Katherine Hayden

Impact of Fuel Quality Regulation and Speed Reductions on Shipping Emissions: Implications for Climate and Air Quality

Atmospheric emissions of gas and particulate matter from a large ocean-going container vessel were sampled as it slowed and switched from high-sulfur to low-sulfur fuel as it transited into regulated coastal waters of California. Reduction in emission factors (EFs) of sulfur dioxide (SO₂), particulate matter, particulate sulfate and cloud condensation nuclei were substantial (≥ 90%). EFs for particulate organic matter decreased by 70%. Black carbon (BC) EFs were reduced by 41%. When the measured emission reductions, brought about by compliance with the California fuel quality regulation and participation in the vessel speed reduction (VSR) program, are placed in a broader context, warming from reductions in the indirect effect of SO₄ would dominate any radiative changes due to the emissions changes. Within regulated waters absolute emission reductions exceed 88% for almost all measured gas and particle phase species. The analysis presented provides direct estimations of the emissions reductions that can be realized by California fuel quality regulation and VSR program, in addition to providing new information relevant to potential health and climate impact of reduced fuel sulfur content, fuel quality and vessel speed reductions.

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.

An Intensive Study of the Size and Composition of Submicron Atmospheric Aerosols at a Rural Site in Ontario, Canada

Atmospheric sampling was conducted at a rural site near Egbert, about 70 km north of Toronto, Ontario, Canada from March 27 to May 8, 2003 to characterize the physical and chemical properties of the ambient aerosol in near real-time. The instrumentation included a tapered element oscillating microbalance (TEOM), an ultrafine condensation particle counter (UCPC), a scanning mobility particle sizer (SMPS), an aerodynamic particle sizer (APS), an aerosol mass spectrometer (AMS), and a particulate nitrate monitor (R&P 8400N) for aerosol measurements. Gas-phase non-methane hydrocarbon compounds (NMHCs) were measured by gas chromatograph-flame ionization detection (GC-FID). Filter samples were also collected for analysis of inorganic ions by ion chromatography (IC). Aerosol properties varied considerably depending upon meteorological conditions and airmass histories. For example, urban and industrial emissions advected from the south strongly influenced the site occasionally, resulting in higher particulate mass with the higher fractions of nitrate and organics. Cleaner northwesterly winds carried aerosols with relatively higher fractions of organics and sulfate. The AMS derived mass size distributions showed that the inorganic species in the particles with vacuum aerodynamic diameters between about 60 nm and 600 nm had mass modal vacuum aerodynamic diameters around 400–500 nm. The particulate organics often exhibited two modes at about 100 nm and 425 nm, more noticeable during fresh pollution events. The small organic mode was well correlated with gas-phase nonmethane hydrocarbons such as ethylbenzene, toluene, and propene, suggesting that the likely sources of small organic particles were combustion related emissions. The particulate nitrate exhibited a diurnal variation with higher concentrations during dark hours and minima in the afternoon. Particulate sulfate and organics showed evidence of photochemical processing with higher levels of sulfate and oxygenated organics in the afternoon. Reasonable agreement among all of the co-located measurements is found, provided the upper size limit of the AMS is considered.

Summertime formaldehyde at a high‐elevation site in Quebec

Measurements of formaldehyde were made during the summer of 1996 at a high-elevation site in Quebec as part of the North American Research Strategy on Tropospheric Ozone-Canada East (NARSTO-CE) measurement program. Gas phase mixing ratios were determined continuously by removing formaldehyde from the air in a glass coil scrubber, and producing a fluorescent dimer through the Hantzsch reaction. Average mixing ratios of formaldehyde were 1.3 and 0.8 ppbv for dry and wet periods, respectively. Highest values of HCHO were observed July 1-2 with a maximum mixing ratio of 4.6 ppbv. Fog water samples were also collected and analyzed for HCHO on five afternoon periods. Comparison of HCHO in the gas and aqueous phases shows reasonable agreement with Henrys law equilibrium. For dry periods July 1-12, relationships were examined between formaldehyde and other chemical species also measured at the site. Data were segregated based on the ratio of NO x to NO y and on the level of anthropogenic hydrocarbons present in the air mass. For the majority of the data, formaldehyde increased with both ozone and products of NO x oxidation (NO z ) and was inversely related to the NO x /NO y ratio. During the high HCHO episode July 1-2, HCHO was correlated with neither ozone nor NO 2 illustrating the different chemistry at the site on these days. A chemical box model was used to examine sources of HCHO July 1-4. The model suggests that biogenic hydrocarbons contribute on average 53% of the locally produced formaldehyde, the remainder resulting from the oxidation of methane (19%), anthropogenic VOCs (16%), acetaldehyde (7%), and organic peroxides (3%). The model cannot account for the July 1-2 formaldehyde mixing ratios from the chemistry measured at the site. This implies that an additional HCHO source not included in the model was responsible for the high levels on those days.

