refluxing the ion-exchanged H-birnessite (Bir-H) sample. The rate of conversion of lithiophorite increases with increasing reflux time. Lithiophorite synthesized by a reflux process has pseudo-hexagonal crystals of 0.1–0.5 µm with a chemical composition of Li0.24Al0.46MnO2.67(H2O)1.25. The results have important implications for the origin and underlying mechanism of lithiophorite formation in the environment.

Lithiophorite is a naturally occurring phyllomanganate which has been identified in soils and ores. Studies on a synthetic version have shed light on the conditions required for the formation of lithiophorite. In this study, we successfully prepared lithiophorite under highly alkaline conditions. In addition, we found that Li+, Al3+ and hydrothermal treatment are all necessary for the formation of lithiophorite. Lithiophorite, birnessite and Li-intercalated gibbsite were examined by infrared (IR) spectroscopy. The Mn oxide sheets of lithiophorite and birnessite were found to have quite similar structural environments. On the other hand, the LiAl2(OH)6 sheets are affected more markedly by the Mn oxide sheets. After intercalation, the symmetry of the six interlayer OH groups of LiAl2(OH)6 is reduced and they are divided into two groups occupying different sites, corresponding to the IR absorption bands at 3480 and 3312 cm−1, respectively.