Predicting net mercury methylation in sediments using diffusive gradient in thin films measurements

Diffusive gradient in thin film (DGT) sediment probes for methylmercury (MMHg) were successfully deployed for up to 30 h in three mudflat sediments in San Francisco Bay for measuring labile fractions of dissolved MMHg in pore water. Our calculations show that the local DGT-induced depletion of MMHg in sediment pore waters should be fully compensated by the natural in situ MMHg production and its subsequent remobilization from the solid phase. DGT results were interpreted in terms of labile pore water concentration and provide MMHg concentration depth profiles with a centimeter resolution. Average concentrations of DGT-labile MMHg were 2.10 ± 0.29 and 1.64 ± 0.30 ng L(-1) at China Camp and Hamilton Army Airfield sediment pore waters, respectively, while the riverine location at Petaluma showed a distinct peak of 7.1 ng L(-1) near the sediment surface. Using isotope-enriched mercury species, high resolution depth profiles of MMHg net production rates ranging from 0.2 to 9.8 ng g(-1) d(-1) were obtained in parallel sediment cores sampled closely to DGT deployment sites. A positive, linear relationship between MMHg net production rates and labile MMHg concentrations acquired through DGT measurements was found and explained 79% of the variability in the data set. The latter illustrates that mercury methylation, a biogeochemical process, strongly affected the quantity of MMHg accumulated by the DGT device in the sediment and suggests that DGT measurements have the potential to predict net methylation rates.