Biogeochemistry

This study was designed to determine the geochemistry and potential toxicity of water draining a large slag pile in Sudbury, Ontario, which runs through a pond complex prior to entering Alice Lake. Slag leaching experiments confirmed slag is a source of sulphate, heavy metals (including Fe, Al, Ni, Co, Cu, Zn, Pb, Cr, Mn) and base cations (Ca, K, Mg, Na). Concentrations of most metals draining through slag in column experiments were similar to metal concentrations measured at the base of the slag pile, although base cations, S and pH were much higher, possibly because of water inputs interacting with the surrounding basic glaciolacustrine landscape. The increase in pH rapidly precipitates metals leading to high accumulation in the surface sediments. Away from the base of the pile, an increase in vegetation cover leads to an increase in DOC and nutrients and transport of metals with strong binding affinities (Cu). Total metal concentration in water and sediment exceed provincial water quality guidelines, particularly near the slag pile, however WHAM7 modeling indicated that the free metal ion concentration in water is very low. Nevertheless, toxicity experiments showed that water with greater concentrations of solutes collected close to the slag pile negatively impacts D. magna suggesting that water draining the slag pile can adversely impact biota in nearby drainage areas.

Author Keywords: geochemistry, heavy metals, leaching, non-ferrous slag, precipitation, toxicity

Phosphorus (P) is an essential macronutrient. In south-central Ontario, foliar P concentrations are low and studies have suggested that P may be limiting forest productivity. Current catchment mass balance estimates however, indicate that P is being retained suggesting that P should not be limiting to tree growth. Phosphorus deposition is measured using bulk deposition collectors, which are continuously open and therefore are subject to contamination by pollen and other biotic material with high P and potassium (K) concentrations and may therefore overestimate net P inputs to forested catchments. Average annual TP and K deposition at three long-term (1984 – 2013) monitoring sites near Dorset, Ontario ranged from 15 to 20 mg·m-2y-1 and 63 to 85 mg·m-2y-1, respectively, and was higher at Paint Lake compared with Plastic Lake and Heney Lake. Phosphorus and K in bulk precipitation were strongly positively correlated, but deposition patterns varied spatially and temporally among the three sites. Total phosphorus and K deposition increased significantly at Plastic Lake and decreased significantly at Paint Lake, but there was no significant trend in TP or K deposition at Heney Lake over the 30 year period. All sites, but especially Paint Lake, exhibited considerable inter-annual variation in TP and K deposition. To quantify the contribution of pollen, which represents an internal source of atmospheric P deposition, Durham pollen collectors during the spring and summer of 2014 were used. The three sites, Paint Lake, Heney Lake, and Plastic Lake had pollen deposition amounts of 5202 grains·cm-2, 7415 grains·cm-2, and 12 250 grains·cm-2, respectively in 2014. Approximately 83% of pollen deposition can be attributed to white pine and red pine that has a concentration of 3 mg·g-1 of P. It was estimated that pollen alone could account for up to one-third of annual bulk P deposition. Extrapolating winter P deposition values to exclude all potential biotic influences (insects, bird feces, leaves), indicates that bulk deposition estimates may double actual net P to forests, which has implications for long-term P availability, especially in harvested sites.

Author Keywords: Atmospheric Deposition, Phosphorus, Pine, Pollen, Potassium, South-Central Ontario

Aquatic consumers frequently face nutritional limitation, caused in part, by imbalances between the nutrients supplied by primary producers and the metabolic demands of the consumers. These nutritional imbalances alter many ecological processes including consumer life-history traits, population dynamics, and food web properties. Given the important ecological role of organismal nutrition, there is a need to have precise and specific indicators of nutritional stress in animals. Despite this need, current methods used to study nutrition are unable to distinguish between different types of nutritional limitation. Here I studied nutritional metabolism in the freshwater zooplankter, Daphnia. A greater understanding of nutritional metabolism would allow for the development of dietary bio-indicators that could improve the study of the nutritional ecology of animal consumers. Specifically, I addressed the question: What affects the biochemical composition of a generalist aquatic consumer? My overall hypothesis was that the quantity and quality of the diet affects the biochemical composition in a nutrient specific manner. To test this hypothesis, I examined various response variables involved in nutrient metabolism such as alkaline phosphatase activity, whole metabolome, and free amino acid composition. For each response variable, I grew Daphnia under various nutritional stressors and determined if responses are nutrient specific or are a general stress response. I found the current method of measuring alkaline phosphatase was not a phosphorus specific indicator, as activity increased in all nutrient stressed treatments. Analyzing the whole metabolome resulted in nutritional stressors being separated in multivariate space, with many identified metabolites being significantly different from nutrient rich Daphnia. Upon further examination the daphnids free amino acids profiles are caused by differences between the supply of amino acids from the algae and the demand within the Daphnia. These differences in supply and demand resulted in the ability to classify the nutritional status of Daphnia with the use of discriminant analysis, a classification multivariate model. In addition to a deeper understanding and advanced knowledge of the physiological changes caused by nutrient limitation, this research has provided strong evidence for the application of nutritional biomarkers/profiles to identified the nutritional status of Daphnia.

