"Trojan Horse" Type Internalization Increases the Bioavailability of Mercury Sulfide Nanoparticles and Methylation after Intracellular Dissolution.

Mercury sulfide nanoparticles (HgS NP ), as natural metal-containing nanoparticles, are the dominant Hg species in anoxic zones. Although the microbial Hg methylation of HgS NP has been previously reported, the importance of this process in Hg methylation has yet to be clarified due to the lack of knowledge on the internalization and transformation of HgS NP . Here, we investigated the internalization and transformation of HgS NP in microbial methylator Geobacter sulfurreducens PCA through total Hg analysis and different Hg species quantification in medium and cytoplasm. We found that the microbial uptake of HgS NP , via a passive diffusion pathway, was significantly higher than that of the Hg 2+ -dissolved organic matter (Hg 2+ -DOM) complex. Internalized HgS NP were dissolved to Hg 2+ in cytoplasm with a maximal dissolution of 41%, suggesting a "Trojan horse" mechanism. The intracellular Hg 2+ from HgS NP exposure at the initial stage (8 h) was higher than that in Hg 2+ -DOM group, which led to higher methylation of HgS NP . Furthermore, no differences in methylmercury (MeHg) production from HgS NP were observed between the hgcAB gene knockout (Δ hgcAB ) and wild-type strains, suggesting that HgS NP methylation may occur through HgcAB-independent pathways. Considering the possibility of a broad range of hgcAB -lacking microbes serving as methylators for HgS NP and the ubiquity of HgS NP in anoxic environments, this study highlights the importance of HgS NP internalization and methylation in MeHg production and demonstrates the necessity of understanding the assimilation and transformation of nutrient and toxic metal nanoparticles in general.