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The steady-state simple mass balance model was applied to natural and semi-natural terrestrial ecosystems across Canada to produce nation-wide critical loads of acidity (maximum sulfur, CLmaxS; maximum nitrogen, CLmaxN; minimum nitrogen, CLminN) and nutrient nitrogen (CLnutN) at 250 m resolution. Parameterisation of the model for Canadian ecosystems was considered with attention to the selection of the chemical criterion for damage at a site-specific resolution, with comparison between protection levels of 5 % and 20 % growth reduction (approximating commonly chosen base-cation-to-aluminum ratios of 1 and 10, respectively). Other parameters explored include modelled base cation deposition and site-specific nutrient and base cation uptake estimates based on North American tree chemistry data and tree species and biomass maps. Critical loads of acidity were estimated to be low (e.g., below 500 eq. ha−1 yr−1) for much of the country, particularly above 60° N latitude, where base cation weathering rates are low due to cold annual average temperature. Exceedances were mapped relative to annual sulfur and nitrogen deposition averaged over 2014–2016. Results show that under a conservative estimate (5 % protection level), 10 % of Canada's protected and conserved areas in the study area experienced exceedance of some level of the soil critical load of acidity, while 70 % experienced exceedance of the soil critical load of nutrient nitrogen.

This study, performed under the umbrella of the Task Force on Hemispheric Transport of Air Pollution (TF-HTAP), responds to the global and regional atmospheric modelling community's need of a mosaic emission inventory of air pollutants that conforms to specific requirements: global coverage, long time series, spatially distributed emissions with high time resolution, and a high sectoral resolution. The mosaic approach of integrating official regional emission inventories based on locally reported data, with a global inventory based on a globally consistent methodology, allows modellers to perform simulations of high scientific quality while also ensuring that the results remain relevant to policymakers. HTAP_v3, an ad hoc global mosaic of anthropogenic inventories, has been developed by integrating official inventories over specific areas (North America, Europe, Asia including Japan and South Korea) with the independent Emissions Database for Global Atmospheric Research (EDGAR) inventory for the remaining world regions. The results are spatially and temporally distributed emissions of SO2, NOx, CO, non-methane volatile organic compounds (NMVOCs), NH3, PM10, PM2.5, black carbon (BC), and organic carbon (OC), with a spatial resolution of 0.1∘ × 0.1∘ and time intervals of months and years, covering the period 2000–2018 (https://doi.org/10.5281/zenodo.7516361, Crippa, 2023, https://edgar.jrc.ec.europa.eu/dataset_htap_v3, last access: June 2023). The emissions are further disaggregated into 16 anthropogenic emitting sectors. This paper describes the methodology applied to develop such an emission mosaic, reports on source allocation, differences among existing inventories, and best practices for the mosaic compilation. One of the key strengths of the HTAP_v3 emission mosaic is its temporal coverage, enabling the analysis of emission trends over the past 2 decades. The development of a global emission mosaic over such long time series represents a unique product for global air quality modelling and for better-informed policymaking, reflecting the community effort expended by the TF-HTAP to disentangle the complexity of transboundary transport of air pollution.

