Effect of phosphate on ferrihydrite transformation and the associated arsenic behavior mediated by sulfate-reducing...

Although PO₄^3- is commonly found in association with iron (oxyhydr)oxide, the effect of PO₄^3- on ferrihydrite reduction, mineralogical transformation, and associated As behavior in sulfate-reducing bacteria (SRB)-rich environments remains unclear. In this study, batch experiments, together with geochemical, mineralogical, and biological analyses, were conducted to elucidate these processes. The results showed that SRB can reduce ferrihydrite via direct and indirect processes, and PO₄^3- promoted ferrihydrite reduction by supporting SRB growth at low and medium PO₄^3- loadings. However, at high loadings, PO₄^3- stabilized the ferrihydrite. PO₄^3- shifted the transformation of ferrihydrite from magnetite and mackinawite to vivianite, which scavenges As effectively by incorporating As into its particle. In systems with 0.5 mM SO₄^2-, PO₄^3- exerted a weak effect on As mobilization. However, in systems with 10 mM SO₄^2-, substantial amounts of As were released into the solution, and PO₄^3- impacted As behavior strongly. Low PO₄^3- loadings increased the mobilization of As because of the competitive adsorption of PO₄^3- on mackinawite. Medium and high PO₄^3- loadings were beneficial for As immobilization because of the substitution of mackinawite by vivianite. These findings have important implications for understanding the biogeochemistry of iron (oxyhydr)oxide and As behavior in SRB-containing sediments.