We evaluate four high-resolution model simulations of pollutant emissions, chemical transformation, and downwind transport for the Athabasca oil sands using the Global Environmental Multiscale -Modelling Air-quality and Chemistry (GEM-MACH) model, and compare model results with surface monitoring network and aircraft observations of multiple pollutants, for simulations spanning a time period corresponding to an aircraft measurement campaign in the summer of 2013. We have focussed here on the impact of different representations of the model's aerosol size distribution and plume-rise parameterization on model results. The use of a more finely resolved representation of the aerosol size distribution was found to have a significant impact on model performance, reducing the magnitude of the original surface PM2.5 negative biases 32 %, from -2.62 to -1.72 mu gm(-3). We compared model predictions of SO2, NO2, and speciated particulate matter concentrations from simulations employing the commonly used Briggs (1984) plume-rise algorithms to redistribute emissions from large stacks, with stack plume observations. As in our companion paper (Gordon et al., 2017), we found that Briggs algorithms based on estimates of atmospheric stability at the stack height resulted in under-predictions of plume rise, with 116 out of 176 test cases falling below the model : observation 1 : 2 line, 59 cases falling within a factor of 2 of the observed plume heights, and an average model plume height of 289m compared to an average observed plume height of 822 m. We used a high-resolution meteorological model to confirm the presence of significant horizontal heterogeneity in the local meteorological conditions driving plume rise. Using these simulated meteorological conditions at the stack locations, we found that a layered buoyancy approach for estimating plume rise in stable to neutral atmospheres, coupled with the assumption of free rise in convectively unstable atmospheres, resulted in much better model performance relative to observations (124 out of 176 cases falling within a factor of 2 of the observed plume height, with 69 of these cases above and 55 of these cases below the 1 : 1 line and within a factor of 2 of observed values). This is in contrast to our companion paper, wherein this layered approach (driven by meteorological observations not co-located with the stacks) showed a relatively modest impact on predicted plume heights. Persistent issues with over-fumigation of plumes in the model were linked to a more rapid decrease in simulated temperature with increasing height than was observed. This in turn may have led to overestimates of near-surface diffusivity, resulting in excessive fumigation.

The oil sands (OS) of Alberta, Canada, which are classified as unconventional oil, are the third-largest oil reserves in the world. We describe here a 6-year effort to improve the emissions data used for air quality (AQ) modeling of the roughly 100 km x 100 km oil extraction and processing industrial complex operating in the Athabasca Oil Sands Region (AOSR) of northeastern Alberta. This paper reviews the national, provincial, and sub-provincial emissions inventories that were available during the three phases of the study, supplemented by hourly SO2 and NOx emissions and stack characteristics for larger point sources measured by a continuous emission monitoring system (CEMS), as well as daily reports of SO2 from one AOSR facility for a 1-week period during a 2013 field campaign when the facility experienced upset conditions. Next it describes the creation of several detailed hybrid emissions inventories and the generation of model-ready emissions input files for the Global Environmental Multiscale-Modelling Air quality and CHemistry (GEM-MACH) AQ modeling system that were used during the 2013 field study and for various post-campaign GEM-MACH sensitivity studies, in particular for a high-resolution model domain with 2.5 km grid spacing covering much of western Canada and centered over the AOSR. Lastly, it compares inventory-based bottom-up emissions with aircraft-observation-based top-down emissions estimates. Results show that emissions values obtained from different data sources can differ significantly, such as a possible 10-fold difference in PM2.5 emissions and approximately 40 and 20% differences for total VOC (volatile organic compound) and SO2 emissions. A novel emissions-processing approach was also employed to allocate emissions spatially within six large AOSR mining facilities in order to address the urban-scale spatial extent of the facilities and the high-resolution 2.5 km model grid. Gridded facility-and process-specific spatial surrogate fields that were generated using spatial information from GIS (geographic information system) shapefiles and satellite images were used to allocate non-smokestack emissions for each facility to multiple grid cells instead of treating these emissions as point sources and allocating them to a single grid cell as is normally done. Facility-and process-specific temporal profiles and VOC speciation profiles were also developed. The pre-2013 vegetation and land-use databases normally used to estimate biogenic emissions and meteorological surface properties were modified to account for the rapid change in land use in the study area due to marked, year-by-year changes in surface mining activities, including the 2013 opening of a new mine. Lastly, mercury emissions data were also processed in addition to the seven criteria-air-contaminant (CAC) species (NO x, VOC, SO2, NH3, CO, PM2.5, and PM10) to support AOSR mercury modeling activities. Six GEM-MACH modeling papers in this special issue used some of these new sets of emissions and land-use input files.

