Mackinawite (FeS), as a ubiquitous reduced iron mineral, is known as a key controller of redox reactions in anaerobic subsurface environment. The reaction of FeS with redox-sensitive toxic element such as arsenic is substantially affected by pH conditions of the given environments. In this study, the interaction of As(V) with FeS was studied under strict anaerobic conditions with various pH conditions. The pH-dependent arsenic removal tests were conducted under wide ranges of pH conditions and X-ray absorption spectroscopy (XAS) was applied to investigate the reaction mechanisms under pH 5, 7, and 9. The removal efficiency of FeS for As(V) showed the higher removal of As(V) under low pH conditions and its removal efficiency decreased with increasing pH, and no As(V) reduction was observed in 1 g/L FeS solution. However, XAS analysis indicated the reduction of As(V) to As(III) occurred during reaction between FeS and As(V). The reduced form of As(III) was particularly identified as an arsenic sulfide mineral (As₂S₃) in all pH conditions (pH 5, 7, and 9). As₂S₃ precipitation was more pronounced in pH 5 where the solubility of FeS is higher than in other pH conditions. The linear combination fitting results of XAS demonstrated that As(V) removal mechanism is concerted processes of As₂S₃ precipitation and surface complexation of both arsenic species..

Keywords: Mackinawite, Arsenic, X-ray absorption spectroscopy