The association between natural organic matter (NOM) and iron (Fe) minerals was widely found in soil and sediments and has been shown to impact the fate of Fe minerals and NOM. Ferrihydrite, a ubiquitous Fe mineral, serves as important sink for NOM and rapidly transforms to secondary Fe minerals in the presence of Fe(II). The associated NOM has been found to influence the Fe(II)-catalyzed ferrihydrite transformation pathway, but it remains unclear how various NOM affects this transformation and the implication. This study specifically investigates how different species of NOM affect Fe(II)-catalyzed ferrihydrite transformation under different C/Fe ratios. A series of Fe isotope tracer experiments were conducted to measure Fe atom exchange and electron transfer between aqueous Fe(II) and ferrihydrite in the presence of diverse NOM species. The fate of Ni during Fe(II)-catalyzed transformation of NOM-Fh coprecipitate was also investigated.
Ferrihydrite was found less susceptible to Fe(II)-catalyzed transformation with increasing C/Fe ratio and fulvic acids and Suwannee River NOM (SRNOM) in the coprecipitates need lower C/Fe ratio than humic acids to completely inhibit formation of secondary Fe minerals. At C/Fe ratios where ferrihydrite transformed to secondary minerals, goethite was dominant in ferrihydrite coprecipitated with humic acids, whereas lepidocrocite was favored in ferrihydrite coprecipitated with fulvic acids and SRNOM. Adsorbed SRNOM may be more inhibitive than coprecipitated SRNOM on Fe(II)-catalyzed ferrihydrite transformation under similar C/Fe ratios. Despite no secondary mineral transformation at high C/Fe ratios, Mössbauer spectra indicated electron transfer still occurred between Fe(II) and ferrihydrite coprecipitated with fulvic acid and SRNOM. In addition, isotope tracer experiments revealed that a significant fraction of structural Fe(III) in the ferrihydrite mixed with the aqueous phase Fe(II) (~85%). After reaction with Fe(II), Mössbauer spectroscopy indicated some subtle changes in the crystallinity, particle size or particle interactions in the coprecipitate.
The effect of coprecipitated SRNOM on Ni(II) distribution during Fe(II)-catalyzed ferrihydrite transformation was investigated with adsorbed Ni(II) and coprecipitated Ni(II). Ni(II) adsorbed on ferrihydrite was more resistant to acid extraction after Fe(II)-catalyzed transformation and suggested that structural incorporation of Ni into secondary Fe minerals occurred. With coprecipitated SRNOM, ferrihydrite did not transform to secondary minerals in the presence of Fe(II) but extensive Fe atom exchange between aqueous Fe(II) and structural Fe(III) still occurred. Limited change in Ni stability was observed, suggesting there was only small portion of Ni redistributed in the presence of Fe(II). Pre-incorporated Ni(II) in Ni-SRNOM-Fh coprecipitate was partially released (6-8 %) in the presence of Fe(II), but the distribution of remaining Ni(II) in the solid did not change measurably. Our observation suggests that the presence of SRNOM limited the redistribution of Ni most likely because of limited transformation of ferrihydrite to secondary minerals.