Importance of hypolimnetic cycling in aging of “new” mercury in a northern temperate lake

Abstract: The aging of “new” mercury (Hg) was investigated in Experimental Lake 658 as part of the Mercury Experiment To Assess Atmospheric Loading In Canada and the United States (METAALICUS). Mercury enriched in 202Hg was added to the epilimnion over a three-year period to simulate direct atmospheric deposition. We evaluated the aging of newly added mercury (HgLake) in the water column using chemical methods and experiments to examine differences in phase partitioning and transport compared to the ambient pool, HgAmb. Aging was sufficiently slow to observe differences in the partitioning characteristics of HgLake and HgAmb. Amended HgLake initially partitioned to a greater extent to epilimnetic particulate matter (log Kd of HgLake =5.08; log Kd of HgAmb =4.9). HgLake was transported rapidly to the hypolimnion by settling particulate matter. Partitioning became more similar after amended Hg was recycled within the hypolimnion through redox processes. Experiments showed the removal of Hg from the aqueous phase by Fe and/or Mn oxyhydroxide–organic matter complexes. Separations using the anion exchange resin DEAE indicated that both HgLake and HgAmb were associated mainly with dissolved organic matter (DOM) and with partial association with sulfide in anoxic waters, but the degree of association of HgLake with DOM was higher in oxic (epilimnetic) waters. In the solid phase, chemical fractionation indicated greater association of HgLake with organic matter, while HgAmb showed greater association with oxyhydroxide and inert phases. Overall, the results suggest that “new” Hg added from the atmosphere is initially more particle-reactive than ambient Hg in the epilimnion, where initial sorption/partitioning occurs mainly to plankton and detrital particles. Once Hg has been deposited at the sediment–water interface, extended equilibration time in combination with microbial and chemical redox processes “age” the “new” Hg, and particle partitioning becomes similar for the added isotope and ambient pools. [Copyright &y& Elsevier]