Koprivnjak, Jean-François

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, twenty lake catchments surrounding Iqaluit, Baffin Island, were assessed for trace element concentrations (Al, As, Ba, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sb, Se, THg, V, Zn) in lake water, catchment soil, lake sediment, and moss (Hylocomium splendens). Additionally, the sources of each trace element were determined through the positive matrix factorization (PMF) model and enrichment factors (only in moss). Geogenic trace elements had the highest median concentrations (Fe>Al>Mn) throughout the study media and across the study catchments. Anthropogenic trace elements had the lowest median concentrations (Pb>As>Cd>THg) across the lake catchments, which were generally several orders of magnitude lower compared to geogenic elements. The PMF model identified trace elements associated with geogenic or anthropogenic sources, i.e., THg (47%), Cd (40%), Zn (34%), and Al (27%) were identified as originating from industrial emission sources deposited onto lakes because they accounted for a large proportion within the model.

Author Keywords: Arctic lake catchments, Biomonitoring, Enrichment factors, Positive matrix factorization model, Trace elements, Water chemistry

In situ chlorophyll sensors are beneficial for monitoring of long-term impacts of algal blooms and accessing water quality issues in bodies of water. However, more research is needed to validate their efficacy and understand how environmental conditions can influence sensor measurements. I assessed the performance of an in situ chlorophyll sensor under controlled environmental conditions and used the same sensor to collect vertical phytoplankton patterns in south-central Ontario boreal lakes. The performance of the sensor was assessed by examining the precision of chlorophyll measurements and determining the suitable timing length that would produce precise results. In general, the sensor was relatively insensitive to conditions under lower algal concentrations and the decent of the sensor should be slowed for vertical lake profiling in lakes with higher algal biomass. Most variation resulted from the movement of particle bound algal cells. We described chlorophyll profile characteristics including surface chlorophyll levels and chlorophyll peak depth and width and investigated the relationships of these features with environmental controls. The lakes showed a typical chlorophyll profile of low phytoplankton biomass lakes. Our results showed that dissolved organic carbon was a strong predictor of epilimnetic biomass while light attenuation and dissolved organic carbon were both strong predictors of peak depth. Light attenuation and surface area were small but significant predictors of peak width. We acknowledged that any uncertainties in sensor chlorophyll readings were not an issue in our lakes due to the overall low chlorophyll biomass.

Author Keywords: chlorophyll, chlorophyll fluorescence, in situ profiling, lakes, phytoplankton biomass, water quality 

The following study measured dissolved organic carbon (DOC) and total mercury (THg) concentrations in acid sensitive lakes in the Republic of Ireland. Sixty-eight upland lakes and 48 lowland lakes were sampled for DOC; the upland lakes were additionally sampled for THg. Spatial variability of DOC was explained by regional precipitation and soil organic matter. A subset of lakes was tested for long-term trends and in contrast to reports of rising DOC in European surface waters, changes in DOC were minor. Spatial variability in THg was explained by DOC and organic matter aromaticity. Long-term THg concentrations increased, likely caused by inputs of terrestrial THg. A subset of lakes was sampled for sediment and soil and the results suggested soils drove THg variation in lake water and sediment. Lake water and sediment THg was low and consistent with background regions, while soil THg was relatively high due to high organic content.

Author Keywords: Dissolved Organic Carbon, Lakes, Organic Matter, Soil, Total Mercury, Water

Ionizing organic chemicals are recognized as constituting a large fraction of the organic chemicals of commerce. Many governments internationally are engaged in the time-consuming and expensive task of chemical risk assessment for the protection of human and environmental health. There are standard models that are consistently used to supplement experimental and monitoring data in such assessments of non-ionizing organics by both government regulators and industry stakeholders. No such standard models exist for ionizing organics. Equilibrium distribution models, the foundational equations within multimedia environmental fate models for non-ionizing organics, were developed for the standard series of biphasic systems: air-water, particle-water, air-particle and organic-aqueous phases within living tissue. Multiple chemical species due to the ionization reaction were considered for each system. It was confirmed that, under select conditions, the properties of the neutral parent are sufficient to predict the overall distribution of the organic chemical. Complications due to biotransformation and paucity of identifiable equilibrium distribution data for ionizing organics limited the development of the model for living tissues. However, the equilibrium distributions of ionizing organics within this biotic system were shown to correlate with the abiotic sediment-water system. This suggests that the model developed for particle-water systems should be adaptable to the biotic system as model input and test data become available. Observational data for soil- and sediment- water systems, i.e., particle-water systems, allowed the development of a primarily non-empirical distribution equation for mono-protic acids; this model was almost entirely theoretically derived. The theoretical approach to model development allowed a quantitative assessment of the role of the neutral ion pair, resulting from the complexation of the organic anion with metal cations. To demonstrate the model's potential usefulness in governmental screening risk assessments, it was applied to a broad range of mono-protic organics including drugs and pesticides using standard property estimation software and generic inputs. The order-of-magnitude agreement between prediction and observation typical of the existing models of non-ionizing organics was generally achieved for the chemicals tested. The model was sensitive to the octanol-water partition coefficient of the most populous species. No calibration set was used in the development of any of the models presented.

