Environmental selenium volatilization is possibly conferred by promiscuous reactions of the sulfur metabolism

Abstract

Selenium deficiency affects many million people worldwide and volatilization of biogenically methylated selenium species to the atmosphere may limit Se entering the food chain. However, there is very little systematic data on volatilization at nanomolar concentrations prevalent in pristine natural environments. Pseudomonas tolaasii cultures efficiently methylated Se at these concentrations. Nearly perfect linear correlations between the spiked Se concentrations and Dimethylselenide, Dimethyldiselenide, Dimethylselenylsulfide and 2-hydroxy-3-(methylselanyl)propanoic acid were observed up to 80 nM. The efficiency of methylation increased linearly with increasing initial Se concentration, arguing that the enzymes involved are not constitutive, but methylation proceeds promiscuously via pathways of S methylation. From the ratio of all methylated Se and S species, one can conclude that between 0.30% and 3.48% of atoms were Se promiscuously methylated at such low concentrations. At concentrations higher than 640 nM (∼50 μg/L) a steep increase in methylation and volatilization was observed, which suggested the induction of specific enzymes. Promiscuous methylation at low environmental concentrations calls into question that view that methylated Se in the atmosphere is a result of a purposeful Se metabolism serving detoxification. Rather, the concentrations of methylated Se in the atmosphere may be “coincidental” i.e., determined by the activity of S cycling microorganisms. Further, a steep increase in methylation efficiency when surpassing a certain threshold concentration (here ∼50 μg/L) calls into question that natural methylation can be estimated from high Se spikes in laboratory systems, yet highlights the possibility of using bacterial methylation as an effective remediation strategy for media higher concentrated in Se.