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The purpose of this study was to synthesize a series of solid solution jarosites by biological oxidation of ferrous iron at pH2.2-4.4 and ambient temperature in media containing mixtures of K(+) (0, 1, 4, 6, 12, 31 mM) and NH4(+) (6.1, 80, 160, 320 mM). The starting material was a liquid medium for Acidithiobacillus ferrooxidans comprised of 120 mM FeSO4 solution and mineral salts at pH2.2. Following inoculation with A. ferrooxidans, the cultures were incubated in shake flasks at 22°C. As bacteria oxidized ferrous iron, ferric iron hydrolyzed and precipitated as jarosite-group minerals (AFe3(SO4)2(OH)6) and/or schwertmannite (idealized formula Fe8O8(OH)6(SO4)·nH2O). The precipitates were characterized by X-ray diffraction (XRD), elemental analysis, and Munsell color. Schwertmannite was the dominant mineral product at low combinations of K(+) (≤ 4 mM) and NH4(+) (≤ 80 mM) in the media. At higher single or combined concentrations, yellowish jarosite phases were produced, and Munsell hue provided a sensitive means of detecting minor schwertmannite in the oxidation products. Although the hydrated ionic radii of K(+) and NH4(+) are similar, K(+) greatly facilitated the formation of a jarosite phase compared to NH4(+). Unit cell and cell volume calculations from refinements of the powder XRD patterns indicated that the jarosite phases produced were mostly ternary (K, NH4, H3O)-solid solutions that were also deficient in structural Fe, especially at low NH4 contents. Thus, ferric iron precipitation from the simulated bioleaching systems yielded solid solutions of jarosite with chemical compositions that were dependent on the relative concentrations of K(+) and NH4(+) in the synthesis media. No phase separations involving discrete, end-member K-jarosite or NH4-jarosite were detected in the un-aged precipitates. |
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