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.

Dissolved Organic Carbon in Lakes of the Athabasca Oil Sands Region: Is Color an Indicator of Acid Sensitivity?

The Athabasca oil sands region (AOSR) in north-eastern Alberta, Canada, contains the world's third largest known bitumen deposit. Oil sands (OS) operations produce emissions known to contribute to acidic and alkaline deposition, which can alter the chemistry of the receiving surface waters, including dissolved organic carbon (DOC). Little is known regarding the natural variability of aquatic DOC among lakes within the AOSR. Surface-water data from 50 lakes were analyzed; variables known to be associated with the light-absorptive properties of DOC (true color [TC]) were evaluated to investigate the potential variability of chromophoric DOC (CDOC). Comparison of TC and DOC revealed two distinct "high" (H) and "low" (L) lake subpopulations, the former being characterized by high relative TC and low DOC, and the latter by the inverse. The H lakes were defined by variables known to be associated with CDOC, while L lakes appeared well-buffered potentially owing to groundwater inputs. The divergent optical properties between subpopulations appeared partially attributable to pH-limited Fe complexation. Trajectory analysis indicated that H lakes most likely to receive atmospheric deposition from OS sources experienced significantly lower pH. These results are contrary to previous studies that found OS emissions to have minimal acidifying effect over lakes throughout the AOSR.

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

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.

High resolution mapping of nitrogen dioxide with TROPOMI: First results and validation over the Canadian oil sands.

TROPOMI, on-board the Sentinel-5 Precursor satellite is a nadir-viewing spectrometer measuring reflected sunlight in the ultraviolet, visible, near-infrared, and shortwave infrared spectral range. From these spectra several important air quality and climate-related atmospheric constituents are retrieved at an unprecedented high spatial resolution, including nitrogen dioxide (NO2). We present the first retrievals of TROPOMI NO2 over the Canadian Oil Sands, contrasting them with observations from the OMI satellite instrument, and demonstrate its ability to resolve individual plumes and highlight its potential for deriving emissions from individual mining facilities. Further, the first TROPOMI NO2 validation is presented, consisting of aircraft and surface in-situ NO2 observations, as well as ground-based remote-sensing measurements between March and May 2018. Our comparisons show that the TROPOMI NO2 vertical column densities are highly correlated with the aircraft and surface in-situ NO2 observations, and the ground-based remote-sensing measurements with a low bias (15-30 %) over the Canadian Oil Sands. PLAIN LANGUAGE SUMMARY: Nitrogen dioxide (NO2) is a pollutant that is linked to respiratory health issues and has negative environmental impacts such as soil and water acidification. Near the surface the most significant sources of NO2 are fossil fuel combustion and biomass burning. With a recently launched satellite instrument (TROPOspheric Monitoring Instrument; TROPOMI) NO2 can be measured with an unprecedented combination of accuracy, spatial coverage, and resolution. This work presents the first TROPOMI NO2 measurements near the Canadian Oil Sands and shows that these measurements have an outstanding ability to detect NO2 on a very high horizontal resolution that is unprecedented for satellite NO2 observations. Further, these satellite measurements are in excellent agreement with aircraft and ground-based measurements.

A single-point modeling approach for the intercomparison and evaluation of ozone dry deposition across chemical transport models (Activity 2 of AQMEII4).

A primary sink of air pollutants and their precursors is dry deposition. Dry deposition estimates differ across chemical transport models, yet an understanding of the model spread is incomplete. Here, we introduce Activity 2 of the Air Quality Model Evaluation International Initiative Phase 4 (AQMEII4). We examine 18 dry deposition schemes from regional and global chemical transport models as well as standalone models used for impact assessments or process understanding. We configure the schemes as single-point models at eight Northern Hemisphere locations with observed ozone fluxes. Single-point models are driven by a common set of site-specific meteorological and environmental conditions. Five of eight sites have at least 3 years and up to 12 years of ozone fluxes. The interquartile range across models in multiyear mean ozone deposition velocities ranges from a factor of 1.2 to 1.9 annually across sites and tends to be highest during winter compared with summer. No model is within 50 % of observed multiyear averages across all sites and seasons, but some models perform well for some sites and seasons. For the first time, we demonstrate how contributions from depositional pathways vary across models. Models can disagree with respect to relative contributions from the pathways, even when they predict similar deposition velocities, or agree with respect to the relative contributions but predict different deposition velocities. Both stomatal and nonstomatal uptake contribute to the large model spread across sites. Our findings are the beginning of results from AQMEII4 Activity 2, which brings scientists who model air quality and dry deposition together with scientists who measure ozone fluxes to evaluate and improve dry deposition schemes in the chemical transport models used for research, planning, and regulatory purposes.

A decadal synthesis of atmospheric emissions, ambient air quality, and deposition in the oil sands region.