Estimates of potential harmful effects on ecosystems in the Canadian provinces of Alberta and Saskatchewan due to acidifying deposition were calculated, using a 1-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: total deposition in precipitation and total deposition to snow-pack 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 sulfur, nitrogen and base cation R-2 values of 0.90, 0.76 and 0.72, respectively), while being biased high for sulfur deposition, and low for nitrogen and base cations (slopes 2.2, 0.89 and 0.40, respectively). Aircraft-based estimates of fugitive dust emissions, shown to be a factor of 10 higher than reported to national emissions inventories (Zhang et al., 2018), were used to estimate the impact of increased levels of fugitive dust on model results. Model comparisons to open snow-pack observations were shown to be biased high, but in reasonable agreement for sulfur 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-collected particles (Wang et al., 2015). Both original and observation-corrected model estimates of sulfur, nitrogen, and base cation deposition were used in conjunction with critical load data created using the NEG-ECP (2001) and CLRTAP (2017) methods for calculating critical loads, using variations on the Simple Mass Balance model for terrestrial ecosystems, and the Steady State Water Chemistry and First-order Acidity Balance models for aquatic ecosystems. Potential ecosystem damage was predicted within each of the regions represented by the ecosystem critical load datasets used here, using a combination of 2011 and 2013 emissions inventories. The spatial extent of the regions in exceedance of critical loads varied between 1 x 10(4) and 3.3 x 10(5) km(2), for the more conservative observation-corrected estimates of deposition, with the variation dependent on the ecosystem and critical load calculation methodology. The larger estimates (for aquatic ecosystems) represent a substantial fraction of the area of the provinces examined. Base cation deposition was shown to be sufficiently high in the region to have a neutralizing effect on acidifying deposition, and the use of the aircraft and precipitation observation-based corrections to base cation deposition resulted in reasonable agreement with snowpack data collected in the oil sands area. However, critical load exceedances calculated using both observations and observation-corrected deposition suggest that the neutralization effect is limited in spatial extent, decreasing rapidly with distance from emissions sources, due to the rapid deposition of emitted primary dust particles as a function of their size. We strongly recommend the use of observation-based correction of model-simulated deposition in estimating critical load exceedances, in future work.

Although a number of studies have assessed the occurrence of atmospheric polycyclic aromatic hydrocarbons (PAHs) in indoor environment, few studies have systemically examined the indoor-outdoor interplay of size-dependent particulate PAHs and potential health risk based on daily lifestyles. In the present study, size-dependent particle and gaseous samples were collected both indoors and outdoors within selected schools, offices and residences located in three districts of Guangzhou, China with different urbanization levels during the dry and wet weather seasons. Results from measurements of PAHs showed that higher total PAH concentrations occurred in residential areas than in other settings and in indoor than in outdoor environments. Compositional profiles and size distribution patterns of particle-bound PAHs were similar indoors and outdoors, predominated by 4-and 5-ring PAHs and the 0.56-1.0 sm particle fraction. Statistical analyses indicated that outdoor sources may have contributed to 38-99% and 62-100% of the variations for indoor particle-bound and gaseous PAH concentrations, respectively. Incremental life cancer risk (ILCR) from human exposure to indoor and outdoor PAHs based on different lifestyles followed the order of adults > children > adolescents > seniors. All average ILCR values for four age groups were below the lower limit of the Safe Acceptable Range (10(-6)). In addition, the ILCR value for adults (average: 7.2 x 10(-7); 95% CI: 5.4 x 10(-8) -2.5 x 10(-6)), estimated from outdoor air PAH levels with 24-h exposure time, was significantly higher than our assessment results (average: 5.9 x 10(-7); 95% Cl: 6.3 x 10(-8)-1.9 x 10(-6)), suggesting the significance of assessing human inhalation exposure risks of indoor and outdoor PAHs in urban air based on daily lifestyles. (C) 2018 Elsevier Ltd. All rights reserved.

