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During the aging process, ferrihydrite was transformed into mineral mixtures composed of different proportions of ferrihydrite, goethite, lepidocrocite and hematite. Such a transformation may affect the fixed ability of arsenic. In this study, the stability of Fe-As composites formed with As(V) and the minerals aged for 0, 1, 4, 10 and 30 days of ferrihydrite were systematically examined, and the effects of molar of ratios Fe/As were also clarified using kinetic methods combined with multiple spectroscopic techniques. The results indicated that As(V) was rapidly adsorbed on minerals during the initial polymerization process, which delayed both the ferrihydrite conversion and the hematite formation. When the Fe/As molar ratio was 1.875 and 5.66, the As(V) adsorbed by ferrihydrite began to release after 6 hr and 12 hr, respectively. The corresponding release amounts of As(V) were 0.55 g/L and 0.07 g/L, and the adsorption rates were 92.43% and 97.50% at 60 days, respectively. However, the As(V) adsorbed by the transformation products aged for 30 days of ferrihydrite began to release after adsorbed 30 days. The corresponding release amounts of As(V) were 0.25 g/L and 0.03 g/L, and the adsorption rates were 84.23% and 92.18% after adsorbed 60 days, for the Fe/As=1.875 and 5.66, respectively. Overall, the combination of As(V) with ferrihydrite and aged products transformed from a thermodynamically metastable phase to a dynamically stable state within a certain duration. Moreover, the aging process of ferrihydrite reduced the sorption ability of arsenate by iron (hydr)oxide but enhanced the stability of the Fe-As composites.

The simultaneous mitigation of toxic arsenic (As) and cadmium (Cd) in rice grain remains a global challenge. Passivation with natural or artificially modified materials has shown great potential to simultaneously reduce the bioavailability of As and Cd in paddy soils. To date, however, limited materials have are available, with unclear underling mechanisms. Here, a natural iron-based desulfurization material is hypothesized to simultaneously mitigate As and Cd availability in paddy soil-rice continuum, since it is rich in calcium (Ca), iron (Fe), Silicon (Si), manganese (Mn), and sulfur (S). The addition of the proposed material promoted rice growth and reduced soil availability of Cd (extracted with 0.01 mg·L

The strong ability of ferrihydrite and its aged minerals for fixing arsenate is a key factor in remediating arsenate-polluted environments. It is therefore crucial to clarify the stability of Fe–As complexes and the release conditions for As(V). The As(V) release amount was evaluated and compared in the presence of six representative anions, namely, phosphate, silicate, sulfate, inositol hexaphosphate, citrate, and oxalate. It was found that the As(V) release amount changed with the aging time of ferrihydrite and that this tendency generally followed two rules. These are, longer aging time leads to lower As(V) release (Rule 1), and longer aging time leads to higher As(V) release (Rule 2). Whether Rule 1 or Rule 2 dominated As release depended on the number of surface groups, size of competing anions, and contribution of As(V) re-adsorption. Characterization results using X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) provided evidence for the predicted mechanisms of As(V) release under various circumstances. In this work, it was demonstrated that when inorganic anions such as sulfate and silicate are present, ferrihydrite with longer aging time led to decreased As(V) release. When organic anions are present, ferrihydrite with less aging time results in reduced As(V) leaching. For anions such as phosphate, the As(V) release amount in relation to the ferrihydrite aging time depends on the concentration of phosphate ions. Nevertheless, the ligand concentration and As(V) loading rate on ferrihydrite should be simultaneously considered for the rule governing As(V) releasing.