Author Keywords: Bio-indictor, Ecological stoichiometry, Metabolism, Nutritional limitation, Nutritional status

Dissolved organic matter (DOM) is a mixture of molecules with dynamic structure and composition that are ubiquitous in aquatic systems. DOM has several important functions in both natural and engineered systems, such as supporting microorganisms, governing the toxicity of metals and other pollutants, and controlling the fate of dissolved carbon. The structure and composition of DOM determine its reactivity, and hence its effectiveness in these ecosystem functions.

While the structure, composition, and reactivity of riverine and marine DOM have been previously investigated, those of allochthonous DOM collected prior to exposure to microbes and sunlight have received scant attention. The following dissertation constitutes the first in-depth study of the structure, composition, and reactivity of allochthonous DOM at its point of origin (i.e. leaf leachates, LLDOM), as detected by measuring its size and optical properties. Concomitantly, novel chemometric methods were developed to interpret size-resolved data obtained using asymmetrical flow field-flow fractionation, including spectral deconvolution and the application of machine learning algorithms such as self-organizing maps to fluorescence data using a dataset of more than 1000 fluorescence excitation-emission matrices.

The size and fluorescence properties of LLDOM are highly distinct. Indeed, LLDOM was correctly classified as one of 13 species/sources with 92.5% accuracy based on its fluorescence composition, and LLDOM was distinguished from riverine DOM sampled from eight different rivers with 98.3% accuracy. Additionally, both fluorescence and size properties were effective conservative tracers of DOC contribution in pH-controlled mixtures of leaf leachates and riverine DOM over two weeks. However, the structure of LLDOM responded differently to pH changes for leaves/needles from different tree species, and for older needles. Structural changes were non-reversible.

Copper-binding strength (log K) differed for the different fluorescent components of DOM in a single allochthonous source by more than an order of magnitude (4.73 compared to 6.11). Biotransformation preferentially removed protein/polyphenol-like fluorescence and altered copper-binding parameters: log K increased from 4.7 to 5.5 for one fluorescent component measured by fluorescence quenching, but decreased from 7.2 to 5.8 for the overall DOM, as measured using voltammetry. The complexing capacity of DOM increased in response to biotransformation for both fluorescent and total DOM. The relationship between fluorescence and size properties was consistent for fresh allochthonous DOM, but differed in aged material.

Since the size and fluorescence properties of LLDOM are strikingly different from those of riverine DOM, deeper investigation into transformative pathways and mixing processes is required to elucidate the contribution of riparian plant species to DOM signatures in rivers.

Author Keywords: Analytical chemistry, Chemometrics, Dissolved organic matter (DOM), Field-flow fractionation, Fluorescence spectroscopy, Parallel factor analysis (PARAFAC)

Despite being an essential nutrient at trace levels, selenium can be devastating to aquatic environments when present in excess. There is no apparent correlation between total aqueous selenium concentrations and observed toxic effects because bioaccumulation varies over several orders of magnitude depending on the chemical species of selenium and the biological species present in the lowest trophic level of the aquatic food chain. Despite being used in toxicity models due to its high bioavailability, free selenomethionine had not been found previously in the environment outside of a biological entity. Here, it is confirmed that selenomethionine is produced during the biological treatment of selenium-contaminated wastewater, and released in the effluent along with other discrete organic selenium species, including selenomethionine oxide.

This identification followed the development of a rigorous preconcentration and cleanup procedure, allowing for the analysis of these organic selenium species in high-ionic strength matrices. A newly optimized anion-exchange chromatographic separation was coupled to inductively-coupled plasma mass spectrometry for the simultaneous quantification of these organic selenium species along with the more ubiquitous selenium oxyanions, selenite and selenate. This separation method was also coupled to electrospray tandem mass spectrometry for structural confirmation of selenomethionine and selenomethionine oxide. High resolution orbitrap mass spectrometry was used to identify another oxidation product of selenomethionine – a cyclic species which was tentatively identified, by coelution, in a selenium-contaminated river water sample. The production and release of selenomethionine, selenomethionine oxide, Se-(methyl) selenocysteine, and methyl selenic acid were observed for various laboratory algal cultures.

Once the presence of free selenomethionine in a water system was confirmed, factors affecting its uptake into algal cultures were examined. The uptake of selenomethionine into Scenedesmus obliquus was noted to be significantly higher under low nitrate conditions, where it was incorporated into selenium-containing proteins more readily than at higher nitrate conditions where other metabolites were produced. With the increasing popularity of biological treatment systems for the remediation of selenium-contaminated waters, these observations, combined with existing knowledge, could be used to make predictions regarding the potential toxicity of selenium in various environmental scenarios.