This review is part of a series synthesizing peer-reviewed literature from the past decade on environmental monitoring in the oil sands region (OSR) of northeastern Alberta. It focuses on atmospheric emissions, air quality, and deposition in and downwind of the OSR. Most published monitoring and research activities were concentrated in the surface-mineable region in the Athabasca OSR. Substantial progress has been made in understanding oil sands (OS)-related emission sources using multiple approaches: airborne measurements, satellite measurements, source emission testing, deterministic modeling, and source apportionment modeling. These approaches generally yield consistent results, indicating OS-related sources are regional contributors to nearly all air pollutants. Most pollutants exhibit enhanced air concentrations within ~20 km of surface-mining activities, with some enhanced >100 km downwind. Some pollutants (e.g., sulfur dioxide, nitrogen oxides) undergo transformations as they are transported through the atmosphere. Deposition rates of OS-related substances primarily emitted as fugitive dust are enhanced within ~30 km of surface-mining activities, whereas gaseous and fine particulate emissions have a more diffuse deposition enhancement pattern extending hundreds of kilometers downwind. In general, air quality guidelines are not exceeded, although these single-pollutant thresholds are not comprehensive indicators of air quality. Odor events have occurred in communities near OS industrial activities, although it can be difficult to attribute events to specific pollutants or sources. Nitrogen, sulfur, polycyclic aromatic compounds (PACs), and base cations from OS sources occur in the environment, but explicit and deleterious responses of organisms to these pollutants are not as apparent across all study environments; details of biological monitoring are discussed further in other papers in this special series. However, modeling of critical load exceedances suggests that, at continued emission levels, ecological change may occur in future. Knowledge gaps and recommendations for future work to address these gaps are also presented. Integr Environ Assess Manag 2022;18:333-360. © 2021 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Depression of ammonia uptake to sulfuric acid aerosols by competing uptake of ambient organic gases.

The neutralization of acidic aerosols by ammonia has been studied through experiments which combine ambient air with laboratory generated sulfuric acid aerosol. Results indicated that acidic aerosol mixed with organic free air and ammonia was neutralized on a time scale<1 min, consistent with expectations. However, in the presence of ambient organic gases and ammonia, the rate of aerosol neutralization is significantly reduced. This reduction in ammonia uptake was concurrent with an increase in the amount of particle phase organics. A steady state in the NH4+/SO4(2-) in the presence of organic gases was established on time scales of 10 min to several hours, corresponding to NH3 uptake coefficients in the range of 4×10(-3)-2×10(-4). The degree to which neutralization was slowed was dependent upon the initial ammonia concentration and the organic mass added to the aerosols. These results suggest that inorganic equilibrium thermodynamic models may overestimate the rate of ammonia uptake and that ambient particles may remain acidic for longer than previously expected.

Extension of a gaseous dry deposition algorithm to oxidized volatile organic compounds and hydrogen cyanide for application in chemistry transport models.

The dry deposition process refers to flux loss of an atmospheric pollutant due to uptake of the pollutant by the Earth's surfaces, including vegetation, underlying soil, and any other surface types. In chemistry transport models (CTMs), the dry deposition flux of a chemical species is typically calculated as the product of its surface layer concentration and its dry deposition velocity (V d); the latter is a variable that needs to be highly empirically parameterized due to too many meteorological, biological, and chemical factors affecting this process. The gaseous dry deposition scheme of Zhang et al. (2003) parameterizes V d for 31 inorganic and organic gaseous species. The present study extends the scheme of Zhang et al. (2003) to include an additional 12 oxidized volatile organic compounds (oVOCs) and hydrogen cyanide (HCN), while keeping the original model structure and formulas, to meet the demand of CTMs with increasing complexity. Model parameters for these additional chemical species are empirically chosen based on their physicochemical properties, namely the effective Henry's law constants and oxidizing capacities. Modeled V d values are compared against field flux measurements over a mixed forest in the southeastern US during June 2013. The model captures the basic features of the diel cycles of the observed V d. Modeled V d values are comparable to the measurements for most of the oVOCs at night. However, modeled V d values are mostly around 1 cm s-1 during daytime, which is much smaller than the observed daytime maxima of 2-5 cm s-1. Analysis of the individual resistance terms and uptake pathways suggests that flux divergence due to fast atmospheric chemical reactions near the canopy was likely the main cause of the large model-measurement discrepancies during daytime. The extended dry deposition scheme likely provides conservative V d values for many oVOCs. While higher V d values and bidirectional fluxes can be simulated by coupling key atmospheric chemical processes into the dry deposition scheme, we suggest that more experimental evidence of high oVOC V d values at additional sites is required to confirm the broader applicability of the high values studied here. The underlying processes leading to high measured oVOC V d values require further investigation.

Technical note: AQMEII4 Activity 1: evaluation of wet and dry deposition schemes as an integral part of regional-scale air quality models.