Black carbon (BC) plays an important role in the Earth's climate system. However, parameterizations of BC size and mixing state have not been well addressed in aerosol-climate models, introducing substantial uncertainties into the estimation of radiative forcing by BC. In this study, we focused on BC emissions from the oil sands (OS) surface mining activities in northern Alberta, based on an aircraft campaign conducted over the Athabasca OS region in 2013. A total of 14 flights were made over the OS source area, in which the aircraft was typically flown in a four-or five-sided polygon pattern along flight tracks encircling an OS facility. Another 3 flights were performed downwind of the OS source area, each of which involved at least three intercepting locations where the well-mixed OS plume was measured along flight tracks perpendicular to the wind direction. Comparable size distributions were observed for refractory black carbon (rBC) over and downwind of the OS facilities, with rBC mass median diameters (MMDs) between similar to 135 and 145 nm that were characteristic of fresh urban emissions. This MMD range corresponded to rBC number median diameters (NMDs) of similar to 60-70 nm, approximately 100% higher than the NMD settings in some aerosol-climate models. The typical in-and out-of-plume segments of a flight, which had different rBC concentrations and photochemical ages, showed consistent rBC size distributions in terms of MMD, NMD and the corresponding distribution widths. Moreover, rBC size distributions remained unchanged at different downwind distances from the source area, suggesting that atmospheric aging would not necessarily change rBC size distribution. However, aging indeed in-fluenced rBC mixing state. Coating thickness for rBC cores in the diameter range of 130-160 nm was nearly doubled (from similar to 20 to 40 nm) within 3 h when the OS plume was transported over a distance of 90 km from the source area.

In this paper, measurements of air pollutants made at a ground site near Fort McKay in the Athabasca oil sands region as part of a multi-platform campaign in the summer of 2013 are presented. The observations included measurements of selected volatile organic compounds (VOCs) by a gas chromatograph-ion trap mass spectrometer (GC-ITMS). This instrument observed a large, analytically unresolved hydrocarbon peak (with a retention index between 1100 and 1700) associated with intermediate-volatility organic compounds (IVOCs). However, the activities or processes that contribute to the release of these IVOCs in the oil sands region remain unclear. Principal component analysis (PCA) with varimax rotation was applied to elucidate major source types impacting the sampling site in the summer of 2013. The analysis included 28 variables, including concentrations of total odd nitrogen (NOy), carbon dioxide (CO2), methane (CH4), ammonia (NH3), carbon monoxide (CO), sulfur dioxide (SO2), total reduced-sulfur compounds (TRSs), speciated monoterpenes (including alpha- and beta-pinene and limonene), particle volume calculated from measured size distributions of particles less than 10 and 1 mu m in diameter (PM10-1 and PM1), particle-surface-bound polycyclic aromatic hydrocarbons (pPAHs), and aerosol mass spectrometer composition measurements, including refractory black carbon (rBC) and organic aerosol components. The PCA was complemented by bivariate polar plots showing the joint wind speed and direction dependence of air pollutant concentrations to illustrate the spatial distribution of sources in the area. Using the 95% cumulative percentage of variance criterion, 10 components were identified and categorized by source type. These included emissions by wet tailing ponds, vegetation, open pit mining operations, upgrader facilities, and surface dust. Three components correlated with IVOCs, with the largest associated with surface mining and likely caused by the unearthing and processing of raw bitumen.

