Importance of organic matter lability for monomethylmercury production in sulfate-rich marine sediments

Sediment cores were collected from two shallow sites in the Venice Lagoon, Italy, in order to study the lability of organic matter and the methylation rate of inorganic Hg(II). Measurements were made of concentrations of total Hg and monomethylmercury (MMHg), Hg(II) methylation rates, concentrations of total organic carbon and total nitrogen in the sediments, and dissolved sulfate, sulfide, and alkalinity in sedimentary pore waters. A positive linear relationship was detected between the specific Hg(II) methylation rate constant and the fraction of total Hg comprised of MMHg (%MMHg/Hg), indicating that short-term Hg(II) methylation rate reflects a long-term accumulation of MMHg in sediment. In addition, the %MMHg/Hg and specific Hg(II) methylation rate constant in sediment increased with decreasing ratios of total organic carbon to total nitrogen (C/N), whereas concentrations of dissolved sulfate, sulfide, and alkalinity in pore water remained constant. This result suggests that the Hg(II) methylation rate was affected by lability of organic matter. In particular, surface sediments, which contained large fractions of fresh algal organic material (C/N = 5.8-7.8), showed higher Hg(II) methylation rates than did deeper sediments (C/N > 10). Our results indicate that the C/N ratio can be used as a proxy for the lability of organic matter that influences Hg(II) methylation rate in sulfate-rich marine sediments.