Arsenate and Arsenite Sorption on Magnetite: Relations to Groundwater Arsenic Treatment Using Zerovalent Iron and Natural Attenuation

Magnetite (Fe₃O₄) is a zerovalent iron corrosion product; it is also formed in natural soil and sediment. Sorption of arsenate (As(V)) and arsenite (As(III)) on magnetite is an important process of arsenic removal from groundwater using zerovalent iron-based permeable reactive barrier (PRB) technology and natural attenuation. We tested eight magnetite samples (one from Phoenix Environmental Ltd, one from Cerac, Inc. and six from Connelly-GPM, Inc.) that contained from 79 to 100% magnetite. The magnetites were reacted in the absence of light with either As(V) or As(III) in 0.01 M NaCl at 23°C at equilibrium pH 2.5–11.5 for 24 h. As(V) sorption showed a continuous drop with increasing pH from 2.5 to 11.5; whereas, As(III) sorption exhibited maxima from pH 7 to 9. Equal amounts of As(V) and As(III) were sorbed at pH 5.6–6.8. Higher amounts of As(III) were sorbed by the magnetites than As(V) at pH values greater than 6.8. The solution speciation test did not show any chemical reduction of As(V) in any magnetite suspension, which is consistent with the X-ray Photoelectron Spectroscopy (XPS) study of a Connelly-GPM magnetite (CC-1048) suspension. Conversely, XPS results show that the As(III) is partially oxidized in the magnetite (CC-1048) suspension. This is also consistent with the batch test results that also show more oxidation occurring at alkaline pH. Complete oxidation of As(III) occurred in a synthetic birnessite (δ-MnO₂) suspension after 24 h of reaction. The minute impurities of Mn (possibly as an oxide form) in the magnetite samples may have been responsible for As(III) oxidation. In addition, the structural Fe(III) in magnetite and hydroxyl radicals in solution could also serve as oxidants for As(III) oxidation. The conversion of As(III) to As(V) in the magnetite suspensions would be beneficial in a remediation scheme for As removal, since As(V) is considered less toxic than As(III). Information from the present study can help predict the sorption behavior and fate of arsenic species in engineered PRB systems and natural environments.