Potential application of microbial iron redox cycles in nitrate removal and their effects on clay mineral properties

Thursday, 18 December 2014
Linduo Zhao1, Hailiang Dong1, Ravi K Kukkadapu2, Brandon R Briggs3 and Qiang Zeng4, (1)Miami University Oxford, Oxford, OH, United States, (2)Pacific Northwest National Lab, Richland, WA, United States, (3)Miami University, Oxford, OH, United States, (4)China University of Geosciences, School of the Earth Sciences and Resources, Beijing, China
Phyllosilicates that are ubiquitous in subsurface can serve as an iron source for microbial respiration. The objective of this research is to determine the ability of the phyllosilicate Fe to remove nitrate in subsurface undergoing microbial-driven redox cycles. In this study, thus, a well-characterized reference clay (NAu-2; nontronite), was subjected to redox cycles in a system containing dissimilatory Fe(III)-reducing bacteria, Shewanella putrefaciens CN32, and nitrate-dependent Fe(II)-oxidizing bacteria, Pseudogulbenkiania sp. Strain 2002. Three redox cycles were conducted in bicarbonate- and PIPES-buffered medium. The extents of Fe(III) reduction, Fe(II) oxidation, nitrate reduction, and its various intermediate products were measured by wet chemical methods. For each cycle, Electron Energy Loss Spectroscopy and Mossbauer spectroscopy confirmed Fe oxidation state. Mineralogical changes were identified by using X-ray diffraction (XRD), 57Fe-Mössbauer spectroscopy, and infrared absorption spectroscopy. For all three cycles, nitrate was completely reduced to nitrogen gas under both bicarbonate- and PIPES- buffered conditions. As redox cycle increased, bio-reduction extents of Fe(III) in NAu-2 decreased by 33% and 48% in PIPES- and bicarbonate-buffered medium, respectively; however, bio-oxidation extents increased by 66% and 55% in the same medium, respectively. Despite the change of OH-stretching vibration band and OH-bending vibration bands in NAu-2 structure along Fe redox cycles, XRD data showed interlayer spacing of NAu-2 to be constant along the same Fe redox cycle. 57Fe-Mössbauer spectroscopy indicated complex reduction and re-oxidation pathways. For example, a distinct Fe(II) doublet and a Fe2.5+  feature due to interfacial Fe(II)-Fe(III) electron transfer on clay mineral are prominent in their RT spectra. Both these Fe(II) are partially oxidized by Fe(II)-oxidizing bacteria. The result of this study shows that Fe in biogenically reduced or oxidized NAu-2 could serve as a renewable iron source for multiple biogenic redox cycles to remove nitrate contaminant in soils and groundwater systems.