Adsorption of As(V), As(III) and methyl arsenic by calcite and the impact of some groundwater species
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The objective of this research was to investigate the retention of arsenate (iAsV), arsenite (iAsIII), monomethyl arsenate (MMAsV) and dimethyl arsenate (DMAsV) by calcite and assess the impact of dissolved Ca2+, Mg2+, phosphate and sulfate on arsenic solubility, adsorption and precipitation phenomena. Adsorption kinetics of iAsV, evaluated at a low and high concentration, was a relatively rapid process, with a fast initial reaction rate within the first few minutes and a subsequent slower reaction rate as equilibrium was approached. The relative adsorption of arsenicals decreased in the following order: iAsV > iAsIII > DMAV > MMAV. In no case was a clear adsorption maximum observed with increasing dissolved arsenic concentration. Dissolved 0.01 M Ca2+ resulted in an increase in iAsV adsorption; however, in the presence of 0.1 M Ca2+ adsorption of iAsV was decreased. The presence of Mg2+ as 0.01 M Mg(NO3)2 resulted in decreased iAsV adsorption probably the result of a lower iAsV affinity for adsorbed Mg2+ as compared to Ca2+. Phosphate and sulfate were highly competitive with iAsV in adsorption to calcite and both resulted in decreased iAsV adsorption. The total prevention of iAsV adsorption at initial equimolar arsenic/phosphate concentrations > 88 µM each could be from the consumption of available calcite surface sites by the specific adsorption of phosphate. Equilibrium modeling, using the geochemical and mineral speciation of equilibrium model (MINTEQA2), indicated that at low concentrations of arsenate or phosphate solid-phase precipitation was not likely and adsorption processes likely controlled solubility. At high concentrations of arsenate Ca3(AsO4)2 · 3 2/3 H2O and Ca3(AsO4)2 · 4 1/4 H2O solid phases could be controlling arsenate solubility. This study indicates that arsenic adsorption response by calcite was different than that of phosphate suggesting that arsenic may not be specifically adsorbed to calcium at the calcite surface. Reduction and biomethylation of arsenic decreased adsorption, suggesting that processes which could affect the speciation of arsenic in the environment, could increase arsenic mobility in environmental systems where calcite and dissolved aqueous calcium play a predominant role in controlling arsenic solubility. Dissolved aqueous concentrations of magnesium, phosphate and sulfate generally reduced the ability of arsenic to be adsorbed to calcite.
Jones, Robert Garret (2007). Adsorption of As(V), As(III) and methyl arsenic by calcite and the impact of some groundwater species. Master's thesis, Texas A&M University. Available electronically from