Surface Chemical Heterogeneity of Bacteriogenic Iron Oxides from a Subterranean Environment

Abstract

This study quantifies the surface chemical heterogeneity of bacteriogenic iron oxides (BIOS) and its end-members (2-line ferrihydrite and intermixed intact and fragmented bacteria). On a dry weight basis, BIOS consisted of 64.5 +/- 1.8% ferrihydrite and 34.5 +/- 1.8% organic matter. Enrichment of Al, Cu, Cr, Mn, Sr, and Zn was shown in the solid versus the aqueous phase (1.9 < log Kd < 4.2). Within the solid-phase Al (69.5%), Cu (78.7%), and Zn (77.9%) were associated with the bacteria, whereas Cr (59.8%), Mn (99.8%), and Sr (79.4%) preferred ferrihydrite. Acid-base titration data from the BIOS and bacteria were fitted using FOCUS pKa spectroscopy. The bacteria spectrum with pKa's of 4.18 +/- 0.37, 4.80 +/- 0.54, 6.98 +/- 0.45, and 9.75 +/- 0.68 was similar to discrete and continuous spectra for intact and fragmented bacteria. The BIOS spectrum recorded pKa's of 4.27 +/- 0.51, 6.61 +/- 0.51, 7.89 +/- 1.10, and 9.65 +/- 0.66 and was deconvoluted to remove overlapping binding site contributions from the bacteria. The resulting residual iron oxide spectrum coincided with discrete MUSIC spectra for goethite and lepidocrocite with pKa values of 4.10 +/- 0.43, 6.53 +/- 0.45, 7.81 +/- 0.76, and 9.51 +/- 0.68. Surface site density analysis showed that acidic sites (pKa < 6) were contributed by the bacteria (37%), whereas neutral sites (6 < pKa < 8) were characteristic of the iron oxide fraction (35%). Basic sites (8 < pKa) were higher in the bacteria (57%), than in the BIOS (44%) or iron oxide fractions (47%). This analysis suggested a high degree of bacterial group masking and a similarity between the BIOS and goethite surface reactivity. An understanding of the BIOS surface chemical heterogeneity and inherent proton and metal binding capacity was obtained through the use of FOCUS apparent pKa spectroscopy.