Aherne, Julian

This study examines the atmospheric (synoptic) controls on snowmelt and snow-free season carbon dioxide (CO2) fluxes at Daring Lake, Northwest Territories. Atmospheric circulation patterns were derived from 500 hPa geopotential height and classified using the self-organizing maps artificial neural network. Snowmelt timing was not found to be influenced by atmospheric circulation patterns or large-scale teleconnection indices, but a shift from meridional to zonal atmospheric circulation marked the transition from pre-melt to melt period. Multiple linear regression identified heating degree days and incoming solar radiation as the most important meteorological predictors of melt length; however, the model would have benefitted from additional variables. Analysis of CO2 (net ecosystem exchange, NEE) during the snow-free season highlighted a strong correlation between NEE and temperature anomalies. Like the snowmelt period, no atmospheric circulation patterns were found to significantly influence NEE; however, these findings prompt further questions regarding snowmelt and CO2 fluxes in the Canadian low Arctic.

Author Keywords: atmospheric circulation, carbon fluxes, net ecosystem exchange, self-organizing maps, snowmelt, synoptic patterns

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

Plastic pollution is a growing concern, owing to its durability, ubiquity, and potential health impacts. The overall objective of this study was to assess the abundance and distribution of microplastics within Lake Scugog catchment, Ontario. This was fulfilled through two tasks (i) the development of a microplastic particle budget for the lake catchment, and (ii) the determination of the dry deposition of atmospheric microplastics in Port Perry, Ontario. The total input of microplastics into Lake Scugog (atmospheric deposition and stream inflow) was 2491 x106 mp/day, while the output (lake outflow and sedimentation) was 1761 x106 mp/day, suggesting that 29% of inputs were retained in the lake. The dry deposition of microplastics in Port Perry was 1257 mp/m2/day, which was high when compared to bulk deposition (37 mp/m2/day) in the same area. By quantifying the major pathways of microplastics better management techniques can be implemented.

Author Keywords: Catchment, Dry Deposition, Microplastics, Ontario, Particle Budget, Plastic pollution

The Hudson Bay region is a sensitive environment, where anthropogenic (e.g., dams, diversions, and/or reservoirs) impacts have increased in recent decades, potentially influencing the functioning of the ecosystem. Dissolved organic matter (DOM) entering Hudson Bay comes from both terrestrial (allochthonous) and aquatic (autochthonous) sources. The chemical composition of DOM is important, as it controls carbon biogeochemistry, nutrient cycling, and heat exchange. In rivers, estuaries, and oceans, photochemical processes and microbial degradation play a significant role in the chemical composition of DOM. Yet, our knowledge is scarce into how photochemical and microbial processes effect DOM composition specifically in Arctic aquatic systems making it difficult to predict how the carbon cycle will respond to a changing environment. This Ph.D. thesis addresses: (1) the composition of photochemically altered autochthonous and allochthonous DOM; (2) the photochemical transformations of DOM in surface waters of Hudson Bay; and (3) the microbial transformations of DOM in Hudson Bay surface waters. Using multiple analytical techniques, this work demonstrated that photochemical and microbial effects were different for light absorbing DOM compounds and ionisable DOM analyzed by Fourier transform-ion cyclotron-resonance-mass spectrometry (FT-ICR-MS). Based on FT-ICR-MS analysis, microbial processes had a greater impact on the molecular composition of allochthonous DOM originating from riverine sources and estuary whereas photochemical processes were the dominant mechanism for degradation of autochthonous DOM in Hudson Bay. Photochemical processes significantly decreased colored dissolved organic matter (CDOM) and fluorescence dissolved organic matter (FDOM) loss whereas microbial degradation was minimal in Hudson Bay river, estuary, and coastal waters. The results of this thesis highlight the importance of photochemical and microbial alteration of DOM in Arctic regions, two processes that are expected to be enhanced under climate change conditions.

Author Keywords: Carbon cycle, Field flow fractionation, Microbial transformation, Optical properties, Photochemical degradation

In this study, the influence of N deposition on the vegetation community of semi-natural oak woodlands in Ireland was assessed through national and regional scale analysis of forest plot data. At both scales, Canonical Correspondence Analysis suggested that N deposition was a predictor of community composition, although site-specific soil characteristics were the strongest predictors of the species dataset. Threshold Indicator Taxon Analysis suggested that the vegetation community demonstrated the most change at 13.2 kg N ha-1 yr-1. While this change point falls within the current recommended critical load range for nutrient nitrogen for acidophilous oak dominated woodlands (10 to 15 kg N ha-1 yr-1), it is notable that 23% of species recorded had individual change points below this range, and could potentially be lost from this habitat if deposition increases. The results from this study suggest that, for acidophilous oak woodlands, habitat conservation policies should be unified with N emission reduction policies.

