Differential accumulation of PAHs, elements, and Pb isotopes by five lichen species from the Athabasca Oil Sands Region in Alberta, Canada.

A 2014 case study investigated the relative accumulation efficiency of polycyclic aromatic hydrocarbons (PAHs), total sulfur (S), total nitrogen (N), major and minor elements and Pb isotopes in five common lichen species at three boreal forest sites in the Athabasca Oil Sands Region (AOSR) in northeastern Alberta, Canada to identify the optimum lichen species for future biomonitoring. Differences in concentrations of PAHs, multiple elements, and Pb isotopes in fruticose (Bryoria furcellata, Cladina mitis, Evernia mesomorpha) and foliose (Hypogymnia physodes and Tuckermannopsis americana) lichens were found along a 100 km distance gradient from the primary oil sands operations. Integration of insights from emission source samples and oil sands mineralogy in consort with aerosol collection indicates incorporation of more fine particulate matter (PM) into foliose than fruticose lichen biomass. Contrasting PAH with element concentrations allowed lichen species specific accumulation patterns to be identified. The ability of lichen species to incorporate different amounts of gas phase (S and N), petrogenic (V, Ni, Mo), clay (low Si/Al and more rare earth elements), and sand (higher Si/Al and Ti) components from the oil sand operations reflects aerosol particle size and lichen physiology differences that translate into differences in PM transport distances and lichen accumulation efficiencies. Based on these findings Hypogymnia physodes is recommended for future PAH biomonitoring and source attribution studies.

Source apportionment of ambient fine and coarse particulate matter at the Fort McKay community site, in the Athabasca Oil Sands Region, Alberta, Canada.

An ambient air particulate matter sampling study was conducted at the Wood Buffalo Environmental Association (WBEA) AMS-1 Fort McKay monitoring station in the Athabasca Oil Sand Region (AOSR) in Alberta, Canada from February 2010 to July 2011. Daily 24h integrated fine (PM2.5) and coarse (PM10-2.5) particulate matter was collected using a sequential dichotomous sampler. Over the duration of the study, 392 valid daily dichotomous PM2.5 and PM10-2.5 sample pairs were collected with concentrations of 6.8±12.9µgm-3 (mean±standard deviation) and 6.9±5.9µgm-3, respectively. A subset of 100 filter pairs was selected for element analysis by energy dispersive X-ray fluorescence and dynamic reaction cell inductively coupled plasma mass spectrometry. Application of the U.S. EPA positive matrix factorization (PMF) receptor model to the study data matrix resolved five PM2.5 sources explaining 96% of the mass including oil sands upgrading (32%), fugitive dust (26%), biomass combustion (25%), long-range Asian transport lead source (9%), and winter road salt (4%). An analysis of historical PM2.5 data at this site shows that the impact of smoke from wildland fires was particularly high during the summer of 2011. PMF resolved six PM10-2.5 sources explaining 99% of the mass including fugitive haul road dust (40%), fugitive oil sand (27%), a mixed source fugitive dust (16%), biomass combustion (12%), mobile source (3%), and a local copper factor (1%). Results support the conclusion of a previous epiphytic lichen biomonitor study that near-field atmospheric deposition in the AOSR is dominated by coarse fraction fugitive dust from bitumen mining and upgrading operations, and suggest that fugitive dust abatement strategies targeting the three major sources of PM10-2.5 (e.g., oil sand mining, haul roads, bulk material stockpiles) would significantly reduce near-field atmospheric deposition gradients in the AOSR and reduce ambient PM concentrations in the Fort McKay community.

Ground-level air pollution changes during a boreal wildland mega-fire.

The 2011 Richardson wildland mega-fire in the Athabasca Oil Sands Region (AOSR) in northern Alberta, Canada had large effects on air quality. At a receptor site in the center of the AOSR ambient PM2.5, O3, NO, NO2, SO2, NH3, HONO, HNO3, NH4+ and NO3- were measured during the April-August 2011 period. Concentrations of NH3, HNO3, NO2, SO2 and O3 were also monitored across the AOSR with passive samplers, providing monthly summer and bi-monthly winter average values in 2010, 2011 and 2012. During the fire, hourly PM2.5 concentrations >450µgm-3 were measured at the AMS 1 receptor site. The 24-h National Ambient Air Quality Standard (NAAQS) of 35µgm-3 and the Canada Wide Standard (CWS) of 30µgm-3 were exceeded on 13days in May and 7days in June. During the fire emission periods, sharp increases in NH3, HONO, HNO3, NH4+, NO3- and total inorganic reactive N concentrations occurred, all closely correlated with the PM2.5 changes. There were large differences in the relative contribution of various N compounds to total inorganic N between the no-fire emission and fire emission periods. While in the absence of fires NO and NO2 dominated, their relative contribution during the fires was ~2 fold smaller, mainly due to increased NH3, NH4+ and NO3-. Concentrations of HONO and HNO3 also greatly increased during the fires, but their contribution to the total inorganic N pool was relatively small. Elevated NH3 and HNO3 concentrations affected large areas of northern Alberta during the Richardson Fire. While NH3 and HNO3 concentrations were not at levels considered toxic to plants, these gases contributed significantly to atmospheric N deposition. Generally, no significant changes in O3 and SO2 concentrations were detected and their ambient concentrations were below levels harmful to human health or sensitive vegetation.

Characterization of PM2.5 and PM10 fugitive dust source profiles in the Athabasca Oil Sands Region.

