Oil sands operations as a large source of secondary organic aerosols.

Worldwide heavy oil and bitumen deposits amount to 9 trillion barrels of oil distributed in over 280 basins around the world, with Canada home to oil sands deposits of 1.7 trillion barrels. The global development of this resource and the increase in oil production from oil sands has caused environmental concerns over the presence of toxic compounds in nearby ecosystems and acid deposition. The contribution of oil sands exploration to secondary organic aerosol formation, an important component of atmospheric particulate matter that affects air quality and climate, remains poorly understood. Here we use data from airborne measurements over the Canadian oil sands, laboratory experiments and a box-model study to provide a quantitative assessment of the magnitude of secondary organic aerosol production from oil sands emissions. We find that the evaporation and atmospheric oxidation of low-volatility organic vapours from the mined oil sands material is directly responsible for the majority of the observed secondary organic aerosol mass. The resultant production rates of 45-84 tonnes per day make the oil sands one of the largest sources of anthropogenic secondary organic aerosols in North America. Heavy oil and bitumen account for over ten per cent of global oil production today, and this figure continues to grow. Our findings suggest that the production of the more viscous crude oils could be a large source of secondary organic aerosols in many production and refining regions worldwide, and that such production should be considered when assessing the environmental impacts of current and planned bitumen and heavy oil extraction projects globally.

Direct detection of atmospheric atomic bromine leading to mercury and ozone depletion.

Bromine atoms play a central role in atmospheric reactive halogen chemistry, depleting ozone and elemental mercury, thereby enhancing deposition of toxic mercury, particularly in the Arctic near-surface troposphere. However, direct bromine atom measurements have been missing to date, due to the lack of analytical capability with sufficient sensitivity for ambient measurements. Here we present direct atmospheric bromine atom measurements, conducted in the springtime Arctic. Measured bromine atom levels reached 14 parts per trillion (ppt, pmol mol-1; 4.2 × 108 atoms per cm-3) and were up to 3-10 times higher than estimates using previous indirect measurements not considering the critical role of molecular bromine. Observed ozone and elemental mercury depletion rates are quantitatively explained by the measured bromine atoms, providing field validation of highly uncertain mercury chemistry. Following complete ozone depletion, elevated bromine concentrations are sustained by photochemical snowpack emissions of molecular bromine and nitrogen oxides, resulting in continued atmospheric mercury depletion. This study provides a breakthrough in quantitatively constraining bromine chemistry in the polar atmosphere, where this chemistry connects the rapidly changing surface to pollutant fate.

Fugitive Emissions of Volatile Organic Compounds from a Tailings Pond in the Oil Sands Region of Alberta.

Tailings ponds in the oil sands (OS) region in Alberta, Canada, have been associated with fugitive emissions of volatile organic compounds (VOCs) and other pollutants to the atmosphere. However, the contribution of tailings ponds to the total fugitive emissions of VOCs from OS operations remains uncertain. To address this knowledge gap, a field study was conducted in the summer of 2017 at Suncor's Pond 2/3 to estimate emissions of a suite of pollutants including 68 VOCs using a combination of micrometeorological methods and measurements from a flux tower. The results indicate that in 2017, Pond 2/3 was an emission source of 3322 ± 727 tons of VOCs including alkanes, aromatics, and oxygenated and sulfur-containing organics. While the total VOC emissions were approximately a factor of 2 higher than those reported by Suncor, the individual VOC species emissions varied by up to a factor of 12. A chemical mass balance (CMB) receptor model was used to estimate the contribution of the tailings pond to VOC pollution events in a nearby First Nations and Metis community in Fort McKay. CMB results indicate that Suncor Pond 2/3 contributed up to 57% to the total mass of VOCs measured at Fort McKay, reinforcing the importance of accurate VOC emission estimation methods for tailings ponds.

Improving Insights on Air Pollutant Mixtures and Their Origins by Enhancing Local Monitoring in an Area of Intensive Resource Development.

