Cr release from Cr-substituted goethite during the aqueous Fe(II)-induced recrystallization

Abstract

The interaction between aqueous Fe(II) (Fe(II)aq) and iron minerals is an important reaction of the iron cycle, and it plays a critical role in impacting the environmental behavior of heavy metals in soils. Metal substitution into iron (hydr)oxides has been reported to reduce Fe atom exchange rates between Fe(II)aq and metal-substituted iron (hydr)oxides and inhibit the recrystallization of iron (hydr)oxides. However, the environmental behaviors of the substituted metal during these processes remain unclear. In this study, Fe(II)aq-induced recrystallization of Cr-substituted goethite (Cr-goethite) was investigated, along with the sequential release behavior of substituted Cr(III). Results from a stable Fe isotopic tracer and Mossbauer characterization studies show that Fe atom exchange occurred between Fe(II)aq and structural Fe(III) (Fe(III)oxide) in Cr-goethites, during which the Cr-goethites were recrystallized. The Cr substitution inhibited the rates of Fe atom exchange and Cr-goethite recrystallization. During the recrystallization of Cr-goethites induced by Fe(II)aq, Cr(III) was released from Cr-goethite. In addition, Cr-goethites with a higher level of Cr-substituted content released more Cr(III). The highest Fe atom exchange rate and the highest amount of released Cr(III) were observed at a pH of 7.5. Under reaction conditions involving a lower pH of 5.5 or a higher pH of 8.5, there were substantially lower rates of Fe atom exchange and Cr(III) release. This trend of Cr(III) release was similar with changes in Fe atom exchange, suggesting that Cr(III) release is driven by Fe atom exchange. The release and reincorporation of Cr(III) occurred simultaneously during the Fe(II)aq-induced recrystallization of Cr-goethites, especially during the late stage of the observed reactions. Our findings emphasize an important role for Fe(II)aq-induced recrystallization of iron minerals in changing soil metal characteristics, which is critical for the evaluation of soil metal activities, especially those in Fe-rich soils.