Iron mineral transformations and their impact on As (im)mobilization at redox interfaces in As-contaminated aquifers

Abstract Iron minerals are the most important arsenic host in As-contaminated deltaic sediments. Arsenic release from Fe minerals to groundwater exposes millions of people worldwide to a severe health threat. To understand the coupling of Fe mineralogy with As (im)mobilization dynamics, we analyzed the geochemistry and mineralogy of a 46 m long sediment core drilled into the redox transition zone where a high As Holocene aquifer is juxtaposed to a low As Pleistocene aquifer in the Red River delta, Vietnam. We specifically concentrated on mm- to cm-scale redox interfaces within the sandy aquifer. Various Fe phases, such as Fe- and Mn- bearing carbonates, pyrite, magnetite, hematite and Fe-hydroxides (goethite, lepidocrocite) with distinct As concentrations were identified by a combination of high-resolution microscopic, magnetic and spectroscopic methods. The concentration of As and its redox species in the different Fe-minerals were quantified by microprobe analysis and synchrotron X-ray absorption. We developed a conceptual model integrating Fe-mineral transformations and related As (im)mobilization across the redox interfaces. Accordingly, As is first mobilized via the methanogenic dissolution of Fe(III) (oxyhydr)oxide mineral coatings on sand grains when reducing groundwater from the Holocene aquifer intruded into the Pleistocene sands. This stage is followed by the formation of secondary Fe(II)-containing precipitates (mainly Fe- and Mn-bearing carbonates with relatively low As