Author Keywords: bioconcentration, chemical equilibrium, environmental modelling, ionizing organic, sorption

Maximum permitted SO2 emissions from an aluminum smelter in Kitimat, B.C., increased after modernization in 2015. An increase in acidic deposition can potentially acidify forest soils. Monitoring was conducted at two long-term soil monitoring plots at near (7 km) and far (41 km) sites downwind from the smelter. Change in soil properties was assessed between 2015 and 2018: for the near plot, there was significant decrease in pH and exchange acidity; far plot soils exhibited significant decrease of base cations and exchange acidity in the 0–5 cm layer only. The average total SO42- deposition at near and far plots were estimated to be between 8.2–12.1 and 6.7–7.4 kg/ha/yr, respectively. It was concluded no soil acidification was detected. Observed changes were attributed to measured differences in organic matter, likely influenced by sampling difficulty and measurement process discrepancies. Estimated SO42- deposition levels pose no risk to soil base cation depletion.

Author Keywords: acid forest soils, acidic deposition, aluminum smelter, exchangeable base cations, long-term monitoring, minimum detectable change

This thesis was designed to quantify absorbance and fluorescence characteristics of dissolved organic matter (DOM) in North Atlantic, Pacific and Arctic Oceans. DOM was described in water masses of distinct sources and formation pathways as well as in regions where environmental forcings such as deep water upwelling, enhanced biological activity and receipt of freshwater discharge were prevalent. Influence of sea ice on DOM in Beaufort Sea mixed layer (0 to 30 m) seawater was investigated based on sea ice extent as well as freshwater fractions of meteoric (f_mw) and sea ice melt water (f_sim) calculated from oxygen isotope ratio (δ18O). The effect of DOM exposure to simulated solar radiation was also assessed to determine the resilience of fluorescent fractions of DOM to photodegradation. This research aims to further our ability to trace DOM in marine environments and better understand its transformation pathways and predict its fate as part of the oceanic carbon cycle in a changing climate.

Author Keywords: Absorbance, Arctic Ocean, Dissolved organic matter, Fluorescence, Parallel Factor Analysis, Sea Ice

Environmental and seasonal processes are important watershed drivers controlling the amount, composition, and fate of dissolved organic matter (DOM) in aquatic ecosystems. We used ten months of water samples and eight months of bioassay incubations from two

contrasting catchments (agriculture and natural, forested) to assess the effects of seasonal variability on the composition, export, and biodegradability of DOM. As expected, the DOM composition and exports were more allochthonous-like and autochthonous-like in

the forest and agriculture streams, respectively. However, we found no relationship between DOM composition and biodegradability in our study, suggesting that broad environmental factors play a large part in determining bioavailability of DOM. We found that both differences between the catchments and seasonal variability in hydrology and water temperature cause shifts in DOM composition that can affect exports and potentially affect its susceptibility to microbial activity. More research is needed to fully understand the impact of land use and temporal variability on bioavailability and delivery to downstream ecosystems.

Author Keywords: Bioavailable dissolved organic carbon, Biodegradability, Dissolved organic matter, Export, Seasonality, Streams

This study assesses the bioavailable metal (Cu, Ni, Zn, Pb) species in the Athabasca-Mackenzie watersheds using diffusive gradient in thin films (DGT) devices. Metal toxicity is not only based on the concentration of metal in natural waters, but also on the nature of metal species. Four main forms in aquatic systems are: free ion, inorganic species, DOM bound (humic) species and metal colloidal species. The free ion and inorganic species and very small humic species are known as DGT-labile species and, are considered to be more bioavailable to micro-organisms due to the size and thus may be toxic to microorganisms. In this study, DGT devices were applied to (1) monitor the DGT-labile metal species in the lower Athabasca River and the Mackenzie River watershed and (2) assess the DGT-labile metal concentrations on temporal and spatial scales. In the lower Athabasca River, comparison between the DGT results and the Windermere Humic Acid Model (WHAM) calculation indicated good agreements for all metals when the precipitated iron(III) hydroxide was assumed as an active binding surface. No significant variations in labile species were found over 2003-2012 (RAMP database) despite the development of oil sands. In the Mackenzie River, no significant difference in DGT-labile metal concentrations and DOC concentrations was found in yearly basis 2012-2014. Only DOC was lower in August (6.98 and 3.85 ppm, respectively; p< 0.05) due to dilution from heavy rain events. Spatially, DGT-labile Cu and Ni in the downstream Mackenzie River were higher than upstream (1.79 and 0.58 ppb for Cu, 1.68 and 0.77 ppb for Ni, 4.06 and 6.91 ppm for DOC; p < 0.05). Overall the in situ measurements of metals constitute a benchmark for future studies in water quality and be helpful in environmental management in Alberta and the Northwest Territories in Canada.

Author Keywords: Athabasca River, DGT, Mackenzie River, Speciation, Trace Metal, WHAM