An "event-based" approach to characterize complex air pollutant mixtures was applied in the Oil Sands region of northern Alberta, Canada. This approach was developed to better-inform source characterization and attribution of the air pollution in the Indigenous community of Fort McKay, within the context of the lived experience of residents. Principal component analysis was used to identify the characteristics of primary pollutant mixtures, which were related to hydrocarbon emissions, fossil fuel combustion, dust, and oxidized and reduced sulfur compounds. Concentration distributions of indicator compounds were used to isolate sustained air pollution "events". Diesel-powered vehicles operating in the mines were found to be an important source during NOx events. Industry-specific volatile organic compound (VOC) profiles were used in a chemical mass balance model for source apportionment, which revealed that nearby oil sands operations contribute to 86% of the total mass of nine VOC species (2-methylpentane, hexane, heptane, octane, benzene, toluene, m,p-xylene, o-xylene, and ethylbenzene) during VOC events. Analyses of the frequency distribution of air pollution events indicate that Fort McKay is regularly impacted by multiple mixtures simultaneously, underscoring the limitations of an exceedance-based approach relying on a small number of air quality standards as the only tool to assess risk.

Convective forcing of mercury and ozone in the Arctic boundary layer induced by leads in sea ice.

The ongoing regime shift of Arctic sea ice from perennial to seasonal ice is associated with more dynamic patterns of opening and closing sea-ice leads (large transient channels of open water in the ice), which may affect atmospheric and biogeochemical cycles in the Arctic. Mercury and ozone are rapidly removed from the atmospheric boundary layer during depletion events in the Arctic, caused by destruction of ozone along with oxidation of gaseous elemental mercury (Hg(0)) to oxidized mercury (Hg(II)) in the atmosphere and its subsequent deposition to snow and ice. Ozone depletion events can change the oxidative capacity of the air by affecting atmospheric hydroxyl radical chemistry, whereas atmospheric mercury depletion events can increase the deposition of mercury to the Arctic, some of which can enter ecosystems during snowmelt. Here we present near-surface measurements of atmospheric mercury and ozone from two Arctic field campaigns near Barrow, Alaska. We find that coastal depletion events are directly linked to sea-ice dynamics. A consolidated ice cover facilitates the depletion of Hg(0) and ozone, but these immediately recover to near-background concentrations in the upwind presence of open sea-ice leads. We attribute the rapid recoveries of Hg(0) and ozone to lead-initiated shallow convection in the stable Arctic boundary layer, which mixes Hg(0) and ozone from undepleted air masses aloft. This convective forcing provides additional Hg(0) to the surface layer at a time of active depletion chemistry, where it is subject to renewed oxidation. Future work will need to establish the degree to which large-scale changes in sea-ice dynamics across the Arctic alter ozone chemistry and mercury deposition in fragile Arctic ecosystems.

Leaf chlorophyll content as a proxy for leaf photosynthetic capacity.

Improving the accuracy of estimates of forest carbon exchange is a central priority for understanding ecosystem response to increased atmospheric CO2 levels and improving carbon cycle modelling. However, the spatially continuous parameterization of photosynthetic capacity (Vcmax) at global scales and appropriate temporal intervals within terrestrial biosphere models (TBMs) remains unresolved. This research investigates the use of biochemical parameters for modelling leaf photosynthetic capacity within a deciduous forest. Particular attention is given to the impacts of seasonality on both leaf biophysical variables and physiological processes, and their interdependent relationships. Four deciduous tree species were sampled across three growing seasons (2013-2015), approximately every 10 days for leaf chlorophyll content (ChlLeaf ) and canopy structure. Leaf nitrogen (NArea ) was also measured during 2014. Leaf photosynthesis was measured during 2014-2015 using a Li-6400 gas-exchange system, with A-Ci curves to model Vcmax. Results showed that seasonality and variations between species resulted in weak relationships between Vcmax normalized to 25°C (Vcmax25) and NArea (R2  = 0.62, P < 0.001), whereas ChlLeaf demonstrated a much stronger correlation with Vcmax25 (R2  = 0.78, P < 0.001). The relationship between ChlLeaf and NArea was also weak (R2  = 0.47, P < 0.001), possibly due to the dynamic partitioning of nitrogen, between and within photosynthetic and nonphotosynthetic fractions. The spatial and temporal variability of Vcmax25 was mapped using Landsat TM/ETM satellite data across the forest site, using physical models to derive ChlLeaf . TBMs largely treat photosynthetic parameters as either fixed constants or varying according to leaf nitrogen content. This research challenges assumptions that simple NArea -Vcmax25 relationships can reliably be used to constrain photosynthetic capacity in TBMs, even within the same plant functional type. It is suggested that ChlLeaf provides a more accurate, direct proxy for Vcmax25 and is also more easily retrievable from satellite data. These results have important implications for carbon modelling within deciduous ecosystems.

Air-water exchange of anthropogenic and natural organohalogens on International Polar Year (IPY) expeditions in the Canadian Arctic.

