Iron-bearing concretions are valuable records of oxidation states of subsurface waters, but the first concretions to form can be altered drastically during later diagenetic events. Distinctive concretions composed of heavy rinds of iron oxide that surround iron-poor, mud-rich cores are common along bases of fluvial cross-bed sets of the Cretaceous Dakota Formation, Nebraska, USA. Concretion rinds thicken inward and cores contain 46 to 89% void space. Millimetre-scale spherosiderites are abundant in palaeosols that developed in floodplain facies. Evolution of rinded concretions began when intraformational clasts were eroded from sideritic soils, transported, abraded and deposited in river channels. Alteration of siderite and formation of rinds occurred much later, perhaps in the Quaternary when sandstone pore waters became oxic. Dakota concretions are analogous to 'rattlestones' in Pleistocene fluvial channels of The Netherlands, and their rinded structure is analogous to that of iron-rich concretions in the aeolian Navajo Sandstone of Utah. In all three deposits, rinded concretions formed when pre-existing, siderite-cemented concretions were oxidized within a sand matrix. Unlike fluvial examples, siderite in the Navajo Sandstone was autochthonous and of late diagenetic origin, having precipitated from carbon dioxide and methane-enriched waters moving through folded and jointed strata. Iron-rich rinds formed in all these strata because concretion interiors remained anaerobic, even as oxygen accumulated in the pore waters of their surrounding, permeable matrix. Iron oxide first precipitated at redox boundaries at concretion perimeters and formed an inward-thickening rind. Acid generated by the oxidation reaction drove siderite dissolution to completion, creating the iron-poor core. Iron-oxide rinds are indicators of the former presence of siderite, a mineral that forms only under reducing conditions, during either early or late diagenesis. Siderite is vulnerable to complete oxidation upon exposure, so the distinctive rinded concretions are valuable clues that aid in deciphering diagenetic histories and for recognizing methanic floodplain palaeoenvironments and wet palaeoclimate.
Although siderite is a widespread early diagenetic mineral in fluvial systems, it is unstable in oxidizing environments and destroyed in permeable rocks that experience uplift and exhumation. The products of siderite oxidation, however, (mm-to cm-scale rhombs, concretions, and complex bands of iron-oxide cement) are widespread in the rock record of fluvial systems. The fluvial channels of the Shinarump Member of the Chinle Formation in southern Utah and northern Arizona, U.S.A., provide an excellent suite of examples of diagenetic features produced by Triassic and Neogene oxidation of early diagenetic siderite. These diagenetic features also provide direct evidence of the level of the water table during deposition of the Shinarump member. Large, in situ, discoidal concretions containing preserved siderite are present in Shinarump floodplain siltstones. Rip-up clasts derived from the siltstones developed iron-oxide rinds during late-stage, near-surface oxidation. These two structures show that floodplain silts contained abundant organic matter and methanic pore water. Groundwater recharging through these silts carried reducing water through underlying sand bodies and discharged into active channels. Degassing of CO 2 and methanogenesis caused rhombic crystals of siderite to precipitate in channel sands during these wet intervals. Some of this siderite may have been oxidized during dry intervals when groundwater circulation reversed, but most siderite in the channel sands was preserved until the Shinarump was exhumed during the Neogene. As oxygenated near-surface water entered joints in the lithified Shinarump, colonies of iron-oxidizing microbes living in the phreatic zone occupied redox boundaries and used the rhombic crystals of siderite in the sandstone and the spherulitic siderite in transported siltstone intraclasts as their sources of energy and carbon. The ferrous iron released from dissolving siderite within the intraclasts was oxidized at the siltstone-sandstone contact, generating rinded concretions similar to those in the Cretaceous Dakota Formation. Complex banding known as wonderstone was produced in the channel sandstones from oxidation of the rhombic siderite; the pattern is a combination of Liesegang bands and microbially mediated cements. The preserved rhombs are pseudomorphs after siderite crystals that were either oxidized during Triassic dry intervals, or escaped Neogene microbial oxidation in the phreatic zone, only to be oxidized abiotically in the vadose zone. Microbes are likely oxidizing Shinarump siderite a few kilometers down dip of outcrops with exposed wonderstone. At such locations, the Shinarump is in contact with overlying watersaturated Quaternary alluvium.
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