Susceptibility of Goethite to Fe²⁺-Catalyzed Recrystallization over Time

Recent work has shown that iron oxides, such as goethite and hematite, may recrystallize in the presence of aqueous Fe²⁺ under anoxic conditions. This process, referred to as Fe²⁺-catalyzed recrystallization, can influence water quality by causing the incorporation/release of environmental contaminants and biological nutrients. Accounting for the effects of Fe²⁺-catalyzed recrystallization on water quality requires knowing the time scale over which recrystallization occurs. Here, we tested the hypothesis that nanoparticulate goethite becomes less susceptible to Fe²⁺-catalyzed recrystallization over time. We set up two batches of reactors in which ⁵⁵Fe²⁺ tracer was added at two different time points and tracked the ⁵⁵Fe partitioning in the aqueous and goethite phases over 60 days. Less ⁵⁵Fe uptake occurred between 30 and 60 days than between 0 and 30 days, suggesting goethite recrystallization slowed with time. Fitting the data with a box model indicated that 17% of the goethite recrystallized after 30 days of reaction, and an additional 2% recrystallized between 30 and 60 days. The decreasing susceptibility of goethite to recrystallize as it reacted with aqueous Fe²⁺ suggested that recrystallization is likely only an important process over short time scales.