Shipboard measurements of organohalogen compounds in air and surface seawater were conducted in the Canadian Arctic in 2007-2008. Study areas included the Labrador Sea, Hudson Bay, and the southern Beaufort Sea. High volume air samples were collected at deck level (6 m), while low volume samples were taken at 1 and 15 m above the water or ice surface. Water samples were taken within 7 m. Water concentration ranges (pg L(-1)) were as follows: α-hexachlorocyclohexane (α-HCH) 465-1013, γ-HCH 150-254, hexachlorobenzene (HCB) 4.0-6.4, 2,4-dibromoanisole (DBA) 8.5-38, and 2,4,6-tribromoanisole (TBA) 4.7-163. Air concentration ranges (pg m(-3)) were as follows: α-HCH 7.5-48, γ-HCH 2.1-7.7, HCB 48-71, DBA 4.8-25, and TBA 6.4 - 39. Fugacity gradients predicted net deposition of HCB in all areas, while exchange directions varied for the other chemicals by season and locations. Net evasion of α-HCH from Hudson Bay and the Beaufort Sea during open water conditions was shown by air concentrations that averaged 14% higher at 1 m than 15 m. No significant difference between the two heights was found over ice cover. The α-HCH in air over the Beaufort Sea was racemic in winter (mean enantiomer fraction, EF = 0.504 ± 0.008) and nonracemic in late spring-early summer (mean EF = 0.476 ± 0.010). This decrease in EF was accompanied by a rise in air concentrations due to volatilization of nonracemic α-HCH from surface water (EF = 0.457 ± 0.019). Fluxes of chemicals during the southern Beaufort Sea open water season (i.e., Leg 9) were estimated using the Whitman two-film model, where volatilization fluxes are positive and deposition fluxes are negative. The means ± SD (and ranges) of net fluxes (ng m(-2) d(-1)) were as follows: α-HCH 6.8 ± 3.2 (2.7-13), γ-HCH 0.76 ± 0.40 (0.26-1.4), HCB -9.6 ± 2.7 (-6.1 to -15), DBA 1.2 ± 0.69 (0.04-2.0), and TBA 0.46 ± 1.1 ng m(-2) d(-1) (-1.6 to 2.0).

Fugitive emissions of polycyclic aromatic compounds from an oil sands tailings pond based on fugacity and inverse dispersion flux calculations.

Alberta's oil sands tailings ponds are suspected to be a source of fugitive emissions of polycyclic aromatic compounds (PACs) to the atmosphere. Here we report, for the first time, fluxes of 6 parent and 21 alkylated PACs based on the measured co-located air and water concentrations using a two-film fugacity-based model (FUG), an inverse dispersion model (DISP) and a simple box model (BOX). Air samples were collected at the Suncor Tailings Pond 2/3 using a high volume air sampler from the "pond" and towards the pond ("non-pond") directions separately. Mean ∑27PACs in air from the "pond" direction was greater than the "non-pond" direction by a factor of 17. Water-air fugacity ratio of 20 PACs quantifiable in water indicated net volatilization from water. Dispersion and box model results also indicated upward fluxes of 22 PACs. Correlation between the estimated flux results of BOX and DISP model was statistically significant (r = 0.99 and p < 0.05), and correlation between FUG and DISP results ranged from 0.54 to 0.85. In this first-ever assessment of PAC fluxes from tailings pond, the three models confirmed volatilization fluxes of PACs indicating Suncor Tailings Pond 2/3 is a source of PAC emissions to the atmosphere. This study addressed a key data gap identified in the Joint Oil Sands Monitoring Emissions Inventory Compilation Report (Government of Alberta and Canada, 2016) which is the lack of consistent real-world tailings pond fugitive emission monitoring of organic chemicals. Our findings highlight the need for measurements from other tailings ponds to determine their overall contribution in releasing PACs to the atmosphere. This paper presents a practical method for estimating PAC emissions from other tailings ponds, which can provide a better understanding of these fugitive emissions, and thereby help to improve the overall characterization of emissions in the oil sands region.

Measured Canadian oil sands CO2 emissions are higher than estimates made using internationally recommended methods.