We quantify methane emissions and their 2010–2017 trends by sector in the contiguous United States (CONUS), Canada, and Mexico by inverse analysis of in situ (GLOBALVIEWplus CH4 ObsPack) and satellite (GOSAT) atmospheric methane observations. The inversion uses as a prior estimate the national anthropogenic emission inventories for the three countries reported by the US Environmental Protection Agency (EPA), Environment and Climate Change Canada (ECCC), and the Instituto Nacional de Ecología y Cambio Climático (INECC) in Mexico to the United Nations Framework Convention on Climate Change (UNFCCC) and thus serves as an evaluation of these inventories in terms of their magnitudes and trends. Emissions are optimized with a Gaussian mixture model (GMM) at 0.5∘×0.625∘ resolution and for individual years. Optimization is done analytically using lognormal error forms. This yields closed-form statistics of error covariances and information content on the posterior (optimized) estimates, allows better representation of the high tail of the emission distribution, and enables construction of a large ensemble of inverse solutions using different observations and assumptions. We find that GOSAT and in situ observations are largely consistent and complementary in the optimization of methane emissions for North America. Mean 2010–2017 anthropogenic emissions from our base GOSAT + in situ inversion, with ranges from the inversion ensemble, are 36.9 (32.5–37.8) Tg a−1 for CONUS, 5.3 (3.6–5.7) Tg a−1 for Canada, and 6.0 (4.7–6.1) Tg a−1 for Mexico. These are higher than the most recent reported national inventories of 26.0 Tg a−1 for the US (EPA), 4.0 Tg a−1 for Canada (ECCC), and 5.0 Tg a−1 for Mexico (INECC). The correction in all three countries is largely driven by a factor of 2 underestimate in emissions from the oil sector with major contributions from the south-central US, western Canada, and southeastern Mexico. Total CONUS anthropogenic emissions in our inversion peak in 2014, in contrast to the EPA report of a steady decreasing trend over 2010–2017. This reflects offsetting effects of increasing emissions from the oil and landfill sectors, decreasing emissions from the gas sector, and flat emissions from the livestock and coal sectors. We find decreasing trends in Canadian and Mexican anthropogenic methane emissions over the 2010–2017 period, mainly driven by oil and gas emissions. Our best estimates of mean 2010–2017 wetland emissions are 8.4 (6.4–10.6) Tg a−1 for CONUS, 9.9 (7.8–12.0) Tg a−1 for Canada, and 0.6 (0.4–0.6) Tg a−1 for Mexico. Wetland emissions in CONUS show an increasing trend of +2.6 (+1.7 to +3.8)% a−1 over 2010–2017 correlated with precipitation.

The photolysis module in Environment and Climate Change Canada's online chemical transport model GEM-MACH (GEM: Global Environmental Multi-scale – MACH: Modelling Air quality and Chemistry) was improved to make use of the online size and composition-resolved representation of atmospheric aerosols and relative humidity in GEM-MACH, to account for aerosol attenuation of radiation in the photolysis calculation. We coupled both the GEM-MACH aerosol module and the MESSy-JVAL (Modular Earth Submodel System) photolysis module, through the use of the online aerosol modeled data and a new Mie lookup table for the model-generated extinction efficiency, absorption and scattering cross sections of each aerosol type. The new algorithm applies a lensing correction factor to the black carbon absorption efficiency (core-shell parameterization) and calculates the scattering and absorption optical depth and asymmetry factor of black carbon, sea salt, dust and other internally mixed components. We carried out a series of simulations with the improved version of MESSy-JVAL and wildfire emission inputs from the Canadian Forest Fire Emissions Prediction System (CFFEPS) for 2 months, compared the model aerosol optical depth (AOD) output to the previous version of MESSy-JVAL, satellite data, ground-based measurements and reanalysis products, and evaluated the effects of AOD calculations and the interactive aerosol feedback on the performance of the GEM-MACH model. The comparison of the improved version of MESSy-JVAL with the previous version showed significant improvements in the model performance with the implementation of the new photolysis module and with adopting the online interactive aerosol concentrations in GEM-MACH. Incorporating these changes to the model resulted in an increase in the correlation coefficient from 0.17 to 0.37 between the GEM-MACH model AOD 1-month hourly output and AERONET (Aerosol Robotic Network) measurements across all the North American sites. Comparisons of the updated model AOD with AERONET measurements for selected Canadian urban and industrial sites, specifically, showed better correlation coefficients for urban AERONET sites and for stations located further south in the domain for both simulation periods (June and January 2018). The predicted monthly averaged AOD using the improved photolysis module followed the spatial patterns of MERRA-2 reanalysis (Modern-Era Retrospective analysis for Research and Applications – version 2), with an overall underprediction of AOD over the common domain for both seasons. Our study also suggests that the domain-wide impacts of direct and indirect effect aerosol feedbacks on the photolysis rates from meteorological changes are considerably greater (3 to 4 times) than the direct aerosol optical effect on the photolysis rate calculations.

