Sunny Cho

A wintertime investigation of atmospheric deposition of metals and polycyclic aromatic hydrocarbons in the Athabasca Oil Sands Region, Canada

With planned expansion of oil sands facilities, there is interest in being able to characterize the magnitude and extent of deposition of metals and polycyclic aromatic hydrocarbons (PAH) in the Athabasca Oil Sands Region (AOSR) of Alberta. A study was undertaken using a bulk collection system to characterize wintertime atmospheric deposition of selected inorganic and organic contaminants in the AOSR. The study was carried out from January to March 2012 at two sampling sites near (within a 20 km circle of oil sands development) and two sampling sites distant (>45 km) to oil sands development. Triplicate bulk samplers were used to estimate precision of the method at one distant site. Monthly deposition samples were analyzed for 36 metals, ultra-low mercury, and 25 PAHs (including alkylated, and parent PAH). At the two sites located within 20 km of oil sands development, 3-month wintertime integrated deposition for some priority metals, alkylated and parent PAH were higher compared to distant sites. Deposition fluxes of metals and PAH were compared to other available bulk deposition studies worldwide. Median bulk measurement uncertainties of metals and both PAH classes were 26% and within ±15%, respectively suggesting that the bulk sampling method is a potential alternative for obtaining future direct measures of wintertime metals and PAH deposition at locations without access to power in the AOSR.

Characterization of organic composition in snow and surface waters in the Athabasca Oil Sands Region, using ultrahigh resolution Fourier transform mass spectrometry

This study was conducted to characterize the composition of dissolved organic compounds present in snow and surface waters in the Athabasca Oil Sands Region (AOSR) with the goal of identifying whether atmospherically-derived organic compounds present in snow are a significant contributor to the compounds detected in surface waters (i.e., rivers and lakes). We used electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR MS) to characterize the dissolved organic compound compositions of snow and surface water samples. The organic profiles obtained for the snow samples show compositional differences between samples from near-field sites (<5 km from oil sands activities) and those from more distant locations (i.e., far-field sites). There are also significant compositional differences between samples collected in near-field sites and surface water samples in the AOSR. The composition of dissolved organic compounds at the upstream Athabasca River site (i.e., Athabasca River at Athabasca) is found to be different from samples obtained from downstream sites in the vicinity of oil sands operations (i.e., Athabasca River at Fort McMurray and Athabasca River at Firebag confluence). The upstream Athabasca River sites tended to share some compositional similarities with far-field snow deposition, while the downstream Athabasca River sites are more similar to local lakes and tributaries. This contrast likely indicates the relative role of regional snowmelt contributions to the Athabasca River vs inputs from local catchments in the reach downstream of Fort McMurray.

Characterizing the PAHs in surface waters and snow in the Athabasca region: Implications for identifying hydrological pathways of atmospheric deposition

The composition of polycyclic aromatic hydrocarbons present in snow and surface waters in the Athabasca Oil Sands Region (AOSR) was characterized in order to identify major contributors to the organics detected in rivers and lakes in the region. PAH concentrations, measured by three monitoring programs in 2011, were used to compare the PAH compositions of snow and surface waters across the AOSR. The 2011 dataset includes total (dissolved+particulate) concentrations of thirty-four parent and alkylated PAH compounds in 105 snow, 272 river, and 3 lake samples. The concentration of PAHs in rivers varies seasonally, with the highest values observed in July. The timing of increases in PAH concentrations in rivers coincides with the high river discharge during the spring freshet, indicating that this major hydrological event may play an important role in delivering PAHs to rivers. However, the composition of PAHs present in rivers during this period differs from the composition of PAHs present in snow, suggesting that direct runoff and release of PAHs accumulated on snow may not be the major source of PAHs to the Athabasca River and its tributaries. Instead, snowmelt may contribute indirectly to increases in PAHs due to hydrological processes such as erosion of stream channels, remobilization of PAH-containing sediments, increased catchment runoff, and snowmelt-induced groundwater inputs during this dynamic hydrologic period. Better understanding of transformations of PAH profiles during transport along surface and subsurface flow paths in wetland-dominated boreal catchments would improve identification of potential sources and pathways in the region. The compositional differences highlight the challenges in identifying the origins of PAHs in a region with multiple potential natural and anthropogenic sources particularly when the potential transport pathways include air, soil and water.

An enhanced approach for the use of satellite-derived leaf area index values in dry deposition modeling in the Athabasca oil sands region

In the Athabasca oil sands region (AOSR) of Northern Alberta, the dry deposition of sulphur and nitrogen compounds represents a major fraction of total (wet plus dry) deposition due to oil sands emissions. The leaf area index (LAI) is a critical parameter that affects the dry deposition of these gaseous and particulate compounds to the surrounding boreal forest canopy. For this study, LAI values based on Moderate Resolution Imaging Spectroradiometer satellite imagery were obtained and compared to ground-based measurements, and two limitations with the satellite data were identified. The satellite LAI data firstly represents one-sided LAI values that do not account for the enhanced LAI associated with needle leaf geometry, and secondly, underestimates LAI in winter-time northern latitude regions. An approach for adjusting satellite LAI values for different boreal forest cover types, as a function of time of year, was developed to produce more representative LAI values that can be used by air quality sulphur and nitrogen deposition models. The application of the approach increases the AOSR average LAI for January from 0.19 to 1.40, which represents an increase of 637%. Based on the application of the CALMET/CALPUFF model system, this increases the predicted regional average dry deposition of sulphur and nitrogen compounds for January by factors of 1.40 to 1.30, respectively. The corresponding AOSR average LAI for July increased from 2.8 to 4.0, which represents an increase of 43%. This increases the predicted regional average dry deposition of sulphur and nitrogen compounds for July by factors of 1.28 to 1.22, respectively. These findings reinforce the importance of the LAI metric for predicting the dry deposition of sulphur and nitrogen compounds. While satellite data can provide enhanced spatial and temporal resolution, adjustments are identified to overcome associated limitations. This work is considered to have application for other deposition model studies where dry deposition represents a significant fraction of total deposition.