GSA Annual Meeting in Denver, Colorado, USA - 2016

Paper No. 93-5
Presentation Time: 9:10 AM


KETTLER, Richard M.1, HE, Yongsheng2, KE, Shan3, LOOPE, David B.1 and WEBER, Karrie A.4, (1)Department of Earth & Atmospheric Sciences, University of Nebraska-Lincoln, Lincoln, NE 68588-0340, (2)School of Earth Sciences and Resources, China University of Geosciences, Beijing, 29 Xueyuan Road, Haidian District, China University of Geosciences, Beijing, 100083, China, (3)State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Xueyuan Rd.29, Haidian District, Beijing, 100083, China, (4)Department of Earth & Atmospheric Sciences and School of Biological Sciences, Lincoln, NE 68588-0118,

The search for biosignatures for Fe(II)-oxidizing bacteria (FeOB) has included measurement of both laboratory and natural fractionation of Fe isotopes. Fe(III)-oxides produced by FeOB in the lab have significantly higher δ56Fe values (by approximately 2‰) than reduced precursors. Values of δ56FeFe(III)mineral56FeFe(II)aq in modern settings are less than expected based on experiment. We have examined Fe-oxide cements that we interpret to be products of FeOB in an evolving groundwater system; an exhumed Navajo SS aquifer. These Fe-oxide cements exhibit extreme variations in δ56Fe values; values published previously are as low as -1.4‰ and we have measured values as low as -0.86‰. Although these values are unusual for Fe-oxides, they are typical for reduced species such as siderite or pyrite. In our model, mantle-derived CO2 and trace CH4 migrated to Navajo SS aquifers sealed by the Jurassic Carmel Formation. The CH4 and CO2 dissolved in formation waters, reduced Fe(III)-oxide that coated sand grains and bleached the rock. The dense, CO2-charged waters descended in the aquifer, degassed locally and produced siderite. The Colorado Plateau was uplifted and the Navajo SS exhumed by erosion. Oxidizing waters invaded the aquifer and oxidized the siderite. FeOB colonized redox interfaces between siderite-cemented sandstone and uncemented sandstone. The FeOB oxidized aqueous Fe(II) liberated from dissolving siderite. Fe-oxide rhombohedra that we interpret to be psuedomorphs after siderite cement have δ56Fe values of -0.59‰. The Fe-oxide rind that comprises the large box-work concretion that encloses these rhombohedra has a δ56Fe value of -0.37‰. We interpret the rind to have been generated by microbial oxidation of Fe(II) that diffused from dissolving siderite in the core of the concretion; whereas the Fe-oxide rhombohedra were produced by abiotic oxidation of siderite (oxidation that occurred with no cm-scale migration of Fe). We interpret the limited fractionation to be the product of near-closed system oxidation of Fe(II). The Fe-oxide mineralization of the Colorado Plateau is an ideal environment to test hypotheses regarding Fe isotope fractionation by FeOB. The concretions have a geometry that lends itself to such tests and the δ56Fe values of reduced precursors are preserved.