Production and Cycling of Methylated Mercury Species in Arctic Marine Waters

Monomethyl mercury (MMHg), a vertebrate neurotoxin which bioaccumulates through foodwebs, is found in some Arctic marine mammals at levels that may be harmful to northern peoples consuming them as food. Unfortunately, sources of MMHg to polar marine food webs remain unknown, in part due to the complex nature of Hg cycling in polar marine waters. Since 2005, we have been sampling the marine waters of the Canadian Arctic Archipelago from the Canadian Coast Guard research icebreaker CCGS Amundsen. Early results demonstrated that elevated concentrations of both MMHg and dimethyl mercury (DMHg, a toxic, gaseous Hg species) are found in sub-surface Arctic marine waters (89±36 pg L-1 and 73±37 pg L-1, respectively) despite low total Hg (THg) concentrations (290±220 pg L-1), suggesting an internal source of methylated Hg. We tested the hypothesis that methylated Hg species are produced directly in the marine water column using stable-isotope Hg tracers. Seawater samples were amended with 198Hg(II) and incubated for 0, 8, 16 or 24 hours to measure the production of MM198Hg, DM198Hg and gaseous elemental 198Hg(0) (GEM) over time. A second tracer, MM199Hg, was also added to quantify MMHg methylation (formation of DM199Hg), demethylation (loss of MM199Hg) and reduction (formation of 199Hg(0)). Preliminary analysis of the data indicates that Hg(II) is methylated in polar marine waters to form both MMHg (first order rate-constant km1 ~6x10-4 d-1) and DMHg (km2 ~5x10-6 d-1). We also found that DMHg production from MMHg is ~50x faster than with Hg(II) as the substrate. Furthermore, at a small number of sites, we measured methylation rates that were elevated by almost a full order of magnitude compared to the average, suggesting that methylation hotspots may exist in Arctic marine waters. However, during the less productive fall season when the CCGS Amundsen cruises were conducted, demethylation of MMHg generally appears to dominate in the water column and can occur via a number of processes, including photodemethylation in surface waters (kpd = 1x10-3 m2 E-1) and dark/biological demethylation (kdm ~0.3 d-1). Using the measured rate constants of methylation and demethylation in a very simple model, we calculate an equilibrium MMHg concentration of 0.003-0.020 ng L-1, which is lower than the actual concentrations measured, suggesting the presence of external sources of MMHg to the water column or that methylation/demethylation activity exhibit a strong seasonality. We are currently examining factors that potentially control the biogeochemical transformations of Hg in marine polar waters, such as productivity and heterotrophic (microbial) respiration. This research will provide valuable input for global and regional Hg models as well as an understanding of the sources of MMHg to Arctic marine foodwebs, which will in turn help design strategies to minimize exposure risks to Northern peoples relying on Arctic animals for food.