The Fe(III)-As(III)-anion precipitation as layered double hydroxide-like compounds such as tooeleite and ferric arsenite hydroxychloride (FC) has been found in As(III)-contaminated acidic mine soils. However, the question of whether As(III) is immobilized by Fe(III) in aqueous nitrate media, a common constituent in soils and metallurgical wastewater, remains unclear. Herein, we investigated the effects and mechanism of nitrate on As(III) immobilization via Fe(III)-As(III)-nitrate precipitation. Our results indicated that new ferric arsenite hydroxynitrate (FN) with variable Fe(III)/As(III)/nitrate molar ratios crystallized in an initial nitrate content range of 11,160–74,400 mg·L−1 at pH 2.3. This FN precipitation resulted in 60.3–87.9% of As(III) removal and a fall-rise immobilization trend as a function of the initial nitrate concentration. The optimal initial nitrate concentration for As(III) fixation was 44,640 mg·L−1. Although FN shared similar morphology and crystal structure with tooeleite and FC, the substitution of NO3− for SO42− and Cl− in the FeO6-AsO3 interlayers caused a significant local structural distortion due to different ionic radii. The characteristic infrared and Raman bands of the nitrate group in FN occurred at 1,363 cm−1, 1,384 cm−1 and 152 cm−1, 722 cm−1, 1,055 cm−1, respectively. The FN induced significantly enhanced As(III) immobilization relative to its tooeleite and FC counterparts at equimolar concentrations of NO3−, SO42−, and Cl− as the media.
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