Description of a Dimethylmercury Automatic Analyzer for the High-Resolution Measurement of Dissolved Gaseous Mercury Species in Surface Ocean Waters.

Our understanding of the significance of dimethylmercury (DMHg) to the mercury (Hg) global ocean biogeochemical cycle is unclear because of the lack of detailed DMHg measurements in the water column. To our knowledge, 30 years of published studies have generated no more than 200 DMHg data points in the ocean surface waters and marine boundary layer (MBL). To improve the precision and reduce the uncertainty in determining DMHg in surface seawater, we developed a simple and robust DMHg automatic analyzer (DAA). This DAA system couples the main sampling and analytic steps, including a continuous flow chamber, with dual Carbotrap preconcentration, a gas chromatographic column, a cold vapor atomic fluorescence spectrometry, and a data logger for signal integration. We compared the operation, performance, and reproducibility between our DAA and the traditional manual analytic method. Its advantages include the ease of operation, the high time resolution and precision (30 min sampling and <5% relative variation), and long-term stability (2 weeks). The DAA can determine DMHg in both the MBL and surface seawater. The estimated detection limits for DMHg with the DAA in the atmosphere and in surface seawater are 10 pg/m3 and 0.2 fM, respectively. The successful DAA field measurement in coastal waters indicates that it can help detect the low DMHg concentration in surface seawater, and the time series DMHg data helped our understanding of the DMHg behavior (sources and sinks) and its flux into the MBL. The comparison of DMHg concentration in various oceans also suggests that the coastal region had the lowest averaged DMHg, up to an order of magnitude lower than other ecosystems.

Formalin-preserved zooplankton are not reliable for historical reconstructions of methylmercury bioaccumulation.

Time-series measurements of methylmercury (MeHg) concentrations in short-lived planktic animals, such as copepods, could allow for an evaluation of mercury (Hg) inputs and transferability to organisms in marine environments. If reliable, MeHg measurements in formalin-preserved marine animals could offer insights into past environmental MeHg levels. In the present study, we examined whether the amount of MeHg changed over time in formalin-preserved copepods for two species, Acartia tonsa, and Temora longicornis. Over a 51 (A. tonsa) and 7 (T. longicornis) week incubation, we found significant changes in MeHg content in both copepods, while the timing of these changes differed between species. Furthermore, we investigated the mechanism behind these temporal changes through a separate incubation experiment of formalin spiked with two levels of organic matter (OM), and stable-isotope-enriched Hg tracers. We found that the methylation of an inorganic 199Hg tracer was significantly higher in OM-enriched solutions in comparison to a control seawater-formalin solution. Our results suggest that formalin-preserved copepods are not fit for studies of past trends due to ongoing and unpredictable abiotic transformations of Hg in chemically preserved animal tissue.