Proton-transfer-reaction mass spectrometry (PTR-MS) allows the detection of a large number of trace gases in air through proton-transfer reaction with H3O+ reagent ions and detection by a mass spectrometer. Measurement sensitivities can be experimentally determined using calibration gases or calculated using the rate constant for the proton-transfer reaction, but rate constants have only been measured for a subset of compounds. Numerous theoretical approaches that describe the ion-molecule collision processes have shown how to accurately calculate capture collision rate constants between an ion and neutral molecules using the polarizability and permanent dipole moment of the molecule. Here we show that polarizability, dipole moment, and resulting capture rate constants for proton-transfer reactions of H3O+ with various different volatile organic compounds (VOCs) can be obtained using the molecular mass, elemental composition, and functionality of VOCs. The polarizabilities of a class of VOCs possessing a specific number of electronegative atoms were linearly correlated with their molecular mass. The dipole moments in a series of VOCs, in which VOCs contain a specific functional group and arbitrary residual hydrocarbon parts, can be approximated as a constant value. The capture rate constants calculated using polarizability and dipole moment, as estimated from molecular mass, elemental composition, and functional group, agreed within 10% with measured values for most VOCs. Those capture rate constants were applied to the calculation of the sensitivities of VOCs detected by our PTR-MS, taking into account the ion transmission efficiency and the degree of fragmentation of protonated VOCs observed in that instrument as well as chemical properties of the VOCs. The resulting calculated sensitivities agreed within 20-50% of those measured by PTR-MS, but several notable exceptions exist. This result shows that the neutral concentration of a VOC detected as a protonated molecule in PTR-MS can be approximated using only molecular mass, elemental composition, and functionality of the VOC. The present study is useful for all PTR-MS instruments regardless of the type of mass analyzer; however, the identification of elemental composition by high mass resolution instrumentation is important. (C) 2017 Elsevier B.V. All rights reserved.

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. (C) 2017 Elsevier Ltd. All rights reserved.

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, forwhich there are existing reporting requirements to the NPRI, were not included in the facility emission reports. The comparisons between the emission reports and measurementbased 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.

Organic acids are known to be emitted from combustion processes and are key photochemical products of biogenic and anthropogenic precursors. Despite their multiple environmental impacts, such as on acid deposition and human-ecosystem health, little is known regarding their emission magnitudes or detailed chemical formation mechanisms. In the current work, airborne measurements of 18 gas-phase low-molecular-weight organic acids were made in the summer of 2013 over the oil sands region of Alberta, Canada, an area of intense unconventional oil extraction. The data from these measurements were used in conjunction with emission retrieval algorithms to derive the total and speciated primary organic acid emission rates, as well as secondary formation rates downwind of oil sands operations. The results of the analysis indicate that approximately 12 t day(-1) of low-molecular-weight organic acids, dominated by C-1-C-5 acids, were emitted directly from off-road diesel vehicles within open pit mines. Although there are no specific reporting requirements for primary organic acids, the measured emissions were similar in magnitude to primary oxygenated hydrocarbon emissions, for which there are reporting thresholds, measured previously (approximate to 20 t day(-1) ). Conversely, photochemical production of gaseous organic acids significantly exceeded the primary sources, with formation rates of up to approximate to 184 t day(-1) downwind of the oil sands facilities. The formation and evolution of organic acids from a La-grangian flight were modelled with a box model, incorporating a detailed hydrocarbon reaction mechanism extracted from the Master Chemical Mechanism (v3.3). Despite evidence of significant secondary organic acid formation, the explicit chemical box model largely underestimated their formation in the oil sands plumes, accounting for 39, 46, 26, and 23% of the measured formic, acetic, acrylic, and propionic acids respectively and with little contributions from biogenic VOC precursors. The model results, together with an examination of the carbon mass balance between the organic acids formed and the primary VOCs emitted from oil sands operations, suggest the existence of significant missing secondary sources and precursor emissions related to oil sands and/or an incomplete mechanistic and quantitative understanding of how they are processed in the atmosphere.

