Water-Rock Interaction Simulations of Iron Oxide Mobilization and Precipitation: Implications of Cross-diffusion Reactions for Terrestrial and Mars 'Blueberry' Hematite Concretions

Modeling of how terrestrial concretions form can provide valuable insights into understanding water-rock interactions that led to the formation of hematite concretions at Meridiani Planum, Mars. Numerical simulations of iron oxide concretions in the Jurassic Navajo Sandstone of southern Utah provide physical and chemical input parameters for emulating conditions that may have prevailed on Mars. In the terrestrial example, iron oxide coatings on eolian sand grains are reduced and mobilized by methane or petroleum. Precipitation of goethite or hematite occurs as Fe interacts with oxygen. Conditions that produced Navajo Sandstone concretions can range from a regional scale that is strongly affected by advection of large pore volumes of water, to small sub-meter scale features that are dominantly controlled by diffusive processes. Hematite concretions are results of a small-scale cross-diffusional process, where Fe and oxygen are supplied from two opposite sides from the 'middle' zone of mixing where concretions precipitate. This is an ideal natural system where Liesegang banding and other self-organized patterns can evolve. A complicating variable here is the sedimentologic (both mineralogic and textural) heterogeneity that, in reality, may be the key factor controlling the nucleation and precipitation habits (including possible competitive growth) of hematite concretions. Sym.8 water-rock interaction simulator program was used for the Navajo Sandstone concretions. Sym.8 is a water-rock simulator that accounts for advective and diffusive mass-transfer, and equilibrium and kinetic reactions. The program uses a dynamic composite media texture model to address changing sediment composition and texture to be consistent with the reaction progress. Initial one-dimensional simulation results indicate precipitation heterogeneity in the range of sub-meters, e.g., possible banding and distribution of iron oxide nodules may be centimeters apart for published diffusivities and water chemistries of the solutes involved. This modeling effort underscores the importance of coupled reactions and mass-transfer in formation of iron oxide concretions in both terrestrial and Mars sediments. Methane is interpreted to be the reactive agent that mobilizes iron in Navajo Sandstone. On Mars volatile volcanic gases may be the reactive agents that mobilize iron from volcanic sediments. In both cases, subsequent diffusive and advective mass-transfer coupled to nonlinear chemical reactions produces localized precipitates.