Aherne, Julian

Decreasing lake calcium (Ca) concentration, in lakes located in base poor

catchments of the Muskoka River Watershed (MRW) in south-central Ontario, is a well- established acid-rain driven legacy effect threatening the health and integrity of aquatic ecosystems that can be compounded by additional Ca removals through forest harvesting. The objectives of this thesis were to assess patterns and temporal trends in key water chemistry parameters for a set of lakes in forested catchments in the MRW in south- central Ontario, to predict the pre-industrial steady state lake Ca concentration and the potential impact of harvesting on lake Ca levels in lakes located in managed MRW Crown forests, and to assess potential effects of various mitigation strategies in Ca depleted managed forests. Mean lake Ca (mg L-1) in 104 lakes across the MRW have decreased by 30% since the 1980's with the rate of decrease slowing over time. Mean Lake SO4 (mg L-1), and Mg (mg L-1) concentration also decreased significantly with time (37% and 29%, respectively) again with a declining rate of decrease, while mean lake pH and DOC increased significantly between the 1980's and the 1990's (16% and 12%, respectively) but exhibited no significant pattern after that. Principal components and GIS spatial analyses of 75 lakes with data from 2011 or 2012 water seasons suggested that smaller lakes, at higher elevation in smaller catchments with higher runoff and minimally impacted by the influence of roads and agriculture are associated with lower Ca concentrations and thus are the lakes at risk of amplified Ca depletion from forest harvesting. Spatial analyses of harvested catchments indicated that, under the proposed 10 year land forest management cut volumes, 38% of 364 lakes in the MRW will fall below the critical 1 mg L-1 Ca threshold compared with 8% in the absence of future harvesting. With respect to potential mitigation measures, soil pH and foliar Ca were indicated by meta-analysis to be more responsive to lime addition studies while soil base saturation and tree growth appeared more responsive to wood-ash addition. Future research should address the spatial extent of lakes at risk and identify when critical levels will be reached under harvesting regimes. Further investigation into the use of Ca-addition as a tool for managing the cumulative effects of past, present and future stressors is recommended.

Author Keywords: calcium, harvesting, lakes, lime, Muskoka River Watershed, wood-ash

The reliability and performance of four passive sampler membrane coatings specific to nitrogen dioxide (NO2) were evaluated through co-exposure at multiple Ontario Ministry of Environment and Climate Change (OMOECC) active monitoring stations. All four coatings performed relatively similar under a wide range of meteorological conditions, notably showing exposure-specific atmospheric uptake rates. Further, indoor and outdoor atmospheric concentrations of NO2 (a marker of traffic-related air pollution) were evaluated at multiple elementary schools in a high-density traffic region of Toronto, Ontario, using a Triethanolamine based passive sampler membrane coating. Samplers were also co-exposed at OMOECC active monitoring stations to facilitate calibration of exposure-specific atmospheric uptake rates. Indoor NO2 atmospheric concentrations were 40 to 50% lower than outdoor concentrations during the spring−summer and autumn−winter periods, respectively. In large cities such as Toronto (Population 2,700,000), the influence of a single major road on outdoor and indoor NO2 concentrations is predominantly masked by spatially-extensive high-density traffic.

Author Keywords: active sampler, membrane coating type, nitrogen dioxide, passive sampler, Toronto, traffic density

A catchment-based study was carried out at three remote acid sensitive Irish lakes to determine concentrations of Hg and POPs and to investigate the factors governing the partitioning of these pollutants in various environmental matrices. Both Hg and POPs are an environmental concern due to their ability to travel long distances via atmospheric transport and their tendency to accumulate in biota and in various environmental compartments. Concentrations of POPs and Hg measured in this study were relatively low and consistent with concentrations measured at background levels around the world. Mercury concentrations appeared to be influenced by various site characteristics, specifically organic matter. Many of the POPs examined in this study appeared to be present as a result of long-range transport and more specifically; the physico-chemical properties of POPs appeared to dictate their distribution within soils, moss and sediment at each of the study catchments.

(MRC) in central Ontario was carried out to determine the range and spatial distribution of soil Ca weathering rates, and investigate the relationships between lake Ca and soil and catchment attributes. The MRC is acid-sensitive, and has a long history of impacts from industrial emission sources in Ontario and the United States. Small headwater catchments were sampled for soil and landscape attributes (e.g. elevation, slope, catchment area) at 84 sites. Soil Ca weathering rates, estimated with the PROFILE model, were low throughout the region (average: 188 eq/(ha·yr)) compared to global averages, and lower than Ca deposition (average: 292 eq/(ha·yr)). Multiple linear regression models of lake Ca (n= 306) were dominated by landscape variables such as elevation, which suggests that on a regional scale, landscape variables are better predictors of lake Ca than catchment soil variables.

Author Keywords: Calcium, Lakes, Regional assessment, Regression, Soils, Weathering

The emission of acid precursors by large point sources in Western Canada

(such as the Athabasca Oil Sands Region) has prompted studies into the possible impact to downwind aquatic and terrestrial ecosystems. Sensitivity of catchments to acidic deposition was estimated for the total lake population of northern Saskatchewan (n=89,947) using regression kriging. Under the Steady State Water Chemistry model, a range of 12-15% of the total catchment population was predicted to be in exceedance of critical loads under 2006 deposition levels and 6% of catchments were estimated to be very sensitive (pH below 6 and acid neutralizing capacity, alkalinity, calcium below 50 eqL-1). Temporal changes in soil and water chemistry estimated for 18 Alberta and Saskatchewan catchments using the Very Simple Dynamic and PROFILE models showed that changes in soil base saturation and lake acid neutralizing capacity between 1850 and 2100 were slight, declining 0.8% and 0.9% by 2012, respectively.

Author Keywords: acidification, critical loads, exceedance, PROFILE, regression kriging, VSD

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

Microplastics, plastic particles less than 5 mm in diameter, are ubiquitous in the environment. This study estimated the abundance of microplastics (MP) in atmospheric deposition from four background monitoring stations in Muskoka-Haliburton, south-central Ontario, Canada and quantified the fate of microplastics to three background headwater lake catchments in Muskoka-Haliburton. Microplastics were observed across all sample media with polyethylene terephthalate and polyamide being predominant. The average atmospheric deposition of anthropogenic particles was 57 particles/m2/day with a plastic deposition rate of 7 MP/m2/day. Atmospheric deposition represented the highest daily microplastic flux rate to the three headwater lake catchments compared, 1.5 to 4 times greater than the flux rate for the inflow streams suggesting that atmospheric deposition can account for all the inflowing microplastics. A large fraction of the microplastics from atmospheric deposition (41 – 73%) were retained in the terrestrial catchment and there was a high retention of microplastics in each of the study lakes (1.44 – 7.39 million MP/day; 30 – 45%) suggesting that a large fraction of the terrestrial catchment export is retained by the lakes and that lakes are a reservoir for microplastics.

Author Keywords: Atmospheric deposition, Microplastics, Ontario, Plastic pollution, Sinks, Sources

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