Mohamed L. Merroun

Elemental selenium (Se 0 ) nanomaterials undergo allotropic transition from thermodynamically‐unstable to more stable phases. This process is significantly different when Se 0 nanoparticles (NPs) are produced via physico‐chemical and biological pathways. While the allotropic transition of physico‐chemically synthesized Se 0 is fast (minutes to hours), the biogenic Se 0 takes months to complete. The biopolymer layer covering biogenic Se 0 NPs might be the main factor controlling this retardation, but this still remains an open question. Phylogenetically‐diverse bacteria reduce selenium oxyanions to red amorphous Se 0 allotrope, which has low market value. Then, red Se 0 undergoes allotropic transition to trigonal (metallic grey) allotrope, the end product having important industrial applications (e.g. semiconductors, alloys). Is it not yet clear whether biogenic Se 0 presents any biological function, or it is mainly a detoxification and respiratory by‐product. The better understanding of this transition would benefit the recovery of Se 0 NPs from secondary resources and its targeted utilization with respect to each allotropic stage. This review article presents and critically discusses the main physico‐chemical methods and biosynthetic pathways of Se 0 (bio)mineralization. In addition, the article proposes a conceptual model for the resource recovery potential of trigonal selenium nanomaterials in the context of circular economy.