Temporal Changes in Photoreducible Mercury, Photoreduction Rates, and the Role of Dissolved Organic Matter in Freshwater Lakes.

Total photoreducible mercury [Hg(II)RED] and photoreduction rates in the surface waters of four lakes in Kejimkujik National Park, Nova Scotia were measured monthly over a summer. The percent of THg that was photoreducible [%Hg(II)RED] decreased significantly in two of the four lakes from early to late summer: North Cranberry (maximum 42% to minimum 14%) and Big Dam East (maximum 51% to minimum 6%). Hg(II)RED was found to have a linear relationship with THg for all combined site data. THg and Hg(II)RED were found to have positive linear relationships with DOC concentrations (R2 = 0.97; n = 36; p < 0.01 and R2 = 0.75; n = 36; p < 0.01, respectively). A smaller proportion of THg was found to be photoreducible with increasing DOC concentration.

Mercury photoreduction and photooxidation in lakes: Effects of filtration and dissolved organic carbon concentration.

Mercury is a globally distributed, environmental contaminant. Quantifying the retention and loss of mercury is integral for predicting mercury-sensitive ecosystems. There is little information on how dissolved organic carbon (DOC) concentrations and particulates affect mercury photoreaction kinetics in freshwater lakes. To address this knowledge gap, samples were collected from ten lakes in Kejimkujik National Park, Nova Scotia (DOC: 2.6-15.4mg/L). Filtered (0.2µm) and unfiltered samples were analysed for gross photoreduction, gross photooxidation, and net reduction rates of mercury using pseudo first-order curves. Unfiltered samples had higher concentrations (p=0.04) of photoreducible divalent mercury (Hg(II)RED) (mean of 754±253pg/L) than filtered samples (mean of 482±206pg/L); however, gross photoreduction and photooxidation rate constants were not significantly different in filtered or unfiltered samples in early summer. DOC was not significantly related to gross photoreduction rate constants in filtered (R2=0.43; p=0.08) and unfiltered (R2=0.02; p=0.71) samples; DOC was also not significantly related to gross photooxidation rate constants in filtered or unfiltered samples. However, DOC was significantly negatively related with Hg(II)RED in unfiltered (R2=0.53; p=0.04), but not in filtered samples (R2=0.04; p=0.60). These trends indicate that DOC is a factor in determining dissolved mercury photoreduction rates and particles partially control available Hg(II)RED in lake water. This research also demonstrates that within these lakes gross photoreduction and photooxidation processes are close to being in balance. Changes to catchment inputs of particulate matter and DOC may alter mercury retention in these lakes and could partially explain observed increases of mercury accumulation in biota.

Assessing the utility of dissolved organic matter photoreactivity as a predictor of in situ methylmercury concentration.

Methylmercury (MeHg) bioaccumulation is a growing concern in ecosystems worldwide. The absorption of solar radiation by dissolved organic matter (DOM) and other photoreactive ligands can convert MeHg into less toxic forms of mercury through photodemethylation. In this study, spectral changes and photoreactivity of DOM were measured to assess the potential to control photoreactions and predict in situ MeHg concentration. Water samples collected from a series of lakes in southwestern Nova Scotia in June, August, and September were exposed to controlled ultraviolet-A (UV-A) radiation for up to 24hr. Dissolved organic matter photoreactivity, measured as the loss of absorbance at 350nm at constant UV-A irradiation, was positively dependent on the initial DOM concentration in lake waters (r2=0.94). This relationship was consistent over time with both DOM concentration and photoreactivity increasing from summer into fall across lakes. Lake in situ MeHg concentration was positively correlated with DOM concentration and likely catchment transport in June (r=0.77) but not the other sampling months. Despite a consistent seasonal variation in both DOM and Fe, and their respective correlations with MeHg, no discernable seasonal trend in MeHg was observed. However, a 3-year dataset from the 6 study lakes revealed a positive correlation between DOM concentration and both Fe (r=0.91) and MeHg concentrations (r=0.51) suggesting a more dominant landscape mobility control on MeHg. The DOM-MeHg relationships observed in these lakes highlights the need to examine DOM photoreactivity controls on MeHg transport and availability in natural waters particularly given future climate perturbations.

Methylmercury photodemethylation is inhibited in lakes with high dissolved organic matter.

Photodemethylation can be one of the primary processes for loss of neurotoxic methylmercury (MeHg) in freshwater lakes. Few studies have quantified seasonal variations in photodemethylation rate constants as a function of dissolved organic matter (DOM). We conducted 1-week irradiation experiments in two seasons to test for spatial and temporal differences in photodemethylation potential in temperate lake waters. Six study lakes in Kejimkujik National Park, Nova Scotia were sampled in summer and fall to include a range of naturally occurring DOM concentrations (4.4-13.4 and 3.9-16.4 mg C L-1, respectively). A negative linear relationship (R2 = 0.76, p = 0.01) was found between DOM concentration and photodemethylation rate constant across seasons, indicating that DOM is a strong predictor of MeHg photodemethylation independent of seasonal effects. The two highest carbon lakes (BDW and PEB) had significantly higher energy-normalized photodemethylation rate constants in summer compared to fall corresponding with lower DOM concentrations in summer relative to fall. Additionally, there were negative linear relationships between MeHg photodemethylation and DOM photomineralization (R2s = 0.58-0.72) and DOM photobleaching (R2s = 0.83-0.90). This key finding suggests that competition for photons within DOM structures may reduce the potential for MeHg photodemethylation in high carbon waters and that this relationship persists across seasons.