The organic component is the most abundant fraction of atmospheric submicron particles, while the formation mechanisms of secondary organic aerosol (SOA) are not fully understood. The effects of sulfate seed aerosols on SOA formation were investigated with a series of experiments carried out using a 9m(3) smog chamber. The presence of FeSO4 or Fe-2(SO4)(3) seed aerosols decreased SOA yields and increased oxidation levels in both ozonolysis and OH-oxidation of a-pinene compared to that in the presence of ZnSO4 or (NH4)(2)SO4. These findings were explained by metal-mediated aerosol-phase oxidation of organics: reactive radicals were generated on FeSO4 or Fe-2(SO4)(3) seed aerosols and reacted further with the organic mass. This effect would help to explain the high O/C ratios of organics in ambient particles that thus far cannot be reproduced in laboratory and model studies. In addition, the gap in the SOA yields between experiments with different seed aerosols was more significant in OH-oxidation experiments compared to ozonolysis experiments, while the gap in estimated O/C ratios was less obvious. This may have resulted from the different chemical compositions and oxidation levels of the SOA generated in the two systems, which affect the branching ratio of functionalization and fragmentation during aerosol oxidation.

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 (similar to 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, (similar to 25 pptv in August-September), an order of magnitude increase in concentration is predicted (250600 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.

Wet deposition is not only a mechanism for removing atmospheric pollutants, but also a process which reflects loadings of atmospheric pollutants. Our previous study on wet deposition examined the effectiveness of short-term control measures on atmospheric particulate pollution, which were partly effective for organic pollutants of current input sources. In the present study, dichlorodiphenyltrichloroethanes (DDTs) and hexachlorocyclohexanes (HCHs), representative of legacy contaminants, were measured in the same samples collected throughout the entire year of 2010 in Guangzhou, a large urban center in South China. Concentrations of Sigma DDT (sum of o,p' and p,p'-DDT, o,p' and p,p'-DDE, o,p' and p,p'DDD, and p,p'-DDMU) and Sigma HCH (sum of alpha-, beta-, gamma-, and delta-HCH) in wet deposition were in the ranges of nd-69 (average: 1.8 ng L-1) and nd-150 ng L-1 (average: 5.1 ng L-1), respectively. In addition, the results of source diagnostics and backward air mass trajectories appeared to suggest the transport of antifouling paint derived DDTs from the coastal region off South China to Guangzhou. The combined wet and dry deposition flux of Sigma HCH in the first quarter (January to March) was greater than that in the fourth quarter (October to December), while those of Sigma DDT were comparable in the first and fourth quarters. Similar trends were also observed for the concentrations of Sigma HCH and Sigma DDT in aerosol samples. These results suggested the short-term pollution control measures implemented during the 16th Asian Games and 10th Asian Para Games (held in November and December 2010, respectively) did not work well for DDTs. The reduced input of HCHs during the fourth quarter was probably associated with the strict ban on lindane for food safety, which also exposed the weakness of control measures focusing mainly on the removal of atmospheric particulate matter. (C) 2017 Elsevier Ltd. All rights reserved.

Health risk of residents dwelling around e-waste recycling zones has been a global concern, but has not been adequately examined. The present study was intended to evaluate the potential health risk of residents through inhalation exposure to size-fractionated particle-bound heavy metals in a typical e waste recycling zone, South China. Anthropogenic metals (Zn, Se, Pb, Sb, As, and Cd) were predominantly enriched in fine particles (D-P < 1.8 mu m), whereas the crustal elements,(Ti, Fe, and Co) tended to accumulate in coarse particles (D-p > 1.8 mu m). Although the daily inhalation intakes of the target metals were significantly lower than those through food consumption and ingestion of house dust, the hazard quotients of total metals for adults (95% CI: 1.0-5.5) and children (95% CI: 3.0-17) were greater than 1. Moreover, the incremental lifetime cancer risks of five carcinogenic metals (Cr, Co, Ni, As, and Cd) for adults and children were 1.3 x 10(-3) (95% CI: 4.1 x 10(-4)-3.0 x 10(-3)) and 3.9 x 10(-3) (95% CI: 1.3 x 10(-3)-8.6 x 10(-3)), respectively, substantially higher than the acceptable cancer risk range of 10(-6)-10(-4). All these findings suggested that health risks were high for local residents dwelling around the e-waste recycling zone through inhalation exposure to particle-bound heavy metals, for both adults and children. (C) 2016 Elsevier B.V. All rights reserved.

