Influence of Coprecipitated Organic Matter on Fe2+(aq)-Catalyzed Transformation of Ferrihydrite: Implications for Carbon Dynamics

Aqueous Fe(II) is known to catalyze the abiotic transformation of ferrihydrite to more stable Fe minerals. However, little is known about the impacts of coprecipitated OM on Fe(II)-catalyzed ferrihydrite transformation and its consequences for C dynamics. Accordingly, we investigated the extent and pathway of Fe(II)-induced transformation of OM-ferrihydrite coprecipitates as a function of C/Fe ratios and aqueous Fe(II) concentrations, and its implications for subsequent C dynamics. The coprecipitated OM resulted in a linear decrease in ferrihydrite transformation with increasing C/Fe ratios. The secondary mineral profiles upon Fe(II) reaction with OM-ferrihydrite coprecipitates depend on Fe(II) concentrations At 0.2 mM Fe(II), OM completely inhibited goethite formation and stimulated lepidocrocite formation. At 2 mM Fe(II), whereas goethite was formed in the presence of OM, OM reduced the amount of goethite and magnetite formation and increased the formation of lepidocrocite. The solid-phase C content remained unchanged after reaction, suggesting that OM remains associated with Fe minerals following ferrihydrite transformation to more stable Fe minerals. However, C desorbability by H2PO4(-) from the resulting Fe minerals following reaction was enhanced. The study indicates a "lepidocrocite favoring effect" by OM and suggests that Fe(II)-catalyzed transformation of ferrihydrite may decrease OM stability in natural environments under moderately reducing conditions.