We present in this technical note the research protocol for phase 4 of the Air Quality Model Evaluation International Initiative (AQMEII4). This research initiative is divided into two activities, collectively having three goals: (i) to define the current state of the science with respect to representations of wet and especially dry deposition in regional models, (ii) to quantify the extent to which different dry deposition parameterizations influence retrospective air pollutant concentration and flux predictions, and (iii) to identify, through the use of a common set of detailed diagnostics, sensitivity simulations, model evaluation, and reduction of input uncertainty, the specific causes for the current range of these predictions. Activity 1 is dedicated to the diagnostic evaluation of wet and dry deposition processes in regional air quality models (described in this paper), and Activity 2 to the evaluation of dry deposition point models against ozone flux measurements at multiple towers with multiyear observations (to be described in future submissions as part of the special issue on AQMEII4). The scope of this paper is to present the scientific protocols for Activity 1, as well as to summarize the technical information associated with the different dry deposition approaches used by the participating research groups of AQMEII4. In addition to describing all common aspects and data used for this multi-model evaluation activity, most importantly, we present the strategy devised to allow a common process-level comparison of dry deposition obtained from models using sometimes very different dry deposition schemes. The strategy is based on adding detailed diagnostics to the algorithms used in the dry deposition modules of existing regional air quality models, in particular archiving diagnostics specific to land use-land cover (LULC) and creating standardized LULC categories to facilitate cross-comparison of LULC-specific dry deposition parameters and processes, as well as archiving effective conductance and effective flux as means for comparing the relative influence of different pathways towards the net or total dry deposition. This new approach, along with an analysis of precipitation and wet deposition fields, will provide an unprecedented process-oriented comparison of deposition in regional air quality models. Examples of how specific dry deposition schemes used in participating models have been reduced to the common set of comparable diagnostics defined for AQMEII4 are also presented.

Estimation of atmospheric emissions of six semivolatile polycyclic aromatic hydrocarbons in southern canada and the United States by use of an emissions processing system.

Polycyclic aromatic hydrocarbons (PAHs) are toxic compounds that are ubiquitous in the atmospheric environment. The input for an emissions processing system that was originally configured forthe study of criteria air pollutants was updated to calculate emissions of six semivolatile PAHs. The goal of the work was to produce emissions estimates with the spatial and temporal resolution needed to serve as input to a regional air quality model for southern Canada and the U.S. Such modeling is helpful in determining reductions in PAH emissions that may be necessary to protect human and ecosystem health. The total annual emission of the six PAHs (sigma6PAH) for both countries was estimated at 18 273 Mg/year. A total of 90% of these emissions arise from U.S. sources. The top six source types account for 73% of emissions and are related to metal production, open burning, incineration, and forest fires. The emission factors used in this study were derived from published compilations. Although this approach has the advantage of quality control during the compilation process, some compilations include factors from older studies that may overestimate emissions since they do not account for recent improvements in emission control technology. When compared to estimates published in the National Emissions Inventory (NEI) for 2002, the U.S. emissions in this study are higher by a factor of 4 (16 424 vs 4102 Mg/year). The cause of this difference has been investigated, and much of it is likely due to our use of data unavailable in the 2002 NEI but inferred here on the basis of the PAH emissions literature. Augmenting the 2002 NEI with this additional information would bring its reported annual emissions to 8213 Mg/year, which is within a factor of 2 of the estimates herein. The results presented for southern Canada are the first published values for all known PAH sources in that country.

Simulating organic aerosol formation during the photooxidation of toluene/NOx mixtures: comparing the equilibrium and kinetic assumption.

Organic compounds contribute an appreciable mass to particulate matter and thus impact the hygroscopic and radiative properties of an aerosol distribution. Being able to predict the chemical and physical properties of aerosols based on their size and composition is critical to assessing their impact on air quality, visibility, and climate change. In this study, a comparison was performed between an equilibrium and a kinetic model for simulating organic aerosol formation during the photooxidation of toluene/NO/isopropyl nitrite mixtures. Both models used an explicit gas-phase toluene scheme (University of Leeds Master Chemical Mechanism version 3.0) and provided a prediction of individual products partitioned to the aerosol phase. After incorporating a heterogeneous wall reaction scheme regenerating NOx from HNO3 and HNO2, the gas-phase scheme was able to simulate the observed toluene decay within 5% and NO decay within 30% for all of the chamber experiments. The models reproduced the general magnitude of the aerosol yields but suggest a weaker trend dependence on aerosol mass loading. A few nonvolatile compounds were predicted to compose the majority of the aerosol-phase mass with multifunctional organic nitrates being the dominant organic aerosol functional group. The hygroscopic diameter growth factor for the organic phase was predicted to be 1.1 at a relative humidity of 79%. We conclude with a list of recommended laboratory experiments to help constrain and validate aerosol process models.