Multiple lines of existing evidence indicate that natural organic matter (NOM) could protect poorly crystalline Fe(III) (oxyhydr)oxides from Fe(II)-catalyzed mineral transformation. Conversely, we find that nano-sized biochar (nano-BC), a pyrogenic form of NOM, promotes the phase transformation of ferrihydrite (Fh) in nano-BC/Fh heteroaggregates in the presence of aqueous Fe(II) and rice root exudates. The nano-BC/Fh heteroaggregates are composed of a core-shell like structure where the inner-layered nano-BC is more compacted and plays the dominant role in accelerating the phase transformation of Fh relative to that in the outer sphere. The extent of phase transformation is more regulated by the reversible redox reactions between quinone and hydroquinone in nano-BC than the electron transfer via its condensed aromatic structures. Furthermore, the reductive organic acids in root exudates contribute to the mineral transformation of nano-BC/Fh associations by donating electrons to Fe(III) through nano-BC. Our results suggest that heteroaggregates between nano-BC and Fe minerals are subjected to partial dissociation during their co-transport, and the stably attached nano-BC is favorable to the phase transformation of poorly crystalline Fe minerals (e.g., Fh), which might have profound implications on biogeochemical cycles of carbon and Fe in the prevailing redox environments.
Keywords: (hydro)quinone; LMWOAs; electron transfer; mineral transformation; nano-biochar; root exudates.