Eimers, Catherine

Row crop agriculture and associated land use practices including tile drainage and conservation tillage have been cited as a probable cause of re-emerging eutrophication in the lower Great Lakes. In this thesis, I sought to quantify and evaluate the effect of agricultural land cover and land use changes on total phosphorus (TP) and nitrate-nitrogen (NO3-N) concentrations and export in north shore Lake Ontario tributaries. This included (a) a long-term data analyses at 12 large watersheds (47 to 278 km²) using historical land cover and water quality data (1971-2010), and (b) a space-for-time study examining 12 small sub-catchments (< 8 km²) with majority (> 50%) row crop, pasture, or forest cover. Concentrations of TP were greatest in urbanized watersheds and declined particularly during the first decades of the study period, while NO3-N concentrations were greatest and steadily increased in agricultural catchments with increasing row crop cover. The space-for-time approach revealed that TP concentrations were similar across agricultural land uses and that export was most dependent on runoff. Meanwhile, NO3-N concentrations and export were greatest in row crop catchments and were positively related to row crop area. These results suggest that increases in row crop cover and associated agricultural practices including increased nutrient amendments and tile drainage may be responsible for increased NO3-N concentrations and export in northern Lake Ontario tributaries.

Author Keywords: agriculture, Lake Ontario, nitrogen, phosphorus, streams, Water quality

Stormwater ponds (SWPs) are a common feature in new urban developments where they are designed to minimize runoff peaks from impervious surfaces and retain particulate matter. As a consequence, SWPs can be efficient at retaining particle-bound nutrients, but may be less efficient at retaining nutrients that are present primarily in the dissolved form, like nitrogen (N). However, the forms of nutrients (e.g. particulate vs. dissolved) likely differ with hydrologic and seasonal conditions and few studies have examined year-round differences in nutrient forms and concentrations at urban SWPs. In order to contrast total suspended solids (TSS), phosphorus (P) and nitrogen (N) levels between low and high flow conditions, sampling was conducted at an urban SWP in Peterborough, ON between November 2012 and October 2013. Only an increase in TSS levels at the outflow between low and high flow conditions was observed, as well as a decrease in TSS levels at the outflow compared to Inflow 1 under low flow conditions. Nitrate-N (NO3-N) was the dominant form of N entering the pond under all flow conditions, whereas the fraction of total-P (TP) that was particulate increased under high flow conditions. Nevertheless, the dissolved fraction of TP was consistently high in these urban inlets. Only NO3-N was significantly greater in the inflows than outflow and only under low flow conditions. Increases in the proportions of organic-N and ammonium-N

in the outlet suggest that biological processing is important for N retention.

Author Keywords: nitrogen, Ontario, phosphorus, stormwater ponds, total suspended solids

Winter nutrient export from forested catchments is extremely variable from year-to-year and across the landscape of south-central Ontario. Understanding the controls on this variability is critical, as what happens during the winter sets up the timing and nature of the spring snowmelt, the major period of export for water and nutrients from seasonally snow-covered forests. Furthermore, winter processes are especially vulnerable to changes in climate, particularly to shifts in precipitation from snow to rain as air temperatures rise. The objective of this thesis was to assess climatic and topographic controls on variability in stream nutrient export from a series of forested catchments in south-central Ontario. The impacts of climate on the timing and magnitude of winter stream nutrient export, with particular focus on the impact of winter rain-on-snow (ROS) events was investigated through a) analysis of long-term hydrological, chemical and meteorological records and b) high frequency chemical and isotopic measurements of stream and snow samples over two winters. The relationship between topography and variability in stream chemistry among catchments was investigated through a) a series of field and laboratory incubations to measure rates and discern controls on nitrogen mineralization and nitrification and b) analysis of high resolution spatial data to assess relationships between topographic metrics and seasonal stream chemistry. Warmer winters with more ROS events were shown to shift the bulk of nitrate (NO3-N) export earlier in the winter at the expense of spring export; this pattern was not observed in other nutrients [i.e. dissolved organic carbon (DOC), total phosphorus (TP), sulphate (SO4), calcium (Ca)]. Hydrograph separation revealed the majority of ROS flow came from baseflow, but the NO3-N concentrations in rainfall and melting snow were so high that the majority of NO3-N export was due to these two sources. Other nutrient concentrations did not show such a great separation between sources, and thus event export of these nutrients was not as great. Proportionally, catchments with varying topography responded similarly to ROS events, but the absolute magnitude of export varied substantially, due to differences in baseflow NO3-N concentrations. Field and laboratory incubations revealed differences in rates of net NO3-N production between wetland soils and upland soils, suggesting that topographic differences amongst catchments may be responsible for differences in baseflow NO3-N. Spatial analysis of digital elevation models revealed strong relationships between wetland coverage and DOC and dissolved organic nitrogen (DON) concentrations in all seasons, but relationships between topography and NO3-N were often improved by considering only the area within 50 or 100m of the stream channel. This suggests nutrient cycling processes occurring near the stream channel may exert a stronger control over NO3-N stream outflow chemistry. Overall, topography and climate exert strong controls over spatial and temporal variability in stream chemistry at forested catchments; it is important to consider the interaction of these two factors when predicting the effects of future changes in climate or deposition.

Author Keywords: biogeochemistry, forest, nitrate, south-central Ontario, stream chemistry, winter

This thesis focuses on the design of a modelling framework consisting of loose-coupling of a sequence of spatial and process models and procedures necessary to predict future flood events for the years 2030 and 2050 in Tabasco Mexico. Temperature and precipitation data from the Hadley Centers Coupled Model (HadCM3), for those future years were downscaled using the Statistical Downscaling Model (SDSM4.2.9). These data were then used along with a variety of digital spatial data and models (current land use, soil characteristics, surface elevation and rivers) to parameterize the Soil Water Assessment Tool (SWAT) model and predict flows. Flow data were then input into the Hydrological Engineering Centers-River Analysis System (HEC-RAS) model. This model mapped the areas that are expected to be flooded based on the predicted flow values. Results from this modelling sequence generate images of flood extents, which are then ported to an online tool (ADAPT) for display. The results of this thesis indicate that with current prediction of climate change the city of Villahermosa, Tabasco, Mexico, and the surrounding area will experience a substantial amount of flooding. Therefore there is a need for adaptation planning to begin immediately.

Author Keywords: Adaptation Planning, Climate Change, Extreme Weather Events, Flood Planning, Simulation Modelling

Extensive research has gone into measuring changes to the carbon storage capacity of Arctic terrestrial environments as well as large water bodies in order to determine a carbon budget for many regions across the Arctic. Inland Arctic waters such as small lakes and ponds are often excluded from these carbon budgets, however a handful of studies have demonstrated that they can often be significant sources of carbon to the atmosphere. This study investigated the CO2 cycling of tundra ponds in the Daring Lake area, Northwest Territories, Canada (64°52'N, 111°35'W), to determine the role ponds have in the local carbon cycle.

Floating chambers, nondispersive infrared (NDIR) sensors and headspace samples were used to estimate carbon fluxes from four selected local ponds. Multiple environmental, chemical and meteorological parameters were also monitored for the duration of the study, which took place during the snow free season of 2013.

Average CO2 emissions for the two-month growing season ranged from approximately -0.0035 g CO2-C m-2 d-1 to 0.12 g CO2-C m-2 d-1. The losses of CO2 from the water bodies in the Daring Lake area were approximately 2-7% of the CO2 uptake over vegetated terrestrial tundra during the same two-month period.

Results from this study indicated that the production of CO2 in tundra ponds was positively influenced by both increases in air temperature, and the delivery of carbon from their catchments. The relationship found between temperature and carbon emissions suggests that warming Arctic temperatures have the potential to increase carbon emissions from ponds in the future.

The findings in this study did not include ebullition gas emissions nor plant mediated transport, therefore these findings are likely underestimates of the total carbon emissions from water bodies in the Daring Lake area. This study emphasizes the need for more research on inland waters in order to improve our understanding of the total impact these waters may have on the Arctic's atmospheric CO2 concentrations now and in the future.

Author Keywords: Arctic, Arctic Ponds, Carbon dioxide, Carbon Fluxes, Climate Change, NDIR sensor

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