Benzene and polycyclic aromatic hydrocarbons (PAHs) are toxic air pollutants that have long been associated with motor vehicle emissions, though the importance of such emissions has never been quantified over an extended domain using a chemical transport model. Herein we present the first application of such a model (GEM-MACH-PAH) to examine the contribution of motor vehicles to benzene and PAHs in ambient air. We have applied the model over a region that is centred on Toronto, Canada, and includes much of southern Ontario and the northeastern United States. The resolution (2.5 km) was the highest ever employed by a model for these compounds in North America, and the model domain was the largest at this resolution in the world to date. Using paired model simulations that were run with vehicle emissions turned on and off (while all other emissions were left on), we estimated the absolute and relative contributions of motor vehicles to ambient pollutant concentrations. Our results provide estimates of motor vehicle contributions that are realistic as a result of the inclusion of atmospheric processing, whereas assessing changes in benzene and PAH emissions alone would neglect effects caused by shifts in atmospheric oxidation and particle–gas partitioning. A secondary benefit of our scenario approach is in its utility in representing a fleet of zero-emission vehicles (ZEVs), whose adoption is being encouraged in a variety of jurisdictions. Our simulations predicted domain-average on-road vehicle contributions to benzene and PAH concentrations of 4 %–21 % and 14 %–24 % in the spring–summer and fall–winter periods, respectively, depending on the aromatic compound. Contributions to PAH concentrations up to 50 % were predicted for the Greater Toronto Area, and the domain maximum was simulated to be 91 %. Such contributions are substantially higher than those reported at the national level in Canadian emissions inventories, and they also differ from inventory estimates at the subnational scale in the US. Our model has been run at a finer spatial scale than reported in those inventories, and furthermore includes physico-chemical processing that alters pollutant concentrations after their release. The removal of on-road vehicle emissions generally led to decreases in benzene and PAH concentrations during both periods that were studied, though atmospheric processing (such as chemical reactions and changes to particle–gas partitioning) contributed to non-linear behaviour at some locations or times of year. Such results demonstrate the added value associated with regional air quality modelling relative to examinations of emissions inventories alone. We also found that removing on-road vehicle emissions reduced spring–summertime surface O3 volume mixing ratios and fall–wintertime PM10 concentrations each by ∼10 % in the model domain, providing further air quality benefits. Toxic equivalents contributed by vehicle emissions of PAHs were found to be substantial (20 %–60 % depending on location), and this finding is particularly relevant to the study of public health in the urban areas of our model domain where human population, ambient concentrations, and traffic volumes tend to be high.

Pandora spectrometers can retrieve nitrogen dioxide (NO2) vertical column densities (VCDs) via two viewing geometries: direct Sun and zenith sky. The direct-Sun NO2 VCD measurements have high quality (0.1 DU accuracy in clear-sky conditions) and do not rely on any radiative transfer model to calculate air mass factors (AMFs); however, they are not available when the Sun is obscured by clouds. To perform NO2 measurements in cloudy conditions, a simple but robust NO2 retrieval algorithm is developed for Pandora zenith-sky measurements. This algorithm derives empirical zenith-sky NO2 AMFs from coincident high-quality direct-Sun NO2 observations. Moreover, the retrieved Pandora zenith-sky NO2 VCD data are converted to surface NO2 concentrations with a scaling algorithm that uses chemical-transport-model predictions and satellite measurements as inputs. NO2 VCDs and surface concentrations are retrieved from Pandora zenith-sky measurements made in Toronto, Canada, from 2015 to 2017. The retrieved Pandora zenith-sky NO2 data (VCD and surface concentration) show good agreement with both satellite and in situ measurements. The diurnal and seasonal variations of derived Pandora zenith-sky surface NO2 data also agree well with in situ measurements (diurnal difference within ±2 ppbv). Overall, this work shows that the new Pandora zenith-sky NO2 products have the potential to be used in various applications such as future satellite validation in moderate cloudy scenes and air quality monitoring.

