Eimers, Catherine

Thawing permafrost due to increasingly warm temperatures in northern subarctic regions is releasing mercury. The consequent formation of thaw ponds in the peatland palsa valley of the Sasapimakwananisikw (SAS) river in Whapmagoostui-Kuujjuarapik, Québec may provide a pool for MMHg formation and a potential risk to aquatic and human life, if these ponds facilitate MMHg export through hydrological connections to nearby waterways. Hg methylation and MMHg demethylation activities were examined in thaw pond sediments using a Hg tracer isotope incubation experiment. Analysis by coupling gas chromatography cold-vapor atomic fluorescence spectrophotometry (GC-CVAFS) with inductively coupled mass spectrometry (ICP-MS) techniques showed that MMHg was produced at a higher rate and within the first 2 h of incubation for both summer and winter seasons. For thaw ponds SAS1A, SAS1B and SAS2A, MMHg was formed at 0.0048 % h-1, 0.0012 % h-1, and 0.0008 % h-1, respectively during winter and at 0.0001 % h-1, 0.0016 % h-1, and 0.0010 % h-1, respectively during summer. Detection of MMHg losses were not as expected likely due to limitations of the combined tracer spike and overestimation of the in situ ambient mercury levels. Physical and chemical properties vary within ponds, among ponds and between winter and summer. SAS1B's location nearby an organic carbon rich palsa may be ideal to study DOC – Hg interactions. Variability in pond characteristics including depth, surface area, age, pH, temperature, colour, oxygen concentration, total dissolved and suspended solids, conductivity, carbon, mercury, ammonium, calcium, magnesium, sulfate, total phosphorous, potassium, and sodium between seasons indicate the challenge of predicting future environmental impacts of climate change related thaw pond creation in the north.

Author Keywords: demethylation, mercury, methylation, methylmercury, SAS, thaw ponds

Decades of acidic deposition have depleted base cation pools in soil over large parts of eastern north America, including the Muskoka-Haliburton region of central Ontario. This region has also experienced a shift in forest species composition over the past 200 years, favouring sugar maple (Acer saccharum Marsh.) at the expense of species such as white pine (Pinus strobus L.) and eastern hemlock (Tsuga canadensis (L.) Carr.). This shift in species composition may have changed soil chemistry over time due to differences in nutrient and metal inputs in litterfall. An analysis of litterfall and soil chemistry was conducted for five tree species commonly found across central Ontario. Stands were established in the Haliburton Forest & Wild Life Reserve and were dominated by one of balsam fir (Abies balsamea (L.) Mill.), eastern hemlock, white pine, sugar maple, or yellow birch (Betula alleghaniensis Britt.). Analysis of mineral soil oxides suggested that these stands were established on similar parent material. Deciduous dominated stands (maple and birch) had greater litterfall mass compared with conifer stands (fir, hemlock, and pine), generally leading to greater macronutrient inputs to the soil. Elemental cycling through the organic horizons was more rapid in deciduous stands, with base cations having the shortest residence times. This suggests that a change from greater conifer dominance to mixed hardwood forests may lead to more rapid elemental cycling and alter the distribution of elements in soil. Forests in the region are typically mixed and the resulting differences in soil chemistry may influence model predictions of soil recovery from acidification. Laboratory leaching tests indicated that both stand type and the acidity of simulated rainwater inputs influenced soil solution chemistry, with deciduous stands generally having a greater buffering capacity than sites dominated by coniferous species. Changes in soil chemistry were examined for each stand type using the Very Simple Dynamic (VSD) biogeochemical model. Simulations showed that soil base saturation began to increase following lows reached around the year 2000, and similar patterns were observed for all stands. When sulphur (S) and nitrogen (N) deposition were held constant at present rates, soil base saturation recovery (toward pre-1900 levels) was marginal by 2100. With additional deposition reductions, further increases in base saturation were minor at all sites. In conjunction with additional deposition reductions, the elimination of future forest harvesting allowed for the greatest potential for recovery in all stands. Overall, these results suggest that changes in forest cover may influence soil chemistry over time, most notably in the organic soil horizons. However, forecasted recovery from acidification is expected to follow similar patterns among stands, since differences in soil chemistry were less significant in the mineral soil horizons which compose a greater proportion of the soil profile.

