Watershed characteristics and chemical properties govern methyl mercury concentrations within headwater streams of boreal forests in Ontario, Canada.

Methyl mercury (MeHg) concentrations in boreal headwater streams are influenced by complex natural processes and disturbances such as forestry management. Understanding drivers of MeHg within boreal streams in Ontario, Canada, is of particular interest as there are legacy MeHg concerns. However, models accounting for the complexity of underlying processes have not yet been developed. We assessed how catchment characteristics and stream water chemistry influence MeHg concentrations within 19 watersheds of the Dryden - Wabigoon Forest in Ontario, Canada, using a structural equation modelling (SEM) approach. Despite the study area encompassing a large variation of boreal forest watersheds in the Canadian Shield, our SEM had substantial explanatory power across the region (χ251 = 45.37, p-value = 0.70, R2 = 0.75). Nitrate concentrations (p-value <0.001), water temperature (p-value = 0.002), and the latent watershed characteristic (p-value <0.001) had a positive influence on MeHg concentrations once variable interactions were accounted. Due to the inherent strengths of applying an SEM approach, we describe two plausible pathways driving MeHg concentrations: 1) indirect effect of forest-derived nutrients increases in-situ MeHg production in Dryden - Wabigoon Forest streams, and 2) direct supply of MeHg from inundated soils following consistent precipitation and inundation events (i.e., fill, sit, and spill).

Climate and landscape conditions indirectly affect fish mercury levels by altering lake water chemistry and fish size.

Mercury pollution is a global environmental problem that threatens ecosystems, and negatively impacts human health and well-being. Mercury accumulation in fish within freshwater lakes is a complex process that appears to be driven by factors such as individual fish biology and water chemistry at the lake-scale, whereas, climate, and land-use/land-cover conditions within lake catchments can be influential at relatively larger scales. Nevertheless, unravelling the intricate network of pathways that govern how lake-scale and large-scale factors interact to affect mercury levels in fish remains an important scientific challenge. Using structural equation models (SEMs) and multiple long-term databases we identified direct and indirect effects of lake-scale and larger-scale factors on mercury levels in Walleye and Northern Pike - two species that are valued in inland fisheries. At the lake-level, the most parsimonious path models contained direct effects of fish weight, DOC, and pH, as well as an indirect effect of DOC on fish mercury levels via fish weight. Interestingly, lakeshed-, climate-, and full-path models that combine the effects of both lakeshed and climate revealed indirect effects of surrounding landscape conditions and latitude via DOC, pH, and fish weight but no direct effects on fish mercury levels. These results are generally consistent across species and lakes, except for some differences between stratified and non-stratified lakes. Our findings imply that understanding climate and land-use driven alterations of water chemistry and fish biology will be critical to predicting and mitigating fish mercury bioaccumulation in the future.

Impacts of forest harvesting on mercury concentrations and methylmercury production in boreal forest soils and stream sediment.

Methylmercury (MeHg) is the most neurotoxic and bioaccumulative form of mercury (Hg) present in the terrestrial and aquatic food sources of boreal ecosystems, posing potential risks to wildlife and human health. Harvesting impacts on Hg methylation and MeHg concentrations in forest soils and stream sediment are not fully understood. In this study, a field investigation was carried out in 4 harvested and 2 unharvested boreal forest watersheds, before and after harvest, to better understand impacts on Hg methylation and MeHg concentration in soils and stream sediment, including their responses to different forest management practices. Changes in total Hg (THg) and MeHg concentrations, first-order potential rate constants for Hg methylation and MeHg demethylation (Kmeth and Kdemeth) as well as total carbon content and carbon-to-nitrogen ratio post-harvest in upland, wetland and riparian soils and stream sediment were assessed and compared. Increases in MeHg production were minimal in upland, wetland or riparian soils after harvest. Sediment in streams with minor buffer protection (∼3 m), greater fractions (>75%) of harvested watershed area and more road construction had significantly increased THg and MeHg concentrations, %-MeHg, Kmeth and total carbon content post-harvest. From these patterns, we infer that inputs of carbon and inorganic Hg into harvest-impacted stream sediment are likely sourced from the harvested upland areas and stimulate in situ MeHg production in stream sediment. These findings indicate the importance of stream sediment as potential MeHg pools in harvested forest watersheds. The findings also demonstrate that forest management practices aiming to mitigate organic matter and Hg inputs to streams can effectively alleviate harvesting impacts on Hg methylation and MeHg concentrations in stream sediment.