Concretions with thick, iron oxide-cemented rinds and lightly cemented, iron-poor sandstone cores are abundant within the Navajo Sandstone near the southeast fl ank of the Escalante anticline (Utah, United States). Previous workers suggested the spheroidal concretions as analogs for Martian "blueberries" (hematite concretions), and linked the origin of concretions and bleaching of the Navajo Sandstone to the buoyant rise of hydrocarbons toward anticlinal crests. We measured azimuths of 163 pipe-like (pipy), joint-associated concretions and those of 58

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.

JSTOR is a not-for-profit service that helps scholars, researchers, and students discover, use, and build upon a wide range of content in a trusted digital archive. We use information technology and tools to increase productivity and facilitate new forms of scholarship. For more information about JSTOR, please contact support@jstor.org.. The University of Chicago Press is collaborating with JSTOR to digitize, preserve and extend access to The Journal of Geology. A B S T R A C TConcretions cemented by iron oxide are abundant and diverse in the Jurassic Navajo Sandstone of southern Utah. Some of these structures are considered terrestrial analogs for concretions imaged on Mars. The Navajo concretions can be spheroidal, pipelike, or tabular with multicompartmented boxworks. These iron oxide concretions typically display a rinded structure: dense sandstone rinds cemented by iron oxide surround pale, iron-poor sandstone cores. Within a single structure, the iron-rich rinds may be single or multiple. Pseudomorphs of siderite are present in local residual, iron-rich cores of boxworks. Workers in the late nineteenth through mid-twentieth centuries, many of whom found evidence for siderite precusors, concluded that many spherical, rinded, iron oxide-cemented concretions were formed by centripetal precipitation of iron oxide inward from the perimeter of the concretion; in contrast, the walls of pipelike concretions of iron oxide grew centrifugally outward. We interpret the Navajo spheroids and boxworks as centripetal products of the oxidation of siderite-cemented (precursor) concretions that were very similar in both size and shape to the current concretions: rinds grew (thickened) inward toward the internal source of Fe(II). Siderite pseudomorphs appear to be absent from spheroids and many boxworks because all siderite was dissolved. In the cores of the larger boxworks some siderite was oxidized in situ; the Fe(II) did not migrate away from the original siderite crystals. The oxidation process was mediated by iron-oxidizing microbes and began at concretion perimeters when oxidizing groundwater started to displace the CO 2 -and methane-bearing water that had precipitated the siderite. In contrast, pipelike concretions are centrifugal-rinds formed around a cylindrical reaction front and thickened outward toward Fe(II) and away from the oxygenated water flowing within the cylinders. The cylindrical shape of the reaction front was produced by self-organizing feedbacks between dissolution of dispersed siderite cement and focused flow through a heterogeneous sandstone matrix.

Concretions, preferentially cemented masses within sediments and sedimentary rocks, are records of sediment diagenesis and tracers of pore water chemistry. For over a century, rinded spheroidal structures that exhibit an Fe(III) oxide-rich exterior and Fe-poor core have been described as oxidation products of Fe(II) carbonate concretions. However, mechanisms governing Fe(III) oxide precipitation within these structures remain an enigma. Here we present chemical and morphological evidence of microbial biosignatures in association with Fe(III) oxides in the Fe(III) oxide-rich rind of spheroidal concretions collected from the Jurassic Navajo Sandstone (southwest United States), implicating a microbial role in Fe biomineralization. The amount of total organic carbon in the exterior Fe(III) oxides exceeded measured values in the friable interior. The mean δ 13 C value of organic carbon from the Fe(III) oxidecemented exterior, δ 13 C of −20.55‰, is consistent with a biogenic signature from autotrophic bacteria. Scanning electron micrographs reveal microstructures consistent with bacterial size and morphology, including a twisted-stalk morphotype that resembled an Fe(II)-oxidizing microorganism, Gallionella sp. Nanoscale associations of Fe, O, C, and N with bacterial morphotypes demonstrate microorganisms associated with Fe(III) oxides. Together these results indicate that autotrophic microorganisms were present during Fe(III) oxide precipitation and present microbial catalysis as a mechanism of Fe(III) oxide concretion formation. Microbial biosignatures in rinded Fe(III) oxide-rich concretions within an exhumed, Quaternary aquifer has broad implications for detection of life within the geological record on Earth as well as other Fe-rich rocky planets such as Mars, where both Fe(II) carbonate and Fe(III) oxide-rich concretions have been identifi ed.

Iron-rich carbonates and the oxidized remains of former carbonates (iron-oxide concretions) underlie bleached Navajo Sandstone over large portions of southern Utah. Iron in the carbonates came from hematite rims on sand grains in the upper Navajo that were dissolved when small quantities of methane accumulated beneath the sealing Carmel Formation. As a second buoyant gas (CO 2 derived from Oligocene-Miocene magmas ) reached the seal and migrated up dip, it dissolved in the underlying water, enhancing the solution's density. This water carried the released ferrous iron and the methane downward. Carbonates precipitated when the descending, reducing water degassed along fractures. The distribution of a broad array of iron-rich features made recognition of the extent of the ancient flow systems possible. Although siderite is not preserved, dense, rhombic, mm-scale, iron-oxide pseudomorphs after ferrous carbonates are common. Distinctive patterns of iron oxide were also produced when large (cm-scale), poikilotopic carbonate crystals with multiple iron-rich zones dissolved in oxidizing waters. Rhombic pseudomorphs are found in the central cores of small spheroids and large (meter-scale), irregular concretions that are defined by thick, tightly cemented rinds of iron-oxide-cemented sandstone. The internal structure and distribution of these features reveal their origins as ironcarbonate concretions that formed within a large-scale flow system that was altered dramatically during Neogene uplift of the Colorado Plateau. With rise of the Plateau, the iron-carbonate concretions passed upward from reducing formation water to shallow, oxidizing groundwater flowing parallel to modern drainages. Finally they passed into the vadose zone. Absolute dating of different portions of these widespread concretions could thus reveal uplift rates for a large portion of the Plateau. Iron-rich masses in other sedimentary rocks may reveal flow systems with similar histories.

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