Sunlight Mediated Biogeochemodynamics of Mercury in the Everglades Aquatic Ecosystem: A Case Study

Competition of photochemical reduction of Hg(II) with methylation process may reduce local Hg toxicity in aquatic ecosystems as the produced dissolved gaseous mercury (DGM) can be emitted back to the atmosphere. Diel changes of DGM levels in natural freshwaters driven by sunlight have been observed widely, especially in the large northern lakes. The Florida Everglades aquatic ecosystem is a special wetland ecosystem, which receives rich solar radiation and strong influence of aquatic plants (e.g., cattails and sawgrass) but generally has still water with enriched organic matter. Biogeochemical cycling of Hg in this system has been of special interest because of involvement of both photochemical redox of Hg and solar-driven transport of DGM by the aquatic vegetation. We here report a study of sunlight-mediated biogeochemodynamics of aquatic Hg in a natural area of the Everglades in a cool season (late February and early March) and a warm season (early June). The DGM levels were found to be very low both in the cool season (4.1 +/- 2.2 (1.1-8.6) pg/L, n = 17, T = 20 +/- 2.5 deg C) and in the warm season (3.9 +/- 1.5 (1.4-8.0) pg/L, n = 19, T = 25 +/- 1.8 deg C), exhibiting little seasonal change over the time studied. These values were all much lower than those found in summer season in the northern lakes (20-72 pg/L), in a southern small lake in Cookeville, TN (e.g., 39 pg/L in early Aug.), and in the Everglades ENR (4-33 pg/L). Only moderate to very weak diel trends were observed (e.g., highest daily difference between max and min DGM = 3.7 pg/L). In situ incubations of freshwater samples in sunlight led to moderate increases in DGM production (e.g, from 4.4 to 18 pg/L in 3.4 h), but dark incubations of initially solar-exposed water samples showed significant decreases in DGM (e.g., from 9.8 to 1.2 pg/L in 5 h). Spike of 1000 pg/L Hg(II) led to only moderate increases of DGM (e.g., from 6.7 to 32 in 10 min and to 54 pg/L in 54 min), while little enhancing effect of Fe(III) on photochemical production of DGM was seen, in contrast to the large positive effect of Fe(III) seen in some northern lake waters. These data collectively suggest that oxidation loss of produced DGM could play a significant role in Hg photochemodynamics in the system studied. Yet, in addition to the oxidation, sunlight-driven transport of DGM by the aquatic plants must be considered in order to explain the unusually low DGM levels and related observations. Further study on the driving forces and mechanism for Hg biogeochemodynamics in the ecosystem is highly of interest.