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Arsenate–Ferrihydrite Systems from Minutes to Months: A Macroscopic and IR Spectroscopic Study of an Elusive Equilibrium

Swedlund, Peter J., Holtkamp, Hannah, Song, Yantao, Daughney, Christopher J.
Environmental Science & Technology 2014 v.48 no.5 pp. 2759-2765
arsenic, equations, ferrihydrite, models, pH, sorption, spectral analysis
Sorption by ferrihydrite is an important control on As(V) concentrations in many oxic aquatic systems. There are significant discrepancies in reported sorption constants (log(KAₛ)), which presents a problem for quantifying and understanding this important system. A review of reported ferrihydrite–As(V) sorption studies indicated a positive correlation between reaction time used in the experiments and the log(KAₛ) values derived from the data. In this paper, we study the kinetics of As(V) sorption over ≈3000 h in nine systems with varying pH and As(V)/Fe. Ferrihydrite was stable in all systems containing As(V), and the [As(V)] in solution decreased linearly as a function of log(t) (termed Elovich kinetics) over the full 3000 h in most systems. A stable [As(V)] was only observed in systems with low As(V)/Fe and low pH. Apparent As(V) sorption constants were derived from the data at specific time intervals using the diffuse layer model and equations describing log(KAₛ) values as a function of time provide a way to describe this elusive equilibrium. IR spectra support the hypothesis that slow interparticle diffusion is responsible for the slow approach to equilibrium. This work resolves discrepancies in previous studies of As(V)–ferrihydrite and provides equations to allow for system appropriate log(KAₛ) values to be used.