Author Keywords: base cation decline, forest harvesting, litterfall, mineral weathering, soil acidification, VSD model

Lake of the Woods (LOW) is a large international waterbody which suffers from frequent and widespread algae blooms. Previous studies have highlighted the importance of the lake's largest tributary, the Rainy River (RR) and its significance in total phosphorus (TP) delivery to the LOW. Unfortunately, little is known about TP contributions from the RR and its tributaries within the Canadian portion of the watershed. This thesis examines patterns and sources of TP from four tributaries on the Canadian side of the lower RR region, two of which are predominantly natural, and two that are predominantly agricultural. Relationships between water quality parameters, land use and geologic characteristics were observed over a complete hydrologic year (Oct 1, 2018 - Sept 31, 2019), and through an intensive sampling campaign using a nested watershed approach during the spring high flow and summer low flow periods. Results revealed that TP and total suspended sediment (TSS) concentrations (>100 µg/L and >20 mg/L respectively), and loads (>20 kg/km2 and >3500 kg/km2, respectively), were greater at agricultural sites compared with natural sites (<65 µg/L TP and <15 mg/L TSS concentration, and <20 kg/km2 TP and <4000 kg/km2 TSS export). Total P, TSS, Fe, and Al were significantly positively correlated (R2= 0.26-0.59; p<0.05) and intensive sampling revealed that these relationships were strongest during the spring and at the agricultural sites (R2= 0.73-0.98; p<0.05). In contrast, the summer intensive sampling revealed that TP and redox sensitive Fe were significantly correlated (R2= 0.72; p<0.005), whereas redox insensitive Al and TSS were not, suggesting TP may be sourced via redox processes in the summer due to favourable hydrologic conditions. This was observed not only at sites with high wetland influence, but also at sites with more agricultural presence suggesting that redox sourced TP may also originate from mineral stream bed sediment during low flow periods. This research suggested two primary TP sources in the lower RR region: erosion in the spring, and redox processes (internal release) in the summer. It is recommended that intensive monitoring continue in Canada, and further research be conducted to fully understand the significance of internal P release in the tributaries.

Author Keywords: erosion, land use, nutrients, particulates, redox, water quality

This thesis proposes an agro-ecological zoning (AEZ) methodology of southern Ontario for the characterization and mapping of agro-ecological zones during the historical term (1981-2010), and their shifts into the long-term (2041-2070) projected climate period. Agro-ecological zones are homogenous areas with a unique combination of climate, soil, and landscape features that are important for crop growth. Future climate variables were derived from Earth System Models (EMSs) using a high emission climate forcing scenario from the Intergovernmental Panel on Climate Change 5th Assessment Report. The spatiotemporal shifts in agro-ecological zones with projected climate change are analyzed using the changes to the length of growing period (LGP) and crop heat units (CHU), and their manifestation in agro-climatic zones (ACZ). There are significant increases to the LGP and CHU into the long-term future. Two historical ACZs exist in the long-term future, and have decreased in area and shifted northward from their historical locations.

Author Keywords: Agro-climatic Zones, Agro-ecological Zones, Agro-ecological Zoning, Climate Change, Crop Heat Units, Length of Growing Period

