Sequestration of Oxyanions of V(V), Mo(VI), and W(VI) Enhanced through Enzymatic Formation of Fungal Manganese Oxides

Abstract

Biogenic Mn oxides (BMOs) have become captivating with regard to elemental sequestration, especially at circumneutral pH conditions. The interaction of BMOs with oxyanions, such as vanadate (V), molybdate (VI), and tungstate (VI), remains uncertain. This study examined the sequestration of V(V), Mo(VI), and W(VI) (up to ~1 mM) by BMOs formed by the Mn(II)-oxidizing fungus, Acremonium strictum KR21-2. When A. strictum KR21-2 was incubated in liquid cultures containing either Mo(VI) or W(VI) with soluble Mn2+, the oxyanions were sequestered in parallel with enzymatic Mn(II) oxidation with the maximum capacities of 8.8 mol% and 28.8 mol% (relative to solid Mn), respectively. More than 200 μM V(V) showed an inhibitory effect on growth and Mn(II) oxidizing ability. Sequestration experiments using preformed primary BMOs that maintained the enzymatic Mn(II) oxidizing activity, with and without exogenous Mn2+, demonstrated the ongoing BMO deposition in the presence of absorbent oxyanions provided a higher sequestration capacity than the preformed BMOs. X-ray diffraction displayed a larger decline of the peak arising from (001) basal reflection of turbostratic birnessite with increasing sequestration capacity. The results presented herein increase our understanding of the role of ongoing BMO formation in sequestration processes for oxyanion species at circumneutral pH conditions.