Stability of biological and inorganic hemimorphite: Implications for hemimorphite precipitation in non-sulfide Zn deposits

Hemimorphite, Zn4Si2O7(OH)2·H2O, one of the most common minerals in non-sulfide Zn deposits, together with smithsonite and hydrozincite, is one of the most abundant minerals in the “calamine” deposits in SW Sardinia. In spite of their importance for the development of ore genesis models, the stability properties of hemimorphite are poorly known. This paper presents solubility experiments on two different types of hemimorphite: a “geological” hemimorphite from a supergene non-sulfide Zn deposit, of supposed abiotic origin, and a hemimorphite precipitated by bacterial activity. Both specimens were characterized, before and after the experiment, by Synchrotron Radiation X-ray powder diffraction, Scanning Electron Microscopy, and X-ray Absorption Spectroscopy. The calculated solubility product constants (logKs) are similar for both “geological” and biogenic hemimorphite (30.3 ± 0.4 and 30.5 ± 0.1, respectively). During the solubility experiment, biological hemimorphite undergoes an amorphous to crystalline phase transition, and the distinctive features (mineralized bacterial sheaths and organic filaments), that allowed us to demonstrate its biological origin, are no longer recognizable by Scanning Electron Microscopy. The results of this study may be useful for developing ore genesis models, including evolution in a supergene environment, and in general for performing geochemical speciation and equilibrium calculations. Moreover, our findings open the way for a new interpretation of hemimorphite-forming processes, and suggest the possibility that bacteria may have played a role in the formation of this mineral in ore deposits.