Bacterial Metabolites and Particle Size Determine Cerium Oxide Nanomaterial Biotransformation

Soil is a major receptor of manufactured nanomaterials (NMs) following unintentional releases or intentional uses. Ceria NMs have been shown to undergo biotransformation in plant and soil organisms with a partial Ce(IV) reduction into Ce(III), but the influence of environmentally widespread soil bacteria is poorly understood. We used high-energy resolution fluorescence-detected X-ray absorption spectroscopy (HERFD-XAS) with an unprecedented detection limit to assess Ce speciation in a model soil bacterium (Pseudomonas brassicacearum) exposed to CeO₂ NMs of different sizes and shapes. The findings revealed that the CeO₂ NM's size drives the biotransformation process. No biotransformation was observed for the 31 nm CeO₂ NMs, contrary to 7 and 4 nm CeO₂ NMs, with a Ce reduction of 64 ± 14% and 70 ± 15%, respectively. This major reduction appeared quickly, from the early exponential bacterial growth phase. Environmentally relevant organic acid metabolites secreted by Pseudomonas, especially in the rhizosphere, were investigated. The 2-keto-gluconic and citric acid metabolites alone were able to induce a significant reduction in 4 nm CeO₂ NMs. The high biotransformation measured for <7 nm NMs would affect the fate of Ce in the soil and biota.