Secondary organic aerosol (SOA) formation from photooxidation of alpha-pinene has been investigated in a photochemical reaction chamber under varied inorganic seed particle acidity levels at moderate relative humidity. The effect of particle acidity on SOA yield and chemical composition was examined under high-and low-NOx conditions. The SOA yield (4.2-7.6 %) increased nearly linearly with the increase in particle acidity under high-NOx conditions. In contrast, the SOA yield (28.6-36.3 %) was substantially higher under low-NOx conditions, but its dependency on particle acidity was insignificant. A relatively strong increase in SOA yield (up to 220 %) was observed in the first hour of alpha-pinene photooxidation under high-NOx conditions, suggesting that SOA formation was more effective for early alpha-pinene oxidation products in the presence of fresh acidic particles. The SOA yield decreased gradually with the increase in organic mass in the initial stage (approximately 0-1 h) under high-NOx conditions, which is likely due to the inaccessibility to the acidity over time with the coating of alpha-pinene SOA, assuming a slow particle-phase diffusion of organic molecules into the inorganic seeds. The formation of later-generation SOA was enhanced by particle acidity even under low-NOx conditions when introducing acidic seed particles after alpha-pinene photooxidation, suggesting a different acidity effect exists for alpha-pinene SOA derived from later oxidation stages. This effect could be important in the atmosphere under conditions where alpha-pinene oxidation products in the gas-phase originating in forested areas (with low NOx and SOx) are transported to regions abundant in acidic aerosols such as power plant plumes or urban regions. The fraction of oxygen-containing organic fragments (CxHyO1+ 33-35% and CxHyO2+ 16-17 %) in the total organics and the O / C ratio (0.52-0.56) of alpha-pinene SOA were lower under high-NOx conditions than those under low-NOx conditions (39-40, 17-19, and 0.61-0.64 %), suggesting that alpha-pinene SOA was less oxygenated in the studied high-NOx conditions. The fraction of nitrogen-containing organic fragments (CxHyNz+ and CxHyOzNp+) the total organics was enhanced with the increases in particle acidity under high-NOx conditions, indicating that organic nitrates may be formed heterogeneously through a mechanism catalyzed by particle acidity or that acidic conditions facilitate the partitioning of gas-phase organic nitrates into particle phase. The results of this study suggest that inorganic acidity has a significant role to play in determining various organic aerosol chemical properties such as mass yields, oxidation state, and organic nitrate content. The acidity effect being further dependent on the timescale of SOA formation is also an important parameter in the modeling of SOA.

Worldwide heavy oil and bitumen deposits amount to 9 trillion barrels of oil distributed in over 280 basins around the world(1), with Canada home to oil sands deposits of 1.7 trillion barrels(2). 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(3,4) and acid deposition(5,6). The contribution of oil sands exploration to secondary organic aerosol formation, an important component of atmospheric particulate matter that affects air quality and climate(7), 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(8), and this figure continues to grow(9). 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.

