The photochemistry of manganese and the origin of banded iron formations

Abstract

The photochemical oxidation of Fe(2+) -hydroxide complexes dissolved in anoxic Precambrian oceans has been suggested as a mechanism to explain the deposition of Banded Iron Formations (BIFs). Photochemical studies have not yet addressed the low levels of manganese in many of these deposits, which probably precipitated from solutions bearing similar concentrations of Fe2+ and Mn2+. Depositional models must also explain the stratigraphic separation of iron and manganese ores in manganiferous BIFs. In this study, solutions containing 0.56 M NaCl and approximately 180 micromoles MnCl2 with or without 3 to 200 micromoles FeCl2 were irradiated with filtered and unfiltered UV light from a medium-pressure mercury-vapor lamp for up to 8 hours. The solutions were deaerated and buffered to pH approximately 7, and all experiments were conducted under O2-free (< 1 ppm) atmospheres. In experiments with NaCl + MnCl2, approximately 20% of the Mn2+ was oxidized and precipitated as birnessite in 8 hours. Manganese precipitation was only observed when light with lambda < 240 nm was used. In experiments with NaCl + MnCl2 + FeCl2, little manganese was lost from solution, while Fe2+ was rapidly oxidized to Fe3+ and precipitated as gamma-FeOOH or as amorphous ferric hydroxide. The Mn:Fe ratio of these precipitates was approximately 1:50, similar to the ratios observed in BIFs. A strong upper limit on the rate of manganese photo-oxidation during the Precambrian is estimated to be 0.1 mg cm-2 yr-1, a factor of 10(3) slower than the rate of iron photo-oxidation considered reasonable in BIF depositional basins. Thus, a photochemical model for the origin of oxide facies BIFs is consistent with field observations, although models that invoke molecular O2 as the oxidant of Fe2+ and Mn2+ are not precluded. Apparently, oxide facies BIFs could have formed under anoxic, as well as under mildly oxygenated atmospheres.