Natural organic matter inhibits Ni stabilization during Fe(II)-catalyzed ferrihydrite transformation

Trace metals, such as nickel (Ni), are often found associated with ferrihydrite (Fh) in soil and sediment and have been shown to redistribute during Fe(II)-catalyzed transformation of Fh. Fe(II)-catalyzed transformation of Fh, however, is often inhibited when natural organic matter (NOM) is associated with Fh. To explore whether NOM affects the behavior of Ni during Fe(II)-catalyzed transformation of Fh, we tracked Ni distribution, Fe atom exchange, and mineral transformation of Fh and Fh coprecipitated with Suwannee River natural organic matter (SRNOM-Fh). As expected, in the absence of Fe(II), Fh and SRNOM-Fh did not transform to secondary Fe minerals after two weeks. We further observed little difference in Ni adsorption on SRNOM-Fh compared to Fh. In the presence of Fe(II), however, we found that Ni associated with SRNOM-Fh was more susceptible to acid extraction than Fh. Specifically, we found almost double the amount of Ni remaining in the Fh after mild extraction compared to SRNOM-Fh. XRD showed that Fh transformed to goethite and magnetite whereas SRNOM-Fh did not transform despite ⁵⁷Fe isotope tracer experiments confirmed that SRNOM-Fh underwent extensive atom exchange with aqueous Fe(II). Our findings suggest that Fe atom exchange may not be sufficient for obvious Ni stabilization and that transformation to secondary minerals may be necessary for Ni stabilization to occur.