Effects of Calcium on Arsenate Adsorption and Arsenate/Iron Bioreduction of Ferrihydrite in Stimulated Groundwater

The reduction and transformation of arsenic-bearing ferrihydrite by arsenate-iron reducing bacteria is one of the main sources of arsenic enrichment in groundwater. During this process the coexistence cations may have a considerable effect. However, the ionic radius of calcium is larger than that of iron and shows a low affinity for ferrihydrite, and the effect of coexisting calcium on the migration and release of arsenic in arsenic-bearing ferrihydrite remains unclear. This study mainly explored the influence of adsorbed Ca2+ on strain JH012-1-mediated migration and release of arsenate in a simulated groundwater environment, in which 3 mM ferrihydrite and pH 7.5. Ca2+ were pre-absorbed on As(V)-containing ferrihydrite with a As:Fe ratio of 0.2. Solid samples were analyzed by X-ray diffraction (XRD), scanning electron microscopic (SEM), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The results show that calcium and arsenate can synergistically adsorb on ferrihydrite due to the electrostatic interactions, and the adsorbed Ca2+ mainly exists on the surface through the outer-sphere complex. Adsorbed Ca2+ entering the stimulated groundwater was easily disturbed and led to an extra release of 3.5 mg/L arsenic in the early stage. Moreover, adsorbed Ca2+ inhibited biogenic ferrous ions from accumulating on ferrihydrite. As a result, only 12.30% Fe(II) existed in the solid phase, whereas 29.35% existed without Ca2+ adsorption. Thus, the generation of parasymplesite was inhibited, which is not conducive to the immobilization of arsenic in groundwater.