U.S. Department of Energy


Date of this Version



Environ. Sci. Technol. 2003, 37, 1268-1276


Microbial reduction of Fe(III) in illite was studied to evaluate the possibility of microbial utilization of Fe(III) in sedimentary clays and to determine the effects of bioreduction on clay composition and structure. A subsurface bacterium (Shewanella putrefaciens CN32) and illite separates (<0.2 µm) from St. Peter Formation sandstone in Ogle County, IL, were used in laboratory experiments. Illite suspensions buffered at pH 7 with bicarbonate were inoculated with CN32 and provided with H2 as an electron donor. In selected treatments, anthraquinone- 2,6-disulfonate (AQDS), was included as an electron shuttle to facilitate the bioreduction. Fe(II) production in inoculated treatments was determined by extraction with 0.5 N HCl and compared to uninoculated controls to establish the extent of biological reduction. The resulting solids were characterized by Mössbauer spectroscopy and scanning and transmission electron microscopy (SEM and TEM). The characterization of the starting illite material revealed that it contained a minor component of goethite (α-FeOOH) in addition to fibrous illite. The starting material (both goethite and illite) contained 6% (w/ w) total Fe, and 82% of the total Fe was Fe(III). Approximately 30% of total Fe was associated with goethite. At the end of a 30-day incubation, residual goethite and illite remained. The extent of reduction was much greater in the presence ofAQDS(25%) than in its absence (0%). Modeling of Mössbauer spectra of the bioreduced material indicated that both goethite and illite were reduced but to a different extent. Additionally, TEM evidence suggested that there was a dramatic change in illite morphology upon bioreduction from fibrous needles to plates. The ability of bacteria to utilize Fe(III) in illite has important implications for microbial functions and survival mechanisms, as well as many geological processes, in the subsurface.