Biomass burning activities can produce large quantities of smoke and result in adverse air quality conditions in regional environments. In Canada, the Environment and Climate Change Canada (ECCC) operational FireWork (v1.0) air quality forecast system incorporates near-real-time biomass burning emissions to forecast smoke plumes from fire events. The system is based on the ECCC operational Regional Air Quality Deterministic Prediction System (RAQDPS) augmented with near-real-time wildfire emissions using inputs from the Canadian Forest Service (CFS) Canadian Wildland Fire Information System (CWFIS). Recent improvements to the representation of fire behaviour and fire emissions have been incorporated into the CFS Canadian Forest Fire Emissions Prediction System (CFFEPS) v2.03. This is a bottom-up system linked to CWFIS in which hourly changes in biomass fuel consumption are parameterized with hourly forecasted meteorology at fire locations. CFFEPS has now also been connected to FireWork. In addition, a plume-rise parameterization based on fire-energy thermodynamics is used to define the smoke injection height and the distribution of emissions within a model vertical column. The new system, FireWork v2.0 (FireWork–CFFEPS), has been evaluated over North America for July–September 2017 and June–August 2018, which are both periods when western Canada experienced historical levels of fire activity with poor air quality conditions in several cities as well as other fires affecting northern Canada and Ontario. Forecast results were evaluated against hourly surface measurements for the three pollutant species used to calculate the Canadian Air Quality Health Index (AQHI), namely PM2.5, O3, and NO2, and benchmarked against the operational FireWork v1.0 system (FireWork-Ops). This comparison shows improved forecast performance and predictive skills for the FireWork–CFFEPS system. Modelled fire-plume injection heights from CFFEPS based on fire-energy thermodynamics show higher plume injection heights and larger variability. The changes in predicted fire emissions and injection height reduced the consistent over-predictions of PM2.5 and O3 seen in FireWork-Ops. On the other hand, there were minimal fire emission contributions to surface NO2, and results from FireWork–CFFEPS do not degrade NO2 forecast skill compared to the RAQDPS. Model performance statistics are slightly better for Canada than for the US, with lower errors and biases. The new system is still unable to capture the hourly variability of the observed values for PM2.5, but it captured the observed hourly variability for O3 concentration adequately. FireWork–CFFEPS also improves upon FireWork-Ops categorical scores for forecasting the occurrence of elevated air pollutant concentrations in terms of false alarm ratio (FAR) and critical success index (CSI).

We examine the potential benefits of very high resolution for air-quality forecast simulations using a nested system of the Global Environmental Multiscale – Modelling Air-quality and Chemistry chemical transport model. We focus on simulations at 1 and 2.5 km grid-cell spacing for the same time period and domain (the industrial emissions region of the Athabasca oil sands). Standard grid cell to observation station pair analyses show no benefit to the higher-resolution simulation (and a degradation of performance for most metrics using this standard form of evaluation). However, when the evaluation methodology is modified, to include a search over equivalent representative regions surrounding the observation locations for the closest fit to the observations, the model simulation with the smaller grid-cell size had the better performance. While other sources of model error thus dominate net performance at these two resolutions, obscuring the potential benefits of higher-resolution modelling for forecasting purposes, the higher-resolution simulation shows promise in terms of better aiding localized chemical analysis of pollutant plumes, through better representation of plume maxima.

This study assesses the impact of revised volatile organic compound (VOC) and organic aerosol (OA) emissions estimates in the GEM-MACH (Global Environmental Multiscale–Modelling Air Quality and CHemistry) chemical transport model (CTM) on air quality model predictions of organic species for the Athabasca oil sands (OS) region in Northern Alberta, Canada. The first emissions data set that was evaluated (base-case run) makes use of regulatory-reported VOC and particulate matter emissions data for the large oil sands mining facilities. The second emissions data set (sensitivity run) uses total facility emissions and speciation profiles derived from box-flight aircraft observations around specific facilities. Large increases in some VOC and OA emissions in the revised-emissions data set for four large oil sands mining facilities and decreases for others were found to improve the modeled VOC and OA concentration maxima in facility plumes, as shown with the 99th percentile statistic and illustrated by case studies. The results show that the VOC emission speciation profile from each oil sand facility is unique and different from standard petrochemical-refinery emission speciation profiles used for other regions in North America. A significant increase in the correlation coefficient is reported for the long-chain alkane predictions against observations when using the revised emissions based on aircraft observations. For some facilities, larger long-chain alkane emissions resulted in higher secondary organic aerosol (SOA) production, which improved OA predictions in those plumes. Overall, the use of the revised-emissions data resulted in an improvement of the model mean OA bias; however, a decrease in the OA correlation coefficient and a remaining negative bias suggests the need for further improvements to model OA emissions and formation processes. The weight of evidence suggests that the top-down emission estimation technique helps to better constrain the fugitive organic emissions in the oil sands region, which are a challenge to estimate given the size and complexity of the oil sands operations and the number of steps in the process chain from bitumen extraction to refined oil product. This work shows that the top-down emissions estimation technique may help to constrain bottom-up emission inventories in other industrial regions of the world with large sources of VOCs and OA.

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  ×  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 (NOx, 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.

