The footprints of ancient CO2-driven flow systems: Ferrous carbonate concretions below bleached sandstone

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 (CO2 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 fl ow 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 defi ned 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 fl ow 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 fl owing 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 fl ow systems with similar histories

THE GEOLOGIC CONTEXT OF WONDERSTONE: A COMPLEX, OUTCROP-SCALED PATTERN OF IRONOXIDE CEMENT

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 CO2 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

Life and Liesegang: Outcrop-Scale Microbially Induced Diagenetic Structures and Geochemical Self-Organization Phenomena Produced by Oxidation of Reduced Iron

The Kanab Wonderstone is sandstone (Shinarump Member, Chinle Formation) that is cemented and stained with iron oxide. The iron-oxide cementation and staining in these rocks have been considered examples of the Liesegang phenomenon, but we will show that they comprise a microbially induced structure. The spacing of bands of iron-oxide stain follow the Jablczynski spacing law (wherein the spacing between bands of iron-oxide stain increases as one traverses a series of bands) characteristic of Liesegang. Bands of iron-oxide cement exhibit more variable spacing and exhibit a weak but significant correlation between band thickness and distance between bands of cement. The pore-filling cement contains morphotypes that are similar in size and habit to those exhibited by microaerophilic iron-oxidizing bacteria. Other disseminated iron-oxide mineralization occurs as rhombohedra interpreted to be pseudomorphs after siderite. We interpret the cement to be produced by microbially mediated oxidation of siderite (a typical early diagenetic mineral in fluvial sandstones). Iron-oxidizing bacteria colonized the redox interface between siderite-cemented sand and porous sandstone. Microbes oxidized aqueous Fe(II), generating acid that caused siderite dissolution. The iron-oxide cement is the microbial product of a geochemical drive for organization; whereas the iron-oxide stain is true Liesegang. Together, they comprise a distinctive microbially induced structure with high preservation potential. Key Words: Biosignatures—Iron oxides—Diagenesis—Iron-oxidizing bacteria—Shinarump

Petrogenesis and rare earth element mineralization of the Elk Creek carbonatite, Nebraska, USA

Although carbonatites are the primary source of the world&rsquo;s rare earth elements (REEs), the processes responsible for ore-grade REE enrichment in carbonatites are still poorly understood. In this study, we present a petrologic, geochemical, and isotopic evaluation of the Elk Creek carbonatite in southeast Nebraska to constrain the origin of REE mineralization. The Elk Creek carbonatite is a multilithologic carbonatite comprised of an early apatite-dolomite carbonatite, a middle/heavy REE-enriched magnetite-dolomite carbonatite, and a late-stage light REE-enriched, barite-dolomite carbonatite, as well as a suite of breccias. Neodymium, strontium, and carbon isotopic data from the early apatite-dolomite carbonatite, &epsilon;Nd(T)&nbsp;=&nbsp;2.3 to 3.4, 87Sr/86Sr(i)&nbsp;=&nbsp;0.702704 to 0.702857, and &delta;13C&nbsp;=&nbsp;&minus;3.3 to &minus;3.4, indicate that the parental magma and REEs were derived from the mantle, and textural and chemical data suggest that hydrothermal processes played an important role in reaching ore-grade enrichment. Higher initial 87Sr/86Sr values (&sim;0.7041) of REE-mineralized lithologies are evidence that these fluids were derived, in part, from meteoric water that interacted with the country rock. Modeling of the C-O isotopic data reveals that some of the isotopic variation results from closed-system Rayleigh fractionation of an evolving carbonatitic magma between 300 and 500&nbsp;&deg;C, but an excursion to heavier &delta;18O is likely the result of interaction with H2O-CO2-fluids at temperatures from 400 to 100&nbsp;&deg;C. Hydrothermal dolomite has higher 87Sr/86Sr values than early-formed magmatic dolomite, consistent with metasomatism by fluids derived, in part, from a more radiogenic source such as the Precambrian-age wall rock. Rare earth element mineralization occurs primarily in fine-grained, cavity filling minerals including monazite, bastn&auml;site, parisite, and synchysite along with barite, dolomite, quartz, and iron oxides. We interpret the LREE enrichment at Elk Creek to be the product of hydrothermal fluids derived from the evolving carbonatite magma and fluids from the wall rock. The REEs likely became enriched in late-stage fluids from the evolving magma as well as being remobilization by the dissolution of earlier formed minerals. Middle/heavy REE-enrichment in the magnetite-dolomite carbonatite is hosted in hydrothermal dolomite and is attributed to variations in the composition of hydrothermal fluids. &nbsp;</p

Metastable equilibria among dicarboxylic acids and the oxidation state during aqueous alteration on the CM2 chondrite parent body

Linear saturated dicarboxylic acids are present in carbonaceous chondrite samples at concentrations that suggest aqueous alteration under conditions of metastable equilibrium. In this study, previously published values of dicarboxylic acid concentrations measured in Murchison, Yamato-791198, and Tagish Lake carbonaceous chondrites are converted to aqueous activities during aqueous alteration assuming water:rock ratios that range from 1:10 to 10:1. Logarithmic plots of the aqueous activities of any two dicarboxylic acids are proximal to lines whose slope is fixed by the stoichiometry of reactions describing the oxidation–reduction equilibrium between the two species. The precise position of any line is controlled by the equilibrium constant of the reaction relating the species and the hydrogen fugacity for the reaction of interest. Reactions among succinic (C4), glutaric (C5), and adipic (C6) acids obtained from CM2 chondrites show evidence of metastable equilibrium and yield log fH2 values that agree to within 0.3 log units at 298.15 K and 0.6 log units at 473.15 K. At a water:rock ratio of 1:1, metastable equilibrium among succinic, glutaric, and adipic acids results in calculated log fH2 values during aqueous alteration that range from −6.2 at 298.15 K to −3.3 at 373.15 K. These values are consistent with those obtained in previous work on carbonaceous chondrites and with metastable equilibrium at temperatures ranging from 300 to 355 K in contact with cronstedtite + magnetite