Net Methylation of Mercury in Estuarine Sediment Microcosms Amended with Dissolved, Nanoparticulate, and Microparticulate Mercuric Sulfides

The production of methylmercury (MeHg) by anaerobic microorganisms depends in part on the speciation and bioavailability of inorganic mercury to these organisms. Our previous work with pure cultures of methylating bacteria has demonstrated that the methylation potential of mercury decreased during the aging of mercuric sulfides (from dissolved to nanoparticulate and microcrystalline HgS). The objective of this study was to understand the relationship between mercury sulfide speciation and methylation potential in experiments that more closely simulate the complexity of sediment settings. The study involved sediment slurry microcosms that represented a spectrum of salinities in an estuary and were each amended with different forms of mercuric sulfides: dissolved Hg and sulfide, nanoparticulate HgS (3-4 nm in diameter), and microparticulate HgS (>500 nm). The results indicated that net MeHg production was influenced by both the activity of sulfate-reducing microorganisms (roughly represented by the rate of sulfate loss) and the bioavailability of mercury. In the presence of abundant sulfate and carbon sources (supporting relatively high microbial activity), net MeHg production in the slurries amended with dissolved Hg was greater than in slurries amended with nano-HgS, similar to previous experiments with pure bacterial cultures. In microcosms with minimal microbial activity (indicated by low rates of sulfate loss), the addition of either dissolved Hg or nano-HgS resulted in similar amounts of net MeHg production. For all slurries receiving micro-HgS, MeHg production did not exceed abiotic controls. In slurries amended with dissolved and nano-HgS, mercury was mainly partitioned to bulk-scale mineral particles and colloids, indicating that Hg bioavailability was not simply related to dissolved Hg concentration or speciation. Overall, the results suggest that models for mercury methylation potential in the environment will need to balance the relative contributions of mercury speciation and activity of methylating microorganisms.