Sorption and desorption of arsenate and arsenite on calcite

The adsorption and desorption of arsenate (As(V)) and arsenite (As(III)) on calcite was investigated in a series of batch experiments in calcite-equilibrated solutions. The solutions covered a broad range of pH, alkalinity, calcium concentration and ionic strength. The initial arsenic concentrations were kept low (<33 μM) to avoid surface precipitation. The results show that little or no arsenite sorbs on calcite within 24 h at an initial As concentration of 0.67 μM. In contrast, arsenate sorbs readily and quickly on calcite. Likewise, desorption of arsenate from calcite is fast and complete within hours, indicating that arsenate is not readily incorporated into the calcite crystal lattice. The degree of arsenate sorption depends on the solution chemistry. Sorption increases with decreasing alkalinity, indicating a competition for sorption sites between arsenate and (bi)carbonate. pH also affects the sorption behavior, likely in response to changes in arsenate speciation or protonation/deprotonation of the adsorbing arsenate ion. Finally, sorption is influenced by the ionic strength, possibly due to electrostatic effects. The sorption of arsenate on calcite was modeled successfully using a surface complexation model comprising strong and weak sites. In the model, the adsorbing arsenate species were H ₂ AsO ₄ ^- and CaH AsO ₄ ⁰. The model was able to correctly predict the adsorption of arsenate in the wide range of calcite-equilibrated solutions used in the batch experiments and to describe the non-linear shape of the sorption isotherms. Extrapolation of the experimental results to calcite bearing aquifers suggests a large variability in the mobility of arsenic. Under reduced conditions, arsenite, which does not sorb on calcite, will dominate and, hence, As will be highly mobile. In contrast, when conditions are oxidizing, arsenate is the predominant species and, because arsenate adsorbs strongly on calcite, As mobility will be significantly retarded. The estimated retardation factors for arsenate in carbonate aquifers range from 25 to 200.