Siderite

Abstract: REDUCTION of ferric iron (Fe(III)) to ferrous iron (Fe(II)) is one of the most important geochemical reactions in anaerobic aquatic sediments because of its many consequences for the organic and inorganic chemistry of these environments1. In marine environments, sulphate-reducing bacteria produce H2S, which can reduce iron oxyhydroxides2 to form iron sulphides. The presence of siderite (FeCO3) in marine sediments is anomalous, however, as it is unstable in the presence of H2S. Previous work3,4 has suggested a bacterial origin of siderite. Here we describe geochemical and microbiological studies which suggest that contemporary formation of siderite concretions in a salt-marsh sediment results from the activity of sulphate-reducing bacteria. We find that, instead of reducing Fe(III) indirectly through the production of sulphide, some of these bacteria can reduce Fe(III) directly through an enzymatic mechanism, producing siderite rather than iron sulphides. Sulphate-reducing bacteria may thus be an important and previously unrecognized agent for Fe(III) reduction in aquatic sediments and ground waters.

Abstract: This study deals with the geochemistry and sedimentology of a facies transition from interbedded carbonate-shale to banded iron-formation in the Campbellrand carbonate sequence to the overlying Kuruman Iron Formation of the Transvaal Supergroup in South Africa which is approximately 2.3 Ga old. Four major lithologies are (1) limestone and dolomite, (2) shale and interbedded shale carbonate, (3) siderite-rich banded iron-formation, and (4) iron oxide-rich banded iron-formation. These rocks are unaltered and essentially unmetamorphosed with a maximum metamorphic-diagenetic overprint ranging in temperature from 110 degrees to 170 degrees C and with pressures of not more than 2 kbars.The oldest rocks are limestones and lesser dolomite with abundant cryptalgalaminae and intraclastic textures. Interbedded with the limestones and dolomites are carbonaceous shales, some of which are unusually ferruginous or pyrite rich. These carbonates and shales are overlain by meso- and microbanded siderite-chert iron-formation which grades upward into magnetite-, chert-, and carbonate-rich iron-formation.The averages for major and trace elements and rare earth element (REE) contents of the limestones, dolomites, and shales are distinct from those of the two types of iron-formation. The two most chemically diverse rock types are the shales (enriched in alkalis and most trace elements) and the two iron-formation types (siderite and magnetite rich) which are almost totally depleted in all elements except Si, Fe, Mg, and Ca (and CO 2 ). The high Al 2 O 3 contents of the shales (avg 9.55 wt %) correlate well with their high organic carbon contents (avg 3.91 wt %); the limestones and dolomites have average Al 2 O 3 and organic carbon contents of about 3.0 and 0.7 wt percent, respectively; the two iron-formation types have Al 2 O 3 average values of 0.099 wt percent (siderite rich) and 0.066 wt percent (magnetite rich) and corresponding averages for organic carbon of 0.080 wt percent (siderite rich) and 0.012 wt percent (magnetite rich). The REE are generally concentrated in the shales by a factor of about 10 over the iron-formations. The limestones and dolomites have intermediate values, and the iron-formations are most depleted. The iron-formation REE patterns (in a ratio with North American shale composite (NASC)) have pronounced positive Eu anomalies and slight negative Ce anomalies. Both of these anomalies are absent in the shales, but the limestones and dolomites show slight positive Eu anomalies.The siderite-rich iron-formations consist of chert-siderite-ankerite (or ferroan dolomite) with traces of pyrite and stilpnomelane. The siderite in these commonly microbanded assemblages is very fine grained along well-defined bedding planes. It is concluded, from petrographic study, that siderite is a primary precipitate. The ankerites and ferroan dolomites in these siderite-rich occurrences are commonly euhedral (rhombohedral), much coarser grained, and appear to be of later (diagenetic) origin. The magnetite-rich iron-formations consist of chert-magnetite-ankerite (or ferroan dolomite) + or - siderite + or - hematite + or - stilpnomelane + or - minnesotaite. In these oxide-rich iron-formations the ankerites (and ferroan dolomites) are similarly much coarser grained than the finely banded siderite. On the basis of the geochemical data and a reconstruction of the depositional basin for the carbonate-shale to iron-formation transition, we conclude that the limestone-dolomite-shale lithologies originated in a water column quite distinct from that in which the iron-formations were precipitated. We propose a model with a stratified water column in which the surface waters (during a regressive stage in the depositional basin) were the site of much organic carbon productivity and the locus of cryptalgal limestones and intraclastic limestone deposition; with at somewhat greater depth (below the chemocline) deposition of pyritic carbonaceous shale. Our model depicts the deeper waters (during a transgressive stage of the basin with the Kaapvaal craton more deeply submerged) as the site for iron-formation deposition; these deeper waters were depleted in organic carbon and enriched in dissolved ferrous iron relative to the shallower water mass, with continued availability of oxygen along the chemocline separating the two water masses. The ultimate source of the iron (and probably the SiO 2 ) in the iron-formations appears to be a very dilute hydrothermal input in the deep ocean waters, as concluded from mixing calculations of REE values for modern Atlantic Ocean water and hydrothermal solutions from the East Pacific Rise.