The Influence of Seawater on Fe(II)-Catalyzed Ferrihydrite Transformation and Its Subsequent Consequences for C Dynamics.

Short-range-ordered minerals like ferrihydrite often bind substantial organic carbon (OC), which can be altered if the minerals transform. Such mineral transformations can be catalyzed by aqueous Fe(II) (Fe(II)aq) in redox-dynamic environments like coastal wetlands, which are inundated with seawater during storm surges or tidal events associated with sea-level rise. Yet, it is unknown how seawater salinity will impact Fe(II)-catalyzed ferrihydrite transformation or the fate of bound OC. We reacted ferrihydrite with Fe(II)aq under anoxic conditions in the absence and presence of dissolved organic matter (DOM). We compared treatments with no salts (DI water), NaCl-KCl salts, and artificial seawater mixes (containing Ca and Mg ions) with or without SO42-/HCO3-. Both XRD and Mössbauer showed that NaCl-KCl favored lepidocrocite formation, whereas Ca2+/Mg2+/SO42-/HCO3- ions in seawater overrode the effects of NaCl-KCl and facilitated goethite formation. We found that the highly unsaturated and phenolic compounds (HuPh) of DOM selectively bound to Fe minerals, promoting nanogoethite formation in seawater treatments. Regardless of salt presence, only 5-9% of Fe-bound OC was released during ferrihydrite transformation, enriching HuPh relative to aliphatics in solution. This study offers new insights into the occurrence of (nano)goethite and the role of Fe minerals in OC protection in coastal wetlands.