Tree harvesting alters nutrient cycling and removes nutrients held in biomass, and as a result nutrient availability may be reduced, particularly in naturally oligotrophic ecosystems. Selection harvesting is a silvicultural technique limited to tolerant hardwood forests where individual or small groups of trees are removed creating a "gap" in the forest canopy. In order for harvesting machinery to gain access to these individual trees, trees are felled to create pathways, known as skid roads. The objective of this study was to characterize differences in soil chemical and physical properties in gaps, skid roads and uncut areas following selection harvesting in central Ontario as well as documenting differences in the understory vegetation community and sugar maple (Acer saccharum) seedlings chemical composition post harvest. First year seedlings were collected for elemental analysis from unharvested areas, canopy gaps, and skid roads in 2014, eight months after harvesting. In 2015, first and second year sugar maple seedlings were collected. Soil bulk density and water infiltration were measured in the three areas of the catchment as well as soil moisture, organic matter content, exchangeable base cations, and net nitrification. Seedlings in the disturbed sites had lower concentrations of Mg, K, P, and N compared with unharvested sites and soil nitrification was significantly lower in the skid roads. Water infiltration rates in the gap and skid roads were slower than the control and concentrations of metals (e.g. Fe, Al, Ca) and litter mass increased in litter bags deployed over 335 days, likely reflecting an increase in soil erosion in the skid roads. Understory vegetation was markedly different amongst sites, particularly the dominance of Carex spp. in the skid roads. The sustainability of industrial logging is dependent on successful tree regeneration, however, increased soil compaction, establishment and growth of grasses and shrubs, as well as low nutrient concentrations in seedlings may ultimately restrict forest succession.

Author Keywords: Canadian Shield, nitrification, selection harvesting, soil compaction, sugar maple seedling, understory vegetation

Stream solutes are strongly linked to hydrology, and as such, we sought to better understand how hydrology, particularly flooding, influences nitrogen (N) and phosphorus (P) levels. We used a long-term dataset of monthly water quality samples for many Ontario, Canada, catchments to assess the effects of landscape variables, such as land use and physiography, on the export of nutrients during floods, and to characterize overall concentration-discharge patterns. In general, we found that landscape variables could partially explain the export variation in flood waters, but that the importance of specific variables depended on flood characteristics. We also found that overall concentration-discharge relationships for N and P C were positive, but non-linear, with greater concentrations on the rising limb of the hydrograph depending on the nutrient. With these results, we have identified general patterns between nutrients and hydrology, which will be helpful for managing the ecological effects of flooding.

Author Keywords: C-Q relationships, Discharge, Export, Flooding, Nutrients, Thresholds

The spatial and temporal variation in atmospheric nitrogen dioxide (NO2), ammonia (NH3), and 17 elements (V, Cr, Fe, Ni, Cu, Zn, As, Cd, Pb, Mg, Al, Ca, Co, Se, Sb, Mn, and Na) were measured at 40 road side locations along a ~250 km traffic density gradient of 40,000–400,000 vehicles on the King's Highway 401, in Ontario, Canada. Elemental concentrations were measured over a year, using moss bags as passive samplers, for four quarterly three-month exposure periods (October 2015 – October 2016). Gaseous NO2 and NH3 concentrations were measured using Willem's badge passive diffusive samplers for twelve one-week exposure periods (one per month: October 2015–October 2016). Dry deposition of nitrogen was estimated using the inferential method. There were significant linear relationships between NO2 and NH3 and average annual daily traffic (AADT) volumes across the study area; higher concentrations corresponded to higher volume traffic sites. Average NO2 concentrations at sites ranged from 23.5 to 73 μg/m3, with an annual average of 43.7 μg/m3. Ammonia ranged from 2.56 to 13.55 μg/m3, with an annual average of 6.44 μg/m3. There were significant quarterly variations in NO2, with concentrations peaking during the winter months. In contrast, NH3 showed no significant quarterly variation, but a slight peak occurred during the summer. Gaseous NO2 and NH3 were highly positively correlated (r = 0.63), suggesting a common emission source from traffic. Concentrations in exposed moss were determined by subtracting the total concentration of each metal in the exposed sample from the background concentration present in the moss. Relative accumulation factors (RAF) and contamination factors were also calculated to determine the anthropogenic influence on tissue concentrations in exposed moss. All metals showed elevated levels versus background concentrations, with all metals except Ni and Co showing considerable enrichment. The highest levels of contamination were from V, Cr, Fe, Zn, Cd, Sb, Pb and Na. Principal component analysis indicated 5 clear clusters of related elements, with PC1 accounting for 36.2% and PC2 accounting for 25.6% of the variance. Average annual daily traffic was significantly related to Cr, Fe, Cu, Sb, Mn, Al, and Na. Road side monitoring shows consistently higher concentrations than active monitoring sites located further from the edge of the road, indicating a need for increased road side monitoring in Ontario, Canada.

