Arsenic adsorption and oxidation at manganite surfaces. 1. Method for simultaneous of determination of adsorbed and dissolved arsenic species

Arsenic occurs in the +III oxidation state as a metastable species in oxic waters. Under oxic conditions, As(III) is both more mobile in natural waters and less efficiently removed by water treatment processes than As(V). Other oxidants, however, can react with As(III) more rapidly than oxygen. The oxidation of As(III) by manganite occurs on the time scale of hours. Here, a method is introduced for the rapid determination of the total and dissolved concentrations of arsenic species in this heterogeneous system; adsorbed arsenic concentrations are calculated by difference. The oxidation reaction is quenched by the addition of ascorbic acid to effect the reductive dissolution of manganite and concomitant release of adsorbed As(III) and As(V) into solution. Once in solution, As(III) and As(V) are separated using anion-exchange chromatography. Comparison of dissolved and total concentrations of As(III) and As(V) clearly illustrates that the overall conversion rate of As(III) to As(V) in this system would be overpredicted based solely on dissolved As(III) concentrations and underpredicted based solely on dissolved As(V) concentrations. The overall conversion of As(III) to As(V) was more rapid at pH 4 than at pH 6.3 and was unaffected by the presence of boric acid at 95 μM or 3 mM. However, the presence of 200 μM phosphate (at pH 4) decreased the overall rate of conversion of As(III) to As(V). Comparison of total and dissolved As(III) concentrations during the reaction time course demonstrates that the effects of pH and phosphate on adsorbed As(III) concentrations are generally consistent with these kinetic observations. | Arsenic occurs in the +III oxidation state as a metastable species in oxic waters. Under oxic conditions, As(III) is both more mobile in natural waters and less efficiently removed by water treatment processes than As(V). Other oxidants, however, can react with As(III) more rapidly than oxygen. The oxidation of As(III) by manganite occurs on the time scale of hours. Here, a method is introduced for the rapid determination of the total and dissolved concentrations of arsenic species in this heterogeneous system; adsorbed arsenic concentrations are calculated by difference. The oxidation reaction is quenched by the addition of ascorbic acid to effect the reductive dissolution of manganite and concomitant release of adsorbed As(III) and As(V) into solution. Once in solution, As(III) and As(V) are separated using anion-exchange chromatography. Comparison of dissolved and total concentrations of As(III) and As(V) clearly illustrates that the overall conversion rate of As(III) to As(V) in this system would be overpredicted based solely on dissolved As(III) concentrations and underpredicted based solely on dissolved As(V) concentrations. The overall conversion of As(III) to As(V) was more rapid at pH 4 than at pH 6.3 and was unaffected by the presence of boric acid at 95 μM or 3 mM. However, the presence of 200 μM phosphate (at pH 4) decreased the overall rate of conversion of As(III) to As(V). Comparison of total and dissolved As(III) concentrations during the reaction time course demonstrates that the effects of pH and phosphate on adsorbed As(III) concentrations are generally consistent with these kinetic observations.