Lithological and geochemical evidence of Fe and Mn pathways during deposition of Lower Proterozoic banded iron formation in the Krivoy Rog Basin (Ukraine)

Abstract

Abstract Data on stratigraphy, chemical and mineral composition of siliciclastic and ferrugionus rocks of greenschist to epidote-amphibolite metamorphic grade, multi-order cyclicity and banding, isotopic composition of sulphur and carbon and other features of the Krivoy Rog Supergroup metasedimentary rocks are summarized. They provide an insight into the primary sources and the nature of siliciclastic and chemogenic components of banded iron formation (BIF), as well as on pathways of Fe, Mn and Si in the Krivoy Rog palaeobasin at the time of BIF accumulation. Skelevat and Saxagan iron-ore Groups were deposited in a single cyclic transgressive-regressive sequence, probably in a trough-like landlocked basin with complex bottom topography defined by syn-sedimentary faults inherited from the earlier rift structures. Variations in sea level, humidity of climate, continental run-off, oceanic water inflows etc. many times provoked the rapid facies changes ranging from sedimentation of land-derived siliciclastics to deposition of nearly pure chemogenic sediments of the oxide facies BIF in the deeper parts of the basin. Up to seven pairs of schist ( s -) and BIF ( f -) horizons were deposited in the Saxagan Group. Lateral variations of their thicknesses, distribution of free carbon in the rocks and other data indicate that only parts of the basin at a given time were optimal for chemical sedimentation; major part of dissolved Fe, Si and Mn was supplied by constant or event inflow of suboxic ocean water. The Mn content in the Krivoy Rog Supergroup BIFs could serve as an indicator of the fraction of total Fe that precipitated chemically as carbonate. The main part of Fe precipitation in form of Fe(III) hydroxide particles, possibly coated with amorphous silica, is due to a number of oxidation mechanisms operating in the photic surface water layer. On the basis of physicochemical considerations, it is concluded that the Mn CO 3 content in siderite ( c. 2 mol %) contained in the BIF rocks reflects a uniform dissolved Mn concentration ( c. 1 ppm) in the ocean and basin waters. Sedimentation of the typical association of Mg-Fe carbonates and silicates of the carbonate-silicate facies BIF could occur in the near-bottom water only in the case of strong enrichment in dissolved Fe(II) (up to 100–200 ppm) relative to the ocean water (1–10 ppm), which required a stratified brackish-water basin with an estuarine-type circulation. No enrichment in dissolved Mn(II) was possible until p O 2 in the atmosphere raised high enough for precipitation of particulate Mn oxide in the photic zone and its dissolution in the suboxic near-bottom waters.