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.

Estimates of Exceedances of Critical Loads for Acidifying Deposition in Alberta and Saskatchewan

Estimates of potential harmful effects to ecosystems in the Canadian provinces of Alberta and Saskatchewan due to acidifying deposition were calculated, using a one year simulation of a high resolution implementation of the Global Environmental Multiscale – Modelling Air-quality and Chemistry (GEM-MACH) model, and estimates of aquatic and terrestrial ecosystem critical loads. The model simulation was evaluated against two different sources of deposition data; 20 total deposition in precipitation and total deposition to snowpack in the vicinity of the Athabasca oil sands. The model captured much of the variability of observed ions in wet deposition in precipitation (observed versus model sulphur, nitrogen and base cation R 2 values of 0.90, 0.76 and 0.72, respectively), while being biased high for sulphur deposition, and low for nitrogen and base cations (slopes 2.2, 0.89 and 0.40, respectively). Aircraft-observation-based estimates of fugitive dust emissions, shown to be a factor of ten higher than reported values (Zhang et al.., 2017), were used to estimate the impact of 25 increased levels of fugitive dust on model results. Model comparisons to open snowpack observations were shown to be biased high, but in reasonable agreement for sulphur deposition when observations were corrected to account for throughfall in needleleaf forests. The model-observation relationships for precipitation deposition data, along with the expected effects of increased (unreported) base cation emissions, were used to provide a simple observation-based correction to model deposition fields. Base cation deposition was estimated using published observations of base cation fractions in surface 30 collected particles (Wang et al.., 2015). Both original and observation-corrected model estimates of sulphur, nitrogen and base cation deposition were used in conjunction with critical load data created using the NEG-ECP (2001) and CLRTAP (2004, 2016, 2017) protocols for critical loads, using variations on the Simple Mass Balance model for forest and terrestrial ecosystems, and the Steady State Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2017-1094 Manuscript under review for journal Atmos. Chem. Phys. Discussion started: 26 February 2018 c

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

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.

The effects of biodiesels on semivolatile and nonvolatile particulate matter emissions from a light-duty diesel engine

Semivolatile organic compounds (SVOCs) represent a dominant category of secondary organic aerosol precursors that are increasingly included in air quality models. In the present study, an experimental system was developed and applied to a light-duty diesel engine to determine the emission factors of particulate SVOCs (pSVOCs) and nonvolatile particulate matter (PM) components at dilution ratios representative of ambient conditions. The engine was tested under three steady-state operation modes, using ultra-low-sulfur diesel (ULSD), three types of pure biodiesels and their blends with ULSD. For ULSD, the contribution of pSVOCs to total particulate organic matter (POM) mass in the engine exhaust ranged between 21 and 85%. Evaporation of pSVOCs from the diesel particles during dilution led to decreases in the hydrogen to carbon ratio of POM and the PM number emission factor of the particles. Substituting biodiesels for ULSD could increase pSVOCs emissions but brought on large reductions in black carbon (BC) emissions. Among the biodiesels tested, tallow/used cooking oil (UCO) biodiesel showed advantages over soybean and canola biodiesels in terms of both pSVOCs and nonvolatile PM emissions. It is noteworthy that PM properties, such as particle size and BC mass fraction, differed substantially between emissions from conventional diesel and biodiesels.