Mercury and methylmercury cycling in sediments of the mid-Atlantic continental shelf and slope

Abstract

We present a detailed study of the biogeochemical factors controlling mercury (Hg) distribution, methylmercury (MeHg) production, and MeHg efflux in sediments of the mid-Atlantic continental shelf and slope. The mildly reduced surface sediments of the shelf and slope provide ideal conditions for MeHg production. They are sufficiently reduced to support microbial sulfate reduction, but contain very low dissolved sulfide concentrations. The redox zonation of sediments determined the depth distribution of MeHg production, whereas the bioavailability of inorganic Hg for methylation appeared to be the dominant driver of spatial patterns across the shelf and slope. Sediment total Hg concentrations were well predicted by sediment organic matter (SOM) content, with the highest concentrations of Hg and MeHg in the fine-grained organic clays of the slope. However, SOM-normalized Hg concentrations decreased with distance from shore. The changing character of organic matter with distance from shore appeared to affect Hg partitioning and bioavailability for methylation. The percentage of Hg in sediments as MeHg was well predicted by measured methylation rates, but not by demethylation rates. On the basis of measured concentrations in bottom waters and surficial pore waters, the average diffusive efflux of Hg(II) and MeHg from sediments to coastal waters was estimated to be 26 and 0.8 pmol m(-2) d(-1), respectively. Extrapolated globally, the diffusive input of MeHg from shelf and slope sediments is estimated to be 0.01 Mmol per year. As the actual fluxes can be substantially higher than diffusive fluxes, we suggest that shelf and upper slope sediments are a major source of MeHg to the coastal ocean.