The oil and gas (O&G) sector represents a large source of greenhouse gas (GHG) emissions globally. However, estimates of O&G emissions rely upon bottom-up approaches, and are rarely evaluated through atmospheric measurements. Here, we use aircraft measurements over the Canadian oil sands (OS) to derive the first top-down, measurement-based determination of the their annual CO2 emissions and intensities. The results indicate that CO2 emission intensities for OS facilities are 13-123% larger than those estimated using publically available data. This leads to 64% higher annual GHG emissions from surface mining operations, and 30% higher overall OS GHG emissions (17 Mt) compared to that reported by industry, despite emissions reporting which uses the most up to date and recommended bottom-up approaches. Given the similarity in bottom-up reporting methods across the entire O&G sector, these results suggest that O&G CO2 emissions inventory data may be more uncertain than previously considered.

Comparison of micrometeorological and two-film estimates of air-water gas exchange for alpha-hexachlorocyclohexane in the Canadian archipelago.

The air-sea gas exchange of alpha-hexachlorocyclohexane (α-HCH) in the Canadian Arctic was estimated using a micrometeorological approach and the commonly used Whitman two-film model. Concurrent shipboard measurements of α-HCH in air at two heights (1 and 15 m) and in surface seawater were conducted during the Circumpolar Flaw Lead study in 2008. Sampling was carried out during eight events in the early summer time when open water was encountered. The micrometeorological technique employed the vertical gradient in air concentration and the wind speed to estimate the flux; results were corrected for atmospheric stability using the Monin-Obukhov stability parameter. The Whitman two-film model used the concentrations of α-HCH in surface seawater, in bulk air at 1 and 15 m above the surface, and the Henry's law constant adjusted for temperature and salinity to derive the flux. Both approaches showed that the overall net flux of α-HCH was from water to air. Mean fluxes calculated using the micrometeorological technique ranged from -3.5 to 18 ng m(-2) day(-1) (mean 7.4), compared to 3.5 to 14 ng m(-2) day(-1) (mean 7.5) using the Whitman two-film model. Flux estimates for individual events agreed in direction and within a factor of two in magnitude for six of eight events. For two events, fluxes estimated by micrometeorology were zero or negative, while fluxes estimated with the two-film model were positive, and the reasons for these discrepancies are unclear. Improvements are needed to shorten air sampling times to ensure that stationarity of meteorological conditions is not compromised over the measurement periods. The micrometeorological technique could be particularly useful to estimate fluxes of organic chemicals over water in situations where no water samples are available.

Measurement of DDT fluxes from a historically treated agricultural soil in Canada.

Organocohlorine pesticide (OCP) residues in agricultural soils are of concern due to the uptake of these compounds by crops, accumulation in the foodchain, and reemission from soils to the atmosphere. Although it has been about three decades since DDT was banned for agricultural uses in Canada, residues persist in soils of some agricultural areas. Emission of DDT compounds to the atmosphere from a historically treated field in southern Ontario was determined in fall 2004 and spring 2005. The sigmaDDTs concentration in the high organic matter (71%) soil was 19 +/- 4 microg g(-1) dry weight. Concentration gradients in the air were measured at 5, 20, 72, and 200 cm above soil using glass fiber filter-polyurethane foam cartridges. Air concentrations of sigmaDDTs averaged 5.7 +/- 5.1 ng m(-3) at 5 cm and decreased to 1.3 +/- 0.8 ng m(-3) at 200 cm and were 60-300 times higher than levels measured at a background site 30 km away. Soil-air fugacity fractions, fs/(fs + fa), of p,p'-DDE, p,p'-DDD, and p,p'-DDT ranged from 0.42 to 0.91 using air concentrations measured above the soil and > or = 0.99 using background air concentrations, indicating that the soil was a net source to the background air. Fractionation of DDT compounds during volatilization was predicted using either liquid-phase vapor pressures (PL) or octanol-air partition coefficients (KOA). Relative emissions of p,p'-DDE and p,p'-DDT were better described by PL than KOA, whereas either PL or KOA successfully accounted for the fractionation of p,p'-DDT and o,p'-DDT. Soil-to-air fluxes were calculated from air concentration gradients and turbulent exchange coefficients determined from micrometeorological measurements. Average fluxes of sigmaDDTs were 90 +/- 24 ng m(-2) h(-1) in fall and 660 +/- 370 ng m(-2) h(-1) in spring. Higher soil temperatures in spring accounted for the higher fluxes. A volatilization half-life of approximately 200 y was estimated for sigmaDDT in the upper 5 cm of the soil column, assuming the average flux rate for 12 h d-(1) over 8 months of the year. Thus, in the absence of other dissipation processes, the soil will continue to be a source of atmospheric contamination for a very long time.