Enhancement of Hematite Bioreduction by Natural Organic Matter

The effects of natural organic matter (NOM), ferrozine, and AQDS (anthraquinone-2,6-disulfonate) on the reduction of hematite (α-Fe2O3) by Shewanella putrefaciens CN32 were studied. It has been proposed that NOM enhances the reduction of Fe(III) by means of electron shuttling or by Fe(II) complexation. Previously both mechanisms were studied separately using “functional analogues” (AQDS for electron shuttling and ferrozine for complexation) and are presently compared with seven different NOMs. AQDS enhanced hematite reduction within the first 24 h of incubation, and this had been ascribed to electron shuttling. Most of the NOMs enhanced hematite reduction after 1 day of incubation indicating that these materials could also serve as electron shuttles. The effect of ferrozine was linear with concentration, and all of the NOMs exhibited this behavior. Fe(II) complexation only enhanced hematite reduction after sufficient Fe(II) had accumulated in the system. Fe(II) complexation appeared to alleviate a suppression of the hematite reduction rate caused by accumulation of Fe(II) in the system. Addition of Fe(II) to the hematite suspension, prior to inoculation with CN32, significantly inhibited hematite reduction and greatly diminished the effects of all of the organic materials, although some enhancement was observed due to addition of anthroquinone-2,6-disulfonate. These results demonstrate that NOM can enhance iron reduction by electron shuttling and by complexation mechanisms.