Micromodel Investigation of Transport Effect on the Kinetics of Reductive Dissolution of Hematite

Reductive dissolution of hematite in porous media was investigated using a micromodel (8.1 x 4.5 x 0.028 mm) with realistic pore network structures that include distinctive advection domain, macropores and micropores created in silicon substrate. The micromodel pore surface was sputter deposited with a thin layer (230 nm) of hematite. The hematite in the micromodel was reduced by injecting pH-varying solutions (pH 5.0, 6.0, 7.0) containing a reduced form of flavin mononucleotide (FMNH2, 100 mu M), a biogenic soluble electron transfer mediator produced by Shewanella species. The reduction kinetics was determined by measuring effluent Fe(II) (aq) concentration and by spectroscopically monitoring the hematite dissolution front in the micromodel. Batch experiment was also performed to estimate the hematite reduction rate under the well mixed condition. Results showed significant spatial variation in local redox reaction rate that was controlled by the coupled transport and reaction. The overall rate of the redox reaction in the micromodel required a three-domain numerical model to effectively describe reaction kinetics either with distinctive apparent rate parameters or mass transfer coefficients in different pore domains. Results from this study demonstrated the feasibility of a domain-based modeling approach for scaling reaction rates from batch to porous media systems where reactions may be significantly limited by transport.