Decreasing arsenic bioaccessibility/bioavailability in soils with iron amendments.

We investigated the use of various iron amendments (metallic Fe and soluble Fe(II)- and Fe(III)-halide salts) to reduce arsenic (As) bioaccessibility (as a surrogate for oral bioavailability) in contaminated soils. Soluble Fe(II)- and Fe(III)-salts were more effective than metallic Fe in reducing As bioaccessibility. Adding soluble Fe(III)-salts to soil reduces As bioaccessibility in two ways, by increasing the Fe(III) (hydr)oxide content and by lowering the soil pH. A detailed investigation into the effect of soil moisture when adding Fe(III) amendments indicated that the reaction can occur in situ if sufficient (>or=30% moisture) is added. If the amendments are added to the soil without moisture, a reduction in bioaccessibility will occur in the extraction fluid itself (i.e., an experimental artifact not reflecting a true in situ reduction in bioaccessibility). Adding Fe (III)-salts to nine As-contaminated soils at a Fe:As molar ratio of 100:1 reduced the average bioaccessibility in the soils by approximately a factor of two. Greater reductions in As bioaccessibility can be achieved by increasing the Fe:As molar ratio. These results suggest decreasing As bioaccessibility and bioavailability in soil by adding Fe amendments may be an effective strategy to remediate As-contaminated soils.

Effects of dissolved carbonate on arsenic adsorption and mobility.

The effects of high aqueous carbonate concentrations on arsenic mobility and transport in the subsurface were studied in synthetic iron oxide-coated sand column experiments. Elevated aqueous carbonate concentrations in groundwater have been studied and linked, by some authors, to increased aqueous As concentrations in natural waters. This study found that increasing carbonate concentrations had relatively little effect on As(V) adsorption to the iron oxide-coated sand surface at pH 7. The adsorption of As(V) decreased marginally when the CO2(g) partial pressure increased from 10(-3.5) to 10(-1.8) atm, despite a 50-fold increase in total dissolved carbonate (0.072 to 3.58 mM). Increasing the CO2(g) partial pressure to 10(-10) atm resulted in only a slight decrease in As(V) adsorption and increase in mobility, despite a >300-fold increase in total dissolved carbonate (to 22.7 mM). When compared to phosphate, a known competitive anion, carbonate mobilized less adsorbed As(V) than was mobilized by phosphate, even when present in much higher concentrations than phosphate. This was also true for an experiment with lower pore water velocity and an experiment where As(II) was introduced instead of As(V). Our experiments conclude that while carbonate anions do compete with As for adsorption to iron oxide-coated sand, the competitive effect is relatively small with regard to the total concentration of adsorbed As and the potential competitive effects of phosphate.