UNLABELLED: Geological samples were collected from 27 representative locations in the Athabasca Oil Sands Region (AOSR) in Alberta, Canada. These samples were resuspended onto filter substrates for PM2.5 and PM10 size fractions. Samples were analyzed for 229 chemical species, consisting of elements, ions, carbon, and organic compounds. These chemical species are normalized to gravimetric mass to derive individual source profiles. Individual profiles were grouped into six categories typical of those used in emission inventories: paved road dust, unpaved road dust close to and distant from oil sand operations, overburden soil, tailings sands, and forest soils. Consistent with their geological origin, the major components are minerals, organic and elemental carbon, and ions. The sum of five major elements (i.e., Al, Si, K, Ca, and Fe) and their oxidized forms account for 25-40% and 45-82% of particulate matter (PM) mass, respectively. Si is the most abundant element, averaging 17-18% in the Facility (oil sand operations) and 23-27% in the Forest profiles. Organic carbon is the second most abundant species, averaging 9-11% in the Facility and 5-6% in the Forest profiles. Elemental carbon abundance is 2-3 times higher in Facility than Forest profiles. Sulfate abundance is ~7 times higher in the Facility than in the Forest profiles. The ratios of cation/anion and base cation (sum of Na+, Mg2+, K+, and Ca2+)/nitrogen- and sulfur-containing ions (sum of NH4+, NO2-, NO3-, and SO4(2-)) exceed unity, indicating that the soils are basic. Lead (Pb) isotope ratios of facility soils are similar to the AOSR stack and diesel emissions, while those of forest soils have much lower 206Pb/207Pb and 208Pb/207Pb ratios. High-molecular-weight n-alkanes (C25-C40), hopanes, and steranes are more than an order of magnitude more abundant in Facility than Forest profiles. These differences may be useful for separating anthropogenic from natural sources of fugitive dust at receptors. IMPLICATIONS: Several organic compounds typical of combustion emissions and bitumen are enriched relative to forest soils for fugitive dust sources near oil sands operations, consistent with deposition uptake by biomonitors. AOSR dust samples are alkaline, not acidic, indicating that potential acid deposition is neutralized. Chemical abundances are highly variable within emission inventory categories, implying that more specific subcategories can be defined for inventory speciation.

Oil sands development and its impact on atmospheric wet deposition of air pollutants to the Athabasca Oil Sands Region, Alberta, Canada.

Characterization of air pollutant deposition resulting from Athabasca oil sands development is necessary to assess risk to humans and the environment. To investigate this we collected event-based wet deposition during a pilot study in 2010-2012 at the AMS 6 site 30 km from the nearest upgrading facility in Fort McMurray, AB, Canada. Sulfate, nitrate and ammonium deposition was (kg/ha) 1.96, 1.60 and 1.03, respectively. Trace element pollutant deposition ranged from 2 × 10(-5) - 0.79 and exhibited the trend Hg < Se < As < Cd < Pb < Cu < Zn < S. Crustal element deposition ranged from 1.4 × 10(-4) - 0.46 and had the trend: La < Ce < Sr < Mn < Al < Fe < Mg. S, Se and Hg demonstrated highest median enrichment factors (130-2020) suggesting emissions from oil sands development, urban activities and forest fires were deposited. High deposition of the elements Sr, Mn, Fe and Mg which are tracers for soil and crustal dust implies land-clearing, mining and hauling emissions greatly impacted surrounding human settlements and ecosystems.

Factors affecting stomatal uptake of ozone by different canopies and a comparison between dose and exposure.

Measured ozone (O(3)) and carbon dioxide (CO(2)) concentrations and fluxes over five different canopies (mixed coniferous-deciduous forest, deciduous forest, corn, soybean and pasture) in the eastern USA were analyzed to investigate the stomatal uptake of O(3). It was found that the ambient O(3) concentration levels had little effect on stomatal conductance. However, the accumulated stomatal uptake of O(3), upon reaching a threshold value on any given day, appears to reduce the rate of further O(3) uptake substantially. This may explain why the maximum O(3) deposition velocity often appeared in the early morning hours over some forest canopies. Substantially reduced CO(2) fluxes over wet canopies compared to dry canopies suggest that stomata were likely partially or totally blocked by water droplets or films when canopies were wet. By using a big-leaf dry deposition model, measured O(3) fluxes were separated into stomatal and non-stomatal portions. It was estimated that stomatal uptake contributed 55-75% of the total daytime O(3) fluxes and 40-60% of the total daytime plus nighttime fluxes, depending on canopy type. This suggests that about half of the total O(3) flux occurred through the non-stomatal pathway. At three locations (deciduous forest, corn and soybean sites), O(3) concentrations of 30-60 ppb and of 60-85 ppb contributed equally to the accumulated stomatal fluxes, while at the other two locations (mixed coniferous-deciduous forest and pasture sites), concentrations of 30-60 ppb contributed twice as much as those from 60 to 85 ppb.

Cumulative impact of 40 years of industrial sulfur emissions on a forest soil in west-central Alberta (Canada).

The impact of 40 years of sulfur (S) emissions from a sour gas processing plant in Alberta (Canada) on soil development, soil S pools, soil acidification, and stand nutrition at a pine (Pinus contorta x Pinus banksiana) ecosystem was assessed by comparing ecologically analogous areas subjected to different S deposition levels. Sulfur isotope ratios showed that most deposited S was derived from the sour gas processing plant. The soil subjected to the highest S deposition contained 25.9 kmol S ha(-1) (uppermost 60 cm) compared to 12.5 kmol S ha(-1) or less at the analogues receiving low S deposition. The increase in soil S pools was caused by accumulation of organic S in the forest floor and accumulation of inorganic sulfate in the mineral soil. High S inputs resulted in topsoil acidification, depletion of exchangeable soil Ca2+ and Mg2+ pools by 50%, podzolization, and deterioration of N nutrition of the pine trees.