Stability of Ferrihydrite and Organic Matter in Ferrihydrite-Organic Matter Associations

Abstract:

Iron oxides can bind particularly large amounts of organic matter (OM) and seem to be an important control on OM storage in many soils. To better understand the interactions between Fe oxides and OM, we produced ferrihydrite-OM associations by adsorption and coprecipitation in laboratory experiments. Because ferrihydrites are often formed in OM-rich solutions, we assume that coprecipitation is a common process in nature. In contrast to adsorption on pre-existing ferrihydrite surfaces, coprecipitation involves adsorption, occlusion (physical entrapment of OM), formation of Fe-OM complexes, and poisoning of ferrihydrite growth. The reactivity of coprecipitates may therefore differ from ferriydrites with adsorbed OM.

Incubation experiments with an inoculum extracted from a Podzol forest-floor were carried out to quantify the mineralization of the adsorbed and coprecipitated organic matter. These experiments showed that the association with ferrihydrite stabilized the associated organic matter, but that differences in the degradability of adsorbed and coprecipitated organic matter were small. We therefore conclude that coprecipitation does not lead to a significant formation of microbial inaccessible organic matter domains.

Microbial reduction experiments were performed using Geobacter bremensis. We observed that increasing amounts of associated OM led to decreasing initial reaction rates and a decreasing degree of dissolution. Reduction of coprecipitated ferrihydrites was faster than reduction of ferrihydrites with adsorbed OM.

Our data demonstrate that the association with ferrihydrite can effectively stabilize labile polysaccharides. Vice versa, these polysaccharides may protect ferrihydrite from reduction by Geobacter-like bacteria. However, a challenge for future studies will be to link formation and degradation of mineral-organic associations to natural porous systems, that is, to the complex interplay of mass transport and microbial distribution in the undisturbed soil.