Atmospheric size-fractionated particles were collected at different heights in an e-waste recycling zone (QY) and urban Guangzhou (GZ), China and analyzed for organophosphate flame retardants (OPFRs). The total air concentrations of eight OPFRs were 130 +/- 130 and 138 +/- 127 ng m(-3) in QY and GZ, respectively. Compositional profiles of chlorinated OPFRs were different between QY and GZ, but the size distribution patterns of all OPFRs were not significantly different at different heights. Estimated atmospheric deposition fluxes of OPFRs were 51 +/- 67 and 55 +/- 13 mu gm(-2) d(-1) in QY and GZ, respectively, and the coarse particles (D-p > 1.8 mu m) dominated both the dry and wet deposition fluxes. Moreover, not all particle-bound OPFRs were inhalable and deposited in the human respiratory tract. The calculated inhalation doses of OPFRs were much lower than the reference doses, suggesting that potential health risk due to inhalation exposure to particle-bound OPFRs in the e-waste recycling zone and urban site was low. (C) 2015 Elsevier B.V. All rights reserved.

Hydrogen cyanide (HCN) is considered a marker for biomass burning emissions and is a component of vehicle exhaust. Despite its potential health impacts, vehicular HCN emissions estimates and their contribution to regional budgets are highly uncertain. In the current study, Proton Transfer Reaction Time of Flight-Mass Spectrometry (PTR-ToF-MS) was used to measure HCN emission factors from the exhaust of individual diesel, biodiesel and gasoline vehicles. Laboratory emissions data as a function of fuel type and driving mode were combined with ambient measurement data and model predictions. The results indicate that gasoline vehicles have the highest emissions of HCN (relative to diesel fuel) and that biodiesel fuel has the potential to significantly reduce HCN emissions even at realistic 5% blend levels. The data further demonstrate that gasoline direct injection (GDI) engines emit more HCN than their port fuel injection (PFI) counterparts, suggesting that the expected full transition of vehicle fleets to GDI will increase HCN emissions. Ambient measurements of HCN in a traffic dominated area of Toronto, Canada were strongly correlated to vehicle emission markers and consistent with regional air quality model predictions of ambient air HCN, indicating that vehicle emissions of HCN are the dominant source of exposure in urban areas. The results further indicate that additional work is required to quantify HCN emissions from the modern vehicle fleet, particularly in light of continuously changing engine, fuel and after-treatment technologies. Crown Copyright (C) 2016 Published by Elsevier Ltd.

The governments of Canada and Alberta are implementing a joint plan for oil sands monitoring that includes investigating emissions, transport and downwind chemistry associated with the Canadian oil sands region. As part of that effort, Environment Canada's Global Environmental Multiscale-Modelling Air-quality And CHemistry (GEM-MACH) system was reconfigured for the first time to create nested forecasts of air quality at model grid resolutions down to 2.5 km, with the highest resolution domain including the Canadian provinces of Alberta and Saskatchewan. The forecasts were used to direct an airborne research platform during a summer 2013 monitoring intensive. Subsequent work with the modelling system has included an in-depth comparison of the model predictions to monitoring network observations, and to field intensive airborne and surface supersite observations. A year of model predictions and monitoring network observations were compared, as were model and aircraft flight track values. The relative impact of different model versions (including modified emissions and feedbacks between weather and air pollution) will be discussed. Model-based predictions of indicators of human-health (i.e., Air Quality Health Index) and ecosystem (i.e. deposition of pollutants) impacts for the region will also be described.

We describe the results from online measurements of nitrated phenols using a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) with acetate as reagent ion in an oil and gas production region in January and February of 2014. Strong diurnal profiles were observed for nitrated phenols, with concentration maxima at night. Based on known markers (CH4, NOx, CO2), primary emissions of nitrated phenols were not important in this study. A box model was used to simulate secondary formation of phenol, nitrophenol (NP), and dinitrophenols (DNP). The box model results indicate that oxidation of aromatics in the gas phase can explain the observed concentrations of NP and DNP in this study. Photolysis was the most efficient loss pathway for NP in the gas phase. We show that aqueous-phase reactions and heterogeneous reactions were minor sources of nitrated phenols in our study. This study demonstrates that the emergence of new ToF-CIMS (including PTR-TOF) techniques allows for the measurement of intermediate oxygenates at low levels and these measurements improve our understanding on the evolution of primary VOCs in the atmosphere.