Author Keywords: community composition, critical load, nitrogen depositioin, oak woodland, species richness, Taxon Indicator Threshold Analysis

The efficacy of the diffusive gradients in thin films (DGT) passive samplers to provide accurate measurements of free metal ions and those complexed with dissolved organic matter (DOM) was investigated. DOM controls the diffusive properties of DOM-complexed metal species in natural systems. Knowing the diffusion coeiffiecent (D) for DOM of different molecular weights (MW) and the major environmental variables influencing D is critical in developing the use of DGT passive samplers and understanding labile species. D and MW were determined for natural and standard DOM. No noticeable changes in DOM MW were observed during the diffusion process, suggesting that DOM remains intact following diffusion across the diffusive gel. Data analysis revealed that MW had the greatest influence on D, with a negative relationship between D and MW, except in tidal areas where ionic strength influence on D was significant. This study provides further characterization of the variables influencing D using the DGT technique.

Author Keywords: Diffusion coefficient, Diffusive gradients in thin films, Dissolved organic matter, Flow field-flow fractionation, Principal Component Analysis, UV-Vis Spectroscopy

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

The objective of this thesis was to assess the influence of anthropogenic sulphur (S) and nitrogen (N) deposition, and harvesting on soil acidity and calcium (Ca2+), magnesium (Mg2+), potassium (K+) and N soil pools in plantation forest soils in Ireland. The response to reductions in anthropogenic S deposition was assessed using temporal trends in soil solution chemistry at two long-term monitoring plots--one on a blanket peat, the other on a peaty podzol. At the peat site, there was little evidence of a response to reductions in throughfall non marine sulphate (nmSO₄2-) and acidity; soil water acidity was determined by organic acids. In addition, temporal variation in soil water did not respond to that in throughfall. In the podzol, reductions in anthropogenic S and H+ deposition led to a significant improvement in soil water chemistry at 75 cm; pH increased and total aluminum (Al_tot) concentrations declined. The impact of harvest scenarios on exchangeable Ca2+, Mg2+ and K+ pools was assessed using input-output budgets at 40 sites (30 spruce, 10 pine). Harvest scenarios were stem-only harvest (SOH), stem plus branch harvest (SBH) and stem, branch and needle harvest (whole-tree harvesting; WTH). Average K+ and Mg2+ budgets were positive under these scenarios. However, exchangeable K+ pools were small and due to uncertainty in K+ budgets, could be depleted within one rotation. Average Ca2+ budgets for spruce were balanced under SOH, but negative under SBH and WTH. Nitrogen deposition was high, between 5 and 19 kg N ha-1 yr-1, but was balanced by N removal in SOH. However, N budgets were under SBH and WTH, indicating that these harvesting methods would lead to depletion of soil N over the long-term. Finally, monitoring of N cycling at a spruce plot indicated that N deposition was contributing to large NO₃- leaching, and as such the site was N saturated. However, N cycling did not fit the criteria of the N saturation hypothesis; instead leaching was directly related to N deposition and supported the model of kinetic N saturation.

Author Keywords: acidic deposition, base cations, input-output budgets, Ireland, nitrogen, whole-tree harvesting

Models of partitioning, uptake, and toxicity of neutral organic chemicals in fish

Alena Kathryn Davidson Celsie

A novel dynamic fugacity model is developed that simulates the uptake of chemicals in fish by respiration as applies in aquatic toxicity tests. A physiologically based toxicokinetic model was developed which calculates the time-course of chemical distribution in four tissue compartments in fish, including metabolic biotransformation in the liver. Toxic endpoints are defined by fugacity reaching a 50% mortality value. The model is tested against empirical data for the uptake of pentachloroethane in rainbow trout and from naphthalene and trichlorobenzene in fathead minnows. The model was able to predict bioconcentration and toxicity within a factor of 2 of empirical data. The sensitivity to partition coefficients of computed whole-body concentration was also investigated. In addition to this model development three methods for predicting partition coefficients were evaluated: lipid-fraction, COSMOtherm estimation, and using Abraham parameters. The lipid fraction method produced accurate tissue-water partitioning values consistently for all tissues tested and is recommended for estimating these values. Results also suggest that quantum chemical methods hold promise for predicting the aquatic toxicity of chemicals based only on molecular structure.

Author Keywords: COSMOtherm, fish model, fugacity, Partition coefficient, tissue-water, toxicokinetics

Microfibres, which are threadlike particles < 5 mm, are the most common type of microplastic reported in the environment. However, few studies have focused on their abundance in background natural environments. This study assessed the abundance of microfibres in rainfall samples (from four precipitation monitoring stations) and across three headwater lake catchments that were in remote, undeveloped areas, away from anthropogenic disturbance and anthropogenic emission sources (i.e., sites were background natural environments). Anthropogenic microfibres were observed in all samples using visual identification methods, with Raman spectroscopy confirming the presence of polyester film and synthetic pigments, e.g., indigo and hostasol green. The estimated annual average atmospheric deposition of microfibres was ~28,800 mf m-2. Meteorological variables, e.g., rain, wind direction, and relative humidity were correlated with the abundance of microfibres. The average abundance of microfibres in headwater lake catchments was 24 mf g-1 in moss, 0.70 mf m-3 in surface trawl, 9,690 mf m-3 in subsurface, 910 mf kg-1 in lake sediment and 576 mf kg-1 in lakeshore sediment.

Author Keywords: Atmospheric Deposition, Background Environments, Headwater Lake Catchments, Microfibres, Microplastics, Rainfall