A series of experiments was designed to assess the relative efficacy of various dust suppressants to suppress PM10 emissions from nepheline syenite tailings. The experiments were conducted in the Trent University Environmental Wind Tunnel, Peterborough, Ontario, and on the tailings ponds at the Unimin Ltd Nephton mine near Havelock, Ontario. Treated surfaces were subjected to particle-free airflow, abrasion with blown sand particles, particle-free airflow after physical disturbance, and were measured independently using a pin penetrometer. In the particle-free wind tunnel tests, three of the surfaces performed well, and PM10 emissions scaled inversely with crust strength. Light bombardment of each surface by saltating sand grains resulted in PM10 emission rates two orders of magnitude higher. All treated surfaces emitted significantly more PM10 after physical disturbance in both the laboratory and field research. The results suggest that the site conditions, inclusive of the potential for dust advection and resuspension, must be taken into account when considering the use of a commercial dust suppressant.

Author Keywords: dust suppression, field testing, mine tailings, wind tunnel experiment

Timber harvest can influence the rate of transfer of organic matter from the terrestrial catchment to streams, which may have both direct and indirect effects on in-stream nutrient pools and dynamics. In the interest of developing sustainable forestry practices, the continued study of the effects of forestry on nutrient dynamics in aquatic systems is paramount, particularly in sensitive nutrient-poor oligotrophic systems. The goal of this study was to investigate the impacts of harvest-related woody debris on stream nutrient status in streams located in the Canadian Shield region of south-central Ontario. Surveys showed greater large (> 10 cm) and small (< 10 cm) woody debris dry masses and associated nutrient pools in streams located in recently (2013) selectively harvested catchments, when compared with catchments not harvested for at least 20 years. Experimental releases of flagging tape underlined the importance of woody debris as a mechanism of coarse particulate organic matter (CPOM) retention. Sediment surveys showed a significant exponential decline in both OM content and nutrients associated with coarse sediment with distance upstream from debris dams. Laboratory leaching experiments suggest that fresh woody debris may be an important short-term source of water-soluble nutrients, particularly phosphorus and potassium. This study suggests that woody debris from timber harvest is both a direct and indirect source of nutrients, as trapped wood and leaves that accumulate behind debris dams can augment stream nutrient export over long time periods.

Author Keywords: nutrient leaching, nutrient pools, organic matter retention, selection harvest, southern Ontario, woody debris

Soil mineralizable nitrogen (N) is the main component of soil N supply in humid temperate regions and should be considered in N fertilizer recommendations. The objectives of this study were to determine the potentially mineralizable N parameters, and improve N fertilizer recommendations by evaluating a suite of soil N tests in southwestern Ontario. The study was conducted over the 2013 and 2014 growing seasons using 19 field sites across southwestern Ontario. The average potentially mineralizable N (N0) and readily mineralizable N (Pool I) were 147 mg kg-1 and 42 mg kg-1, respectively. Pool I was the only soil N test that successfully predicted RY in 2013. The PPNT and water soluble N (WSN) concentration (0-30cm depth) at planting were the best predictors of fertilizer N requirement when combing data from 2013 and 2014. When soils were categorized based on soil texture, the relationships also improved. Our findings suggest that N fertilizer recommendations for grain corn can be improved, however, further field validations are required.

Author Keywords: corn, nitrogen, nitrogen mineralization, soil nitrogen supply, soil N test, southwestern Ontario