Effects of Tungsten and Titanium Oxide Nanoparticles on the Diazotrophic Growth and Metals Acquisition by Azotobacter vinelandii under Molybdenum Limiting Condition

The acquisition of essential metals, such as the metal cofactors (molybdenum (Mo) and iron (Fe)) of the nitrogenase, the enzyme responsible for the reduction of dinitrogen (N-2) to ammonium, is critical to N-2 fixing bacteria in soil. The release of metal nanoparticles (MNPs) to the environment could be detrimental to N-2 fixing bacteria by introducing a new source of toxic metals and by interfering with the acquisition of essential metals such as Mo. Since Mo has been reported to limit nonsymbiotic N-2 fixation in many ecosystems from tropical to cold temperate, this question is particularly acute in the context of Mo limitation. Using a combination of microbiology and analytical chemistry techniques, we have evaluated the effect of titanium (Ti) and tungsten (W) oxide nanoparticles on the diazotrophic growth and metals acquisition in pure culture of the ubiquitous N-2 fixing bacterium Azotobacter vinelandii under Mo replete and Mo limiting conditions. We report that under our conditions (<= 10 mg.L-1) TiO2 NPs have no effects on the diazotrophic growth of A. vinelandii while WO3 NPs are highly detrimental to the growth especially under Mo limiting conditions. Our results show that the toxicity of WO3 NPs to A. vinelandii is due to an interference with the catechol-metalophores assisted uptake of Mo.