Author Keywords: bioremediation, electrospray mass spectrometry, inductively-coupled plasma mass spectrometry, selenium, selenoamino acids, selenomethionine

Decomposition of aquatic macrophytes has an important role in defining lake carbon (C) storage and nutrient dynamics. To test how diversity impacts decomposition dynamics and site-quality effects, I first examined whether the decomposition rate of aquatic macrophytes varies with species richness. Generally, I found neutral effects of mixing, with initial stoichiometry of component species driving decomposition rates. Additionally, external lake conditions can also influence decomposition dynamics. Therefore, I assessed how the decomposition rate of a submersed macrophyte varies across a nutrient gradient in nine lakes. I found decomposition rates varied among lakes. Across all lakes, I found Myriophyllum decomposition rates and changes in stoichiometry to be related to both nutrients and water chemistry. During the incubation changes in detrital stoichiometry were related to lake P and decomposition rates. Aquatic plant community composition and stoichiometry could alter decomposition dynamics in moderately nutrient enriched lakes.

Author Keywords: Aquatic Plants, Decomposition, Diversity, Littoral, Macrophytes, Nutrients

The objective of this thesis was to assess current spatial trends and historic trends in the accumulation of trace metals related to the Athabasca Oil Sands Region (AOSR). The AOSR hosts some of the largest industrial developments in Canada, yet relatively little is known about the transport and fate of trace metal emissions from the region – particularly in the relatively remote areas to the east of the AOSR. Lichens are widely used as biomonitors and are employed in this thesis to assess the range of metals deposition within the Clearwater River and Athabasca River Valleys. Lake sediment cores can retain a historical record of the long-range transport and deposition of metals but can also respond to large regional metal emissions sources. This thesis used lake sediment cores to assess temporal trends in metals accumulation in six road accessible lakes in NW Saskatchewan that are likely to be used by local residents. Results show that metal concentrations (V, Co, Cu, Ni, Pb, Zn, Zr and Cd ) in lichen decline exponentially with distance from the AOSR and approach background levels within a few kilometers . Results from lake sediment cores show that there was no evidence that metal concentrations had increased due to industrial activities in the AOSR.

Author Keywords: Air Emissions, Lakes, Lichens, Oil Sands, Saskatchewan, Trace Metals

Improving current understanding of the factors that control soil carbon (C) dynamics in forest ecosystems remains an important topic of research as it plays an integral role in the fertility of forest soils and the global carbon cycle. Invasive earthworms have the potential to alter soil C dynamics, though mechanisms and effects remain poorly understood. To investigate potential effects of invasive earthworms on forest C the forest floor, mineral soil, fine root biomass, litterfall and litter decomposition rates and total soil respiration (TSR) over a full year were measured at two invaded and one uninvaded deciduous forest sites in southern Ontario. The uninvaded site was approximately 300m from one of the invaded sites and a distinct invasion front between the sites was present. Along the invasion front, the biomass of the forest floor was negatively correlated with earthworm abundance and biomass. There was no significant difference between litterfall, litter decomposition and TSR between the invaded and uninvaded sites, but fine root biomass was approximately 30% lower at the invaded site. There was no significant difference in soil C pools between the invaded and uninvaded sites. Despite profound impacts on forest floor soil C pools, earthworm invasion does not significantly increase TSR, most likely because increased heterotrophic respiration associated with earthworms is largely offset by a decrease in autotrophic respiration caused by lower fine root biomass.

Author Keywords: Biological Invasions, Carbon, Earthworms, Forest Ecosystems, Forest Floor, Soil Respiration

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

In 2012, the Rio Tinto aluminum smelter in Kitimat, British Columbia increased sulphur dioxide (SO2) emissions from 27 to 42 tonnes/day. An initial study was conducted to investigate the effect of the increased sulphur (S) deposition on forest soils. A key uncertainty of the initial study was mineral surface area estimations that were applied to critical load calculations. The current study investigates the effect of organic matter (OM) removal techniques on mineral surface area and the ability to predict mineral surface area using pedotransfer functions (PTFs). Mineral surface area was measured on bulk soil samples using BET gas-adsorption. Organic matter was removed from soil samples prior to surface area measurements using a sodium hypochlorite treatment (NaOCl), loss on ignition (LOI) and no treatment. Removal techniques were found to affect surface area measurements; decreasing in the order of LOI> untreated> NaOCl. Particle-size based PTFs developed from other regions were not significantly correlated with measured surface area. A regionally-specific particle-size based function had stronger predictive value of surface area measurements (adjusted R2=0.82). The PTF that best reflected surface area measurements of bulk soil for the Kitimat area used particle-size data as well as kaolinite, the most abundant clay mineral in the region. Surface area values estimated using the particle-size PTF were applied to the PROFILE model to calculate weathering rates. Weathering rates were then input to critical load calculations using steady-state mass balance. These estimates predicted that none of the 24 measured sites are receiving SO2 deposition in exceedance of their critical load.

Author Keywords: acid deposition, critical loads, mineral surface area, mineral weathering, pedotransfer functions, PROFILE