A Fungal-Mediated Cryptic Selenium Cycle Linked to Manganese Biogeochemistry.

Selenium (Se) redox chemistry is a determining factor for its environmental toxicity and mobility. Currently, millions of people are impacted by Se deficiency or toxicity, and in geologic history, several mass extinctions have been linked to extreme Se deficiency. Importantly, microbial activity and interactions with other biogeochemically active elements can drastically alter Se oxidation state and form, impacting its bioavailability. Here, we use wet geochemistry, spectroscopy, and electron microscopy to identify a cryptic, or hidden, Se cycle involving the reoxidation of biogenic volatile Se compounds in the presence of biogenic manganese [Mn(III, IV)] oxides and oxyhydroxides (hereafter referred to as "Mn oxides"). Using two common environmental Ascomycete fungi, Paraconiothyrium sporulosum and Stagonospora sp., we observed that aerobic Se(IV and VI) bioreduction to Se(0) and Se(-II) occurs simultaneously alongside the opposite redox biomineralization process of mycogenic Mn(II) oxidation to Mn oxides. Selenium bioreduction produced stable Se(0) nanoparticles and organoselenium compounds. However, mycogenic Mn oxides rapidly oxidized volatile Se products, recycling these compounds back to soluble forms. Given their abundance in natural systems, biogenic Mn oxides likely play an important role mediating Se biogeochemistry. Elucidating this cryptic Se cycle is essential for understanding and predicting Se behavior in diverse environmental systems.