Coleman Wasik, Jill2015-10-132015-10-132014-07https://hdl.handle.net/11299/174845University of Minnesota Ph.D. dissertation. July 2014. Major: Water Resources Science. Advisor: Daniel Engstrom. 1 computer file (PDF); xv, 140 pages.Elevated mercury deposition resulting from human activities has caused wide-spread mercury contamination of aquatic systems around the world. Peatlands are generally considered to be sinks for mercury deposited to the landscape, but also act as biogeochemical reactors wherein inorganic mercury is transformed into bioaccumulative, organic methylmercury (MeHg). Recent, short-term investigations have demonstrated that sulfate deposition alone can increase MeHg production in, and flux from, peatlands through the stimulation of sulfate-reducing bacteria, a group of known mercury methylators. However, over longer periods of time the interaction between the biogeochemical cycles of mercury and sulfur is complicated by variability in climate, hydrology, and sulfur and mercury deposition rates. These complexities were addressed by experimentally altering sulfate-loading to a 2.5-ha peatland in northern Minnesota over eight years. The peatland was initially divided into control and experimental treatments and sulfate was added to the latter three times each field season in simulated rainfall events. Porewaters were sampled before and after each sulfate addition and peat samples were collected five times from sites located within the raised central bog and along the peatland margins. The lagg margin is generally considered to be the primary site of mercury methylation in peatlands. However, sulfate addition caused more pronounced and persistent increases in MeHg in the central bog sites, relative to the margin sites, demonstrating that sulfate delivery to the central bog can greatly expand the areal extent of mercury methylation in peatlands. MeHg production also responded to sulfate release following severe summer drought. The increase was much higher in experimental-treatment sites than in control sites suggesting that the experimental treatment was "primed" to quickly respond to new sulfate inputs. In early 2006 sulfate addition was halted to the upgradient one-third of the original experimental treatment in order to monitor how MeHg production changed as sulfate deposition declined. Although drought appeared to slow the recovery process by increasing sulfate availability and mobilizing MeHg, three years after sulfate additions ceased MeHg in the recovery treatment was significantly lower than in the experimental treatment. This indicates that MeHg production in peatlands formerly affected by elevated sulfate deposition may return to background conditions and highlights the potential benefits that further controls on atmospheric sulfur emissions may have on MeHg production in peatlands and consequent mercury burdens in aquatic foodwebs. The long-term nature of this study allowed for an in-depth exploration of the effects that hydrologic flucutations on mercury cycling in peatlands and calls attention to the potential negative consequences that changing precipitation patterns and evapotranspirative demands may have on MeHg production in these systems.enatmospheric depositiondroughtmercurymethylmercurypeatlandsulfateThesis or Dissertation