Amy Leithead

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.

Differences between measured and reported volatile organic compound emissions from oil sands facilities in Alberta, Canada.

Significance Validation of volatile organic compound (VOC) emission reports, especially from large industrial facilities, is rarely attempted. Given uncertainties in emission reports, their evaluation and validation will build confidence in emission inventories. It is shown that a top-down approach can provide measurement-based emission rates for such emission validation. Comparisons with emission reports from Alberta oil sands surface mining facilities revealed significant differences in VOC emissions between top-down emissions rates and reports. Comparison with VOC species emission reports using currently accepted estimation methods indicates that emissions were underestimated in the reports for most species. This exercise shows that improvements in the accuracy and completeness of emissions estimates from complex facilities would enhance their application to assessing the impacts of such emissions. Large-scale oil production from oil sands deposits in Alberta, Canada has raised concerns about environmental impacts, such as the magnitude of air pollution emissions. This paper reports compound emission rates (E) for 69–89 nonbiogenic volatile organic compounds (VOCs) for each of four surface mining facilities, determined with a top-down approach using aircraft measurements in the summer of 2013. The aggregate emission rate (aE) of the nonbiogenic VOCs ranged from 50 ± 14 to 70 ± 22 t/d depending on the facility. In comparison, equivalent VOC emission rates reported to the Canadian National Pollutant Release Inventory (NPRI) using accepted estimation methods were lower than the aE values by factors of 2.0 ± 0.6, 3.1 ± 1.1, 4.5 ± 1.5, and 4.1 ± 1.6 for the four facilities, indicating underestimation in the reported VOC emissions. For 11 of the combined 93 VOC species reported by all four facilities, the reported emission rate and E were similar; but for the other 82 species, the reported emission rate was lower than E. The median ratio of E to that reported for all species by a facility ranged from 4.5 to 375 depending on the facility. Moreover, between 9 and 53 VOCs, for which there are existing reporting requirements to the NPRI, were not included in the facility emission reports. The comparisons between the emission reports and measurement-based emission rates indicate that improvements to VOC emission estimation methods would enhance the accuracy and completeness of emission estimates and their applicability to environmental impact assessments of oil sands developments.

Understanding the primary emissions and secondary formation of gaseous organic acids in the oil sands region of Alberta, Canada

Transformation flights were designed as Lagrangian experiments such that air parcels in plumes were repeatedly sampled at different times (1 hour apart), by flying virtual screens (at multiple altitudes) up to 120km downwind of the OS. There were no industrial emissions between the screens such that pollutant differences 20 between screens can be ascribed to a combination of photochemistry, dilution and deposition. Meteorological parameters associated with the transformation flights are given in Liggio et al., 2016. In the current work, the secondary formation of organic acids and their evolution over time is investigated using primarily F19 (but also F20) as it was the most successful Lagrangian experiment, having the best agreement between air parcel transport times and aircraft flight times at each plume intercept (Liggio et al., 2016). 25

THE DETECTION OF POLYCYCLIC AROMATIC COMPOUNDS IN AIR SAMPLES BY GC×GC-TOFMS

Multidimensional Gas Chromatography-Time of Flight Mass Spectrometry is a relatively new, highly versatile and productive technique that is ideally suited for the detection of PACs in environmental samples. Air samples collected in Slocan Park in Vancouver and in Langley, BC (a semi-rural site) during the PACIFIC 2001 field study and aerosol samples from St. Anicet in Quebec (a rural site) collected in 2006 were analyzed for their PAC content. In addition to the parent PAH, many alkylated-PAH, oxygen, sulphur and nitrogen heterocyclic analogues of the parent PAH were detected. Many of the PAHs observed at these sites were also found in diesel exhaust.

Quantifying the Primary Emissions and Photochemical Formation of Isocyanic Acid Downwind of Oil Sands Operations

Isocyanic acid (HNCO) is a known toxic species and yet the relative importance of primary and secondary sources to regional HNCO and population exposure remains unclear. Off-road diesel fuel combustion has previously been suggested to be an important regional source of HNCO, which implies that major industrial facilities such as the oil sands (OS), which consume large quantities of diesel fuel, can be sources of HNCO. The OS emissions of nontraditional toxic species such as HNCO have not been assessed. Here, airborne measurements of HNCO were used to estimate primary and secondary HNCO for the oil sands. Approximately 6.2 ± 1.1 kg hr-1 was emitted from off-road diesel activities within oil sands facilities, and an additional 116-186 kg hr-1 formed from the photochemical oxidation of diesel exhaust. Together, the primary and secondary HNCO from OS operations represent a significant anthropogenic HNCO source in Canada. The secondary HNCO downwind of the OS was enhanced by up to a factor of 20 relative to its primary emission, an enhancement factor significantly greater than previously estimated from laboratory studies. Incorporating HNCO emissions and formation into a regional model demonstrated that the HNCO levels in Fort McMurray (∼10-70 km downwind of the OS) are controlled by OS emissions; > 50% of the monthly mean HNCO arose from the OS. While the mean HNCO levels in Fort McMurray are predicted to be below the 1000 pptv level associated with potential negative health impacts, (∼25 pptv in August-September), an order of magnitude increase in concentration is predicted (250-600 pptv) when the town is directly impacted by OS plumes. The results here highlight the importance of obtaining at-source HNCO emission factors and advancing the understanding of secondary HNCO formation mechanisms, to assess and improve HNCO population exposure predictions.

Modelling Regional Aerosols: Impact of Cloud Processing on Gases and Particles over Eastern North America and in Its Outflow During ICARTT 2004

A regional aerosol model, AURAMS (A Unified Regional Air-quality Modelling System), is used to simulate gases and aerosols over eastern North America for the ICARTT field campaign period during summer 2004. The model performance is evaluated against both ground-based and airborne observations during the field campaign. A model sensitivity study is used to assess the impact of cloud processing on the aerosol characteristics in the air masses over eastern North America and its outflow to the North Atlantic during the study period.