Studies of the stability of the oxides schafarzikite, FeSb2O4, and tripuhyite, FeSbO4, have been undertaken to clarify the roles these secondary minerals may have in determining the dispersion of antimony in oxidizing environments. Solubilities were determined at 298.15 K in aqueous HNO3, and these data were used to calculate values of ΔGfϴ at the same temperature. The derived Δ Gfϴ (s, 298.15 K) values for FeSb2O4 and FeSbO4 are – 959.4±4.3 and – 836.8±2.2 kJ mol–1, respectively. These results have been compared with electrochemically derived data, extrapolated from 771–981 K. The present study shows conclusively that although the mobility of Sb above the water table is limited by simple Sb(III) and Sb(V) oxides and stibiconite-group minerals, depending upon the prevailing redox potential and pH, tripuhyite is an important ultimate sink for Sb in the supergene environment. It is highly insoluble even in strongly acidic conditions and its anomalous stability at ambient temperatures causes the common mineral goethite, FeOOH, to react to form tripuhyite at activities of Sb(OH)5(aq) as low as 10–11. The comparatively limited numbers of reported occurrences of tripuhyite in the supergene zone are almost certainly due to the fact that its physical properties, especially colour and habit, are remarkably similar to those of goethite. In contrast, the small number of reported occurrences of schafarzikite can be related to its decomposition to tripuhyite as redox potentials rise at the top of the supergene zone and the fact that it decomposes to sénarmontite, Sb2O3, in acidic conditions, releasing Fe2+ ions into solution. In general, the findings confirm the immobility of Sb in near-surface conditions. Geochemical settings favouring the formation of the above minerals have been assessed using the results of the present study and data from the literature.

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In order to clarify the roles that secondary minerals may have in determining the extent of dispersion of Sb in the supergene environment, syntheses and stability studies of the Sb(V) oxides byströ mite, MgSb 2 O 6 , ordoñ ezite, ZnSb 2 O 6 and rosiaite, PbSb 2 O 6 , have been undertaken. Solubilities in aqueous HNO 3 were determined at 298.2 K and the data obtained used to calculate values of DG f at the same temperature. The derived DG f (s, 298.2 K) values for MgSb 2 O 6 (À1554.1 Ô3.6 kJ mol À1 ), ZnSb 2 O 6 (À1257.0 Ô2.6 kJ mol À1 ) and PbSb 2 O 6 (À1154.2 Ô2.6 kJ mol À1 ) have been used in subsequent calculations to determine their relative stabilities and relationships with other secondary Sb minerals.

Synthesis and solubility studies of brizziite, NaSbO3, have been undertaken to determine the possible role of this rare secondary phase in the immobilization of Sb under supergene conditions and the conditions responsible for its formation in the supergene zone. Solubility studies were undertaken at T = 298.15 K. A value of ΔGfө) (NaSbO3, s, 298.15 K) = –806.66 ± 1.4 kJ mol–1 was derived. Calculations involving tripuhyite, FeSbO4, byströmite, MgSb2O6, ordoñezite, ZnSb2O6 and rosiaite, PbSb2O6, show that brizziite is a thermodynamically stable phase only at negligible activities of Pb2+(aq) at high pH and high salinity. Calculations involving mopungite Na[Sb(OH)6] combined with reported mineral associations suggest that mopungite is the thermodynamically unstable precursor to brizziite and its presence in natural settings must be due to kinetic stability. This explains why brizziite is such a rare secondary phase and therefore why it cannot exert any significant influence on the dispersion of Sb in the supergene environment.