Environment and Climate Change Canada's online air quality forecasting model, GEM-MACH, was extended to simulate atmospheric concentrations of benzene and seven polycyclic aromatic hydrocarbons (PAHs): phenanthrene, anthracene, fluoranthene, pyrene, benz(a)anthracene, chrysene, and benzo(a)pyrene. In the expanded model, benzene and PAHs are emitted from major point, area, and mobile sources, with emissions based on recent emission factors. Modelled PAHs undergo gas–particle partitioning (whereas benzene is only in the gas phase), atmospheric transport, oxidation, cloud processing, and dry and wet deposition. To represent PAH gas–particle partitioning, the Dachs–Eisenreich scheme was used, and we have improved gas–particle partitioning parameters based on an empirical analysis to get significantly better gas–particle partitioning results than the previous North American PAH model, AURAMS-PAH. Added process parametrizations include the particle phase benzo(a)pyrene reaction with ozone via the Kwamena scheme and gas-phase scavenging of PAHs by snow via vapour sorption to the snow surface.The resulting GEM-MACH-PAH model was used to generate the first online model simulations of PAH emissions, transport, chemical transformation, and deposition for a high-resolution domain (2.5 km grid cell spacing) in North America, centred on the PAH data-rich region of southern Ontario, Canada and the northeastern US. Model output for two seasons was compared to measurements from three monitoring networks spanning Canada and the US Average spring–summertime model results were found to be statistically unbiased from measurements of benzene and all seven PAHs. The same was true for the fall–winter seasonal mean, except for benzo(a)pyrene, which had a statistically significant positive bias. We present evidence that the benzo(a)pyrene results may be ameliorated via further improvements to particulate matter and oxidant processes and transport. Our analysis focused on four key components to the prediction of atmospheric PAH levels: spatial variability, sensitivity to mobile emissions, gas–particle partitioning, and wet deposition. Spatial variability of PAHs ∕ PM2.5 at a 2.5 km resolution was found to be comparable to measurements. Predicted ambient surface concentrations of benzene and the PAHs were found to be critically dependent on mobile emission factors, indicating the mobile emissions sector has a significant influence on ambient PAH levels in the study region. PAH wet deposition was overestimated due to additive precipitation biases in the model and the measurements. Our overall performance evaluation suggests that GEM-MACH-PAH can provide seasonal estimates for benzene and PAHs and is suitable for emissions scenario simulations.

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 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 sulfur, nitrogen and base cation R2 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 snowpack 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  ×  104 and 3.3  ×  105 km2, 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.

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 µg m−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 289 m 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.

Many stakeholders are seeking methods to reduce carbon dioxide (CO2) emissions in urban areas, but reliable, high-resolution inventories are required to guide these efforts. We present the development of a high-resolution CO2 inventory available for the Greater Toronto Area and surrounding region in Southern Ontario, Canada (area of ∼ 2.8 × 105 km2, 26 % of the province of Ontario). The new SOCE (Southern Ontario CO2 Emissions) inventory is available at the 2.5 × 2.5 km spatial and hourly temporal resolution and characterizes emissions from seven sectors: area, residential natural-gas combustion, commercial natural-gas combustion, point, marine, on-road, and off-road. To assess the accuracy of the SOCE inventory, we developed an observation–model framework using the GEM-MACH chemistry–transport model run on a high-resolution grid with 2.5 km grid spacing coupled to the Fossil Fuel Data Assimilation System (FFDAS) v2 inventories for anthropogenic CO2 emissions and the European Centre for Medium-Range Weather Forecasts (ECMWF) land carbon model C-TESSEL for biogenic fluxes. A run using FFDAS for the Southern Ontario region was compared to a run in which its emissions were replaced by the SOCE inventory. Simulated CO2 mixing ratios were compared against in situ measurements made at four sites in Southern Ontario – Downsview, Hanlan's Point, Egbert and Turkey Point – in 3 winter months, January–March 2016. Model simulations had better agreement with measurements when using the SOCE inventory emissions versus other inventories, quantified using a variety of statistics such as correlation coefficient, root-mean-square error, and mean bias. Furthermore, when run with the SOCE inventory, the model had improved ability to capture the typical diurnal pattern of CO2 mixing ratios, particularly at the Downsview, Hanlan's Point, and Egbert sites. In addition to improved model–measurement agreement, the SOCE inventory offers a sectoral breakdown of emissions, allowing estimation of average time-of-day and day-of-week contributions of different sectors. Our results show that at night, emissions from residential and commercial natural-gas combustion and other area sources can contribute > 80 % of the CO2 enhancement, while during the day emissions from the on-road sector dominate, accounting for > 70 % of the enhancement.

Traffic emissions contribute significantly to urban air pollution. Measurements were conducted over Highway 401 in Toronto, Canada, with a long-path Fourier transform infrared (FTIR) spectