Xenopoulos, Marguerite A

Phosphorus is the growth-limiting nutrient in freshwater environments. Dissolved organic phosphorus (DOP) refers to phosphorus within dissolved organic matter (DOM). Much of DOP is bioavailable, but it is poorly understood due to its complexity. This thesis explores the export DOP to Lake Erie from its tributaries, by investigating its speciation and concentration seasonally through weekly sampling of two tributaries and spatially across a river to lake transect. The rivermouth was a site of rapid transition, with lower concentrations of DOP in the lake than in the river and a greater proportion of P as DOP in the lake. Phosphomonoesters and aromatic DOM were coupled in the medium-sized Grand River, but not in the Upper Great Lakes-influenced Detroit River. Phosphodiesters and highly processed DOM were coupled in the Detroit River, but only during periods of low terrestrial inputs. Finally, we found that DOP is a large contributor to tributary phosphorus exports.

Author Keywords: dissolved organic matter, dissolved organic phosphorus, enzymatic hydrolysis, Lake Erie, nutrient export, rivermouth

In this study, we attempt to enhance current knowledge of ecological responses to riverine alterations from waterpower by using a bottom-up food up approach. A series of extensive and intensive study components were performed across northern Ontario, Canada, where biological (nutrients, dissolved organic matter (DOM) and periphyton) and physical (water level and thermal regimes) ecological indicators were examined in regards to alterations from dams and waterpower facilities. Overall, we found that the water levels and thermal regimes deviated from their reference condition at sites below the dams, whereas the biological indicators were more resilient to river alterations. Our results suggest that the characteristics of the watershed were influential in controlling the variability of nutrients and DOM resources in rivers within the boreal watersheds of northern Ontario, as well as the for the downstream recovery patterns of the physical indicators. The recovery of the periphyton communities downstream of the dams were also predicted to be cumulatively related to the physical alterations, nutrient availability and the possible displacement of invertebrate communities. Therefore, our bottom-up food web approach was not effective for better understanding how ecological responses from waterpower cascade through aquatic food webs, and instead multiple indicators should be used for examining the ecological responses in these particular river systems.

Author Keywords: dissolved organic matter, ecological indicators, river alteration, waterpower facilities

Understanding the complex genomic architecture underlying quantitative traits can provide valuable insight for the conservation and management of wildlife. Despite improvements in sequencing technologies, few empirical studies have identified quantitative trait loci (QTL) via whole genome sequencing in free-ranging mammal populations outside a few well-studied systems. This thesis uses high-depth whole genome pooled re-sequencing to characterize the molecular basis of the natural variation observed in two sexually selected, heritable traits in white-tailed deer (Odocoileus virginianus, WTD). Specifically, sampled individuals representing the phenotypic extremes from an island population of WTD for antler and body size traits. Our results showed a largely homogenous genome between extreme phenotypes for each trait, with many highly differentiated regions throughout the genome, indicative of a quantitative model for polygenic traits. We identified and validated several potential QTL of putatively small-to-moderate effect for each trait, and discuss the potential for real-world application to conservation and management.

Author Keywords: evolution, extreme phenotypes, genetics, genomics, quantitative traits, sexual selection

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

Increases in flooding due to anthropogenic influences such as climate change and reservoir creation will undoubtedly impact aquatic ecosystems, affecting physical, chemical, and biological processes. We used two approaches to study these impacts: a whole-ecosystem reservoir flooding experiment and a systematic literature review. In the whole-ecosystem experiment, we analyzed the impact of flooding on nutrient release from stored organic matter in an upland forest. We found that flooded organic matter produced N (nitrogen) and P (phosphorus), but that more N was released relative to P, increasing the N:P ratio over time. In the systematic literature review, we linked small (<10 year recurrence interval) and extreme (>100 year recurrence interval) floods to changes in 10 aquatic ecosystem services. Generally, extreme floods negatively impacted aquatic ecosystem service provisioning, while small floods contributed positively. Overall, we found that flood impacts vary depending on ecosystem properties (organic matter content) and flood characteristics (magnitude).

Author Keywords: ecosystem services, flooding, nutrients, reservoirs, rivers

The potential release of nanoparticles into aquatic environments is raising global concerns. As antimicrobials, silver nanoparticles (AgNPs) are among the most prominent form in use. Despite this, their fate, long-term toxicity, and ecological relevance have yet to be investigated largely under natural settings with seasonality and environmental complexity. To better understand the environmental significance, we released AgNPs into Lake 222 at the Experimental Lakes Area over two years. AgNPs remained suspended in the water column and were detected throughout the lake and in the lower food web. Total Ag concentrations ranged from below 0.07 to 18.9 μg L-1 in lake water, and were highly dynamic seasonally both in the epilimnion and hypolimnion depending on the physical, chemical and biological conditions of the lake. Approximately 60% of the measured Ag mass in October was present in the sediment in 2014 and 50% in 2015 demonstrating relatively high sedimentation and removal from the water column. During winter months, Ag was largely absent in the water column under the ice. After ice melt and before summer stratification, Ag concentrations increased in the lake suggesting AgNPs may not be tightly bound to the sediment and are able re-enter the water column during spring mixing events. Despite temporal variation, total Ag was highly synchronous across spatial locations for both years, indicating rapid dispersal upon lake entry. When investigating AgNP sizes using spICPMS, size distributions were similar across spatial locations, with the 40-60 nm size class constituting approximately 60% of all particles identified. Large aggregates (>100 nm) and dissolved Ag were infrequently detected within the lake. Ag accumulated in the lower food web ranging from 0.27-16.82 μg Ag mg C-1 in the bacterioplankton and 0.17-6.45 μg Ag mg C-1 in algae (particulate fraction). Partial least squares models revealed the highest predictors of Ag accumulation were dissolved nutrients including DOC, TDN, TDP in bacterioplankton. Major predictors for particulate Ag included temperature, dissolved oxygen, and sampling date. The diversity of predictors among biological compartments emphasizes the importance of understanding the role of environmental complexity within the lower food web. Despite Ag accumulation we did not detect strong negative effects on the lake food web. An increase in particulate and bacterioplankton chlorophyll-a occurred after addition in contrast to reference lakes, which may indicate a hormetic response to low dose AgNP concentrations. Our findings provide the first whole-lake perspective regarding Ag fate and toxicity, suggesting small scale experiments may overestimate environmental

responses.

Author Keywords: Ecotoxicity, Fate, Lower food web, Silver Nanoparticles, Whole-lake addition

The increasing production and use of silver nanoparticles (AgNPs) raise concerns on environmental exposure and impact. A large scale in situ enclosure study was conducted at the Experimental Lakes Area to determine the effect of AgNPs on natural phytoplankton and zooplankton communities. This study investigated AgNPs of varying concentrations (4, 16 and 64 μg/L), dosing regimens (chronic vs. pulse), and capping agents (poly-vinyl pyrrolidone vs. citrate). Phytoplankton communities were influenced only by the natural limnological properties of the system signifying tolerance to AgNPs. Zooplankton community structure significantly changed with AgNP concentration and dosing regimen indicating AgNP sensitivity. A microcosm study investigating the effect of AgNPs and phosphorus-dosed periphyton before and after grazing by two benthic invertebrate species (snails and caddisfly larvae) showed reduced periphyton stoichiometry with AgNP exposure. Grazers foraged less on silver dosed periphyton indicating a preferential choice in food quality. Phosphorus reduced the detrimental effects of AgNPs across all conditions. These studies verify the need for in situ experimental designs to fully investigate the effects of AgNPs and their interaction with environmental factors, multiple species assemblages, and across trophic levels.

Author Keywords: benthic invertebrate, Experimental Lakes Area, periphyton, phytoplankton, silver nanoparticles, zooplankton

This thesis examines how dissolved organic matter quantity and quality and nutrients influence the flux potential of greenhouse gases (GHG) from sediments collected from streams across southern Ontario as well as Lake Erie. Sediments were collected and incubated in a laboratory setting where headspace gases and interstitial waters were analyzed. Results demonstrated that nutrients (dissolved organic carbon (DOC), total dissolved phosphorous (TDP) and total dissolved nitrogen (TDN)) were commonly significant predictors of CO2, CH4, and N2O fluxes, but spatial discrepancies were observed for the significance of DOM quality and sedimentary characteristics. Land use was not found to be directly related to gas flux potential. Different relationships were observed between the streams and lake, and between the basins of Lake Erie. Overall, results from this study suggest that sediments from freshwater systems have the potential to be sources of GHG, the degree of which depends on nutrient concentrations and DOM structure from watershed inputs.

Author Keywords: dissolved organic matter, greenhouse gases, Lake Erie, nutrients, sediment, streams