Aquatic sciences

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

This study assesses the ability of a unicellular protist, Euglena gracilis, to remove Cu and Ni from solution in mono- and bi-metallic systems. Living Euglena cells and non-living Euglena biomass were examined for their capacity to sorb metal ions. Adsorption isotherms were used in batch systems to describe the kinetic and equilibrium characteristics of metal removal. In living systems results indicate that the sorption reaction occurs quickly (<30 min) in both Cu (II) and Ni (II) mono-metallic systems and adsorption follows a pseudo-second order kinetics model for both metals. Sorption capacity and intensity was greater for Cu than Ni (p < 0.05) and were described by the Freundlich model. In bi-metallic systems sorption of both metals appears equivalent. In non-living systems sorption occurred quickly (10-30 min) and both Cu and Ni equilibrium uptake increased with a concurrent increase of initial metal concentrations. The pseudo-first-order model was applied to the kinetic data and the Langmuir and Freundlich models effectively described single-metal systems. The biosorption capacity of Cu (II) and) was 3x times greater than that of Ni (II). Sorption of one metal in the presence of relatively high concentrations of the other metal was supressed. Generally, it was found that living Euglena remove Cu and Ni more efficiently than non-living Euglena biomass in both mono- and bi-metallic systems. It is anticipated that this work should contribute to the identification of baseline uptake parameters and capacities for Cu and Ni by Euglena as well as to the increasing amount of research investigating sustainable bioremediation.

Author Keywords: accumulation, biosorption, Cu, Euglena gracilis, kinetics, Ni

Urban and agricultural activities may introduce chemical stressors, including contaminants of emerging concern (CECs) and current use pesticides (CUPs) into riverine systems. The objective of this study was to determine if fish collected from sites in a river show biomarkers of exposure to these classes of contaminants, and if the biomarker patterns vary in fish collected from urbanized and agricultural sites. The watershed selected for this study was the Grand River in southern Ontario, which transitions from areas dominated by agricultural land use in the north to highly urbanized locations in the southern part of the watershed. Rainbow darters (Etheostoma caerluem) and fantail darters (Etheostoma flabellare) were collected from the Grand River in June, 2014 for biomarker analysis from two urbanized sites and three agricultural sites (n=20 per site). Over the same period of time, Polar Organic Chemical Integrative Samplers (POCIS) were deployed for 2 weeks at each site to monitor for the presence of CUPs and CECs. The amounts of the target compounds accumulated on POCIS, determined using LC-MS/MS were used to estimate the time weighted average concentrations of the contaminants at each site. Data on the liver somatic index for darters indicate site-specific differences in this condition factor (p<0.05). Significant differences in the concentrations of thiobarbituric acid reactive substances (TBARS) in gill tissue (p<0.05) indicate differences in oxidative stress in fish collected from the various sites. Measured concentrations of ethoxyresorufin-O-deethylase (EROD) in liver tissue were significantly different between sites (p<0.05), indicating differences in CYP1A metabolic activity. Finally, acetylcholinesterase (AChE) activity in brain tissue was significantly different between fish from rural and urban sites (p<0.05). The analysis of these biomarkers indicates that fish may be experiencing different levels of biological stress related to different land uses. These data may be useful in developing mitigation strategies to reduce impacts on fish and other aquatic organisms in the watershed.

Author Keywords: AChE, Biomarker, Darter, EROD, POCIS, TBARS

Daphnia are keystone consumers in many pelagic ecosystems because of their central role in nutrient cycling. Daphnia are also frequently infected, and the parasites causing these infections may rival their hosts in their ability to regulate ecosystem processes. Therefore, parasitic exploitation of Daphnia may alter nutrient cycling in pelagic systems. This thesis integrates existing knowledge regarding the exploitation of Daphnia magna by 2 endoparasites to predict parasite-induced changes in the nutrient cycling of infected hosts and ecosystems. In chapter 1, I I contextualizing the integration of these themes by reviewing the development of the fields of elemental stoichiometry and parasitology. In chapter 2, we show how the bacterial parasite, Pasteuria ramosa, increased the nitrogen (N) and phosphorus (P) release rates of D. magna fed P-poor diets. We used a mass-balance nutrient release model to show that parasite-induced changes in host nutrient accumulation rates and diet-specific changes in host ingestion rates were responsible for the accelerated nutrient release rates that we observed. In chapter 3, we extended our examination of the nutrient mass balance of infected D. magna to include another parasite, the microsporidian H. tvaerminnensis. We found differences in the effects of these two parasites on host nutrient use as well as support for the hypothesis that parasite-induced changes in Daphnia N release are caused by the effects of infection on Daphnia fecundity. In chapter 4, we examined the relationship between P concentrations and the presence and prevalence of H. tvaerminnensis in rock pools along the Baltic Sea. We found that particulate P concentrations were negatively associated with the prevalence of this parasite, a result that is consistent with the increase in P sequestration of H. tvaerminnensis-infected Daphnia that we observed in chapter 3. I discuss the potential implications of the work presented in chapters 2-4 for other parasite-host systems and ecosystems in chapter 5. Overall, the research presented here suggests that parasite-induced changes in host nutrient use may affect the availability of nutrients in the surrounding environment, and the magnitude of this effect may be linked to parasite-induced reductions in fecundity for many invertebrate hosts.

Author Keywords: consumer, ingestion rates, mass-balance, nutrient-recycling, parasitism, phosphorus

In order to effectively manage recreational fisheries, it is important to understand how the resource is being used. In this thesis, long-term creel census data, collected on Lake Opeongo in Algonquin Provincial Park, Ontario, Canada was used to assess fine-scale angler dynamics within a recreational Lake Trout (Salvelinus namaycush) fishery. The spatial distribution of angler reported catch locations of Lake Trout within the lake, was assessed using an Optimized Hotspot Analysis in ArcGIS. Areas of significant clustering of catch locations were revealed during all time periods and varied in size and location both seasonally and temporally. Cormack-Jolly-Seber models were used to evaluate the probability of individual angling boats persisting in the regional fishery and being detected on Lake Opeongo through time, as well as to examine the effect of angler travel distance and gas prices on participation parameters. Time-varying models revealed that the probability of an angler persisting in the fishery varied, while detection estimates remained stable. Travel distance had a negative effect on both parameters while increased gas prices only had a slight negative effect on detection estimates. Additionally, among Lake Opeongo anglers, angling avidity varied as did lake specific fishing experience. Average CUE was found to be higher among angling parties who visited the lake more often than fishing parties who visited relatively few times.

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