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Methyl Arsenic Adsorption and Desorption Behavior on Iron Oxides

Brandon J. Lafferty, Richard H. Loeppert

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Abstract

In virtually all Earth surface environments, methylated forms of arsenic can be found. Because of the widespread distribution and toxicity of methyl-arsenic compounds, their adsorption by soil minerals is of considerable interest. The objective of this study was to compare the adsorption and desorption behavior of methylarsonic acid (MMAsV), methylarsonous acid (MMAsIII), dimethylarsinic acid (DMAsV), dimethylarsinous acid (DMAsIII), arsenate (iAsV), and arsenite (iAsIII) on iron oxide minerals (goethite and 2-line ferrihydrite) by means of adsorption isotherms, adsorption envelopes, and desorption envelopes (using sulfate and phosphate as desorbing ligands). MMAsIII and DMAsIII were not appreciably retained by goethite or ferrihydrite within the pH range of 3 to 11, while iAsIII was strongly adsorbed to both iron oxides. MMAsV and iAsV were adsorbed in higher amounts than DMAsV on goethite and ferrihydrite at all pH values studied. MMAsV and iAsV exhibited high adsorption affinities on both goethite and ferrihydrite from pH 3 to 10, while DMAsV was adsorbed only at pH values below 8 by ferrihydrite and below 7 by goethite. All arsenic compounds were desorbed more efficiently by phosphate than sulfate. MMAsV, iAsV, and DMAsV each exhibited adsorption characteristics suggesting specific adsorption on both goethite and ferrihydrite. Increased methyl substitution resulted in both decreased adsorbed arsenic at low arsenic concentrations in solution and increased ease of arsenic release from the iron oxide surface.

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What this paper is about

In virtually all Earth surface environments, methylated forms of arsenic can be found. Because of the widespread distribution and toxicity of methyl-arsenic compounds, their adsorption by soil minerals is of considerable interest. The objective of this study was to compare the adsorption and desorption behavior of methylarsonic acid (MMAsV), methylarsonous acid (MMAsIII), dimethylarsinic acid (DMAsV), dimethylarsinous acid (DMAsIII), arsenate (iAsV), and arsenite (iAsIII) on iron oxide minerals (goethite and 2-line ferrihydrite) by means of adsorption isotherms, adsorption envelopes, and desorption envelopes (using sulfate and phosphate as desorbing ligands). MMAsIII and DMAsIII were not appreciably retained by goethite or ferrihydrite within the pH range of 3 to 11, while iAsIII was strongly adsorbed to both iron oxides. MMAsV and iAsV were adsorbed in higher amounts than DMAsV on goethite and ferrihydrite at all pH values studied. MMAsV and iAsV exhibited high adsorption affinities on both goethite and ferrihydrite from pH 3 to 10, while DMAsV was adsorbed only at pH values below 8 by ferrihydrite and below 7 by goethite. All arsenic compounds were desorbed more efficiently by phosphate than sulfate. MMAsV, iAsV, and DMAsV each exhibited adsorption characteristics suggesting specific adsorption on both goethite and ferrihydrite. Increased methyl substitution resulted in both decreased adsorbed arsenic at low arsenic concentrations in solution and increased ease of arsenic release from the iron oxide surface.

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Available abstract

In virtually all Earth surface environments, methylated forms of arsenic can be found. Because of the widespread distribution and toxicity of methyl-arsenic compounds, their adsorption by soil minerals is of considerable interest. The objective of this study was to compare the adsorption and desorption behavior of methylarsonic acid (MMAsV), methylarsonous acid (MMAsIII), dimethylarsinic acid (DMAsV), dimethylarsinous acid (DMAsIII), arsenate (iAsV), and arsenite (iAsIII) on iron oxide minerals (goethite and 2-line ferrihydrite) by means of adsorption isotherms, adsorption envelopes, and desorption envelopes (using sulfate and phosphate as desorbing ligands). MMAsIII and DMAsIII were not appreciably retained by goethite or ferrihydrite within the pH range of 3 to 11, while iAsIII was strongly adsorbed to both iron oxides. MMAsV and iAsV were adsorbed in higher amounts than DMAsV on goethite and ferrihydrite at all pH values studied. MMAsV and iAsV exhibited high adsorption affinities on both goethite and ferrihydrite from pH 3 to 10, while DMAsV was adsorbed only at pH values below 8 by ferrihydrite and below 7 by goethite. All arsenic compounds were desorbed more efficiently by phosphate than sulfate. MMAsV, iAsV, and DMAsV each exhibited adsorption characteristics suggesting specific adsorption on both goethite and ferrihydrite. Increased methyl substitution resulted in both decreased adsorbed arsenic at low arsenic concentrations in solution and increased ease of arsenic release from the iron oxide surface.

Key concepts: Ferrihydrite, Goethite, Arsenate, Arsenic, Adsorption, Chemistry, Arsenite, Inorganic chemistry

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