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Published September 15, 2003 | public
Journal Article

Comparison of Arsenic(V) and Arsenic(III) Sorption onto Iron Oxide Minerals: Implications for Arsenic Mobility


Arsenic derived from natural sources occurs in groundwater in many countries, affecting the health of millions of people. The combined effects of As(V) reduction and diagenesis of iron oxide minerals on arsenic mobility are investigated in this study by comparing As(V) and As(III) sorption onto amorphous iron oxide (HFO), goethite, and magnetite at varying solution compositions. Experimental data are modeled with a diffuse double layer surface complexation model, and the extracted model parameters are used to examine the consistency of our results with those previously reported. Sorption of As(V) onto HFO and goethite is more favorable than that of As(III) below pH 5−6, whereas, above pH 7−8, As(III) has a higher affinity for the solids. The pH at which As(V) and As(III) are equally sorbed depends on the solid-to-solution ratio and type and specific surface area of the minerals and is shifted to lower pH values in the presence of phosphate, which competes for sorption sites. The sorption data indicate that, under most of the chemical conditions investigated in this study, reduction of As(V) in the presence of HFO or goethite would have only minor effects on or even decrease its mobility in the environment at near-neutral pH conditions. As(V) and As(III) sorption isotherms indicate similar surface site densities on the three oxides. Intrinsic surface complexation constants for As(V) are higher for goethite than HFO, whereas As(III) binding is similar for both of these oxides and also for magnetite. However, decrease in specific surface area and hence sorption site density that accompanies transformation of amorphous iron oxides to more crystalline phases could increase arsenic mobility.

Additional Information

© 2003 American Chemical Society. Received for review January 9, 2003. Revised manuscript received June 27, 2003. Accepted July 3, 2003. Publication Date (Web): August 13, 2003. This work was partly supported by funding from the National Science Foundation (BES-0201888) and by the generous support of William Davidow. The constructive comments of two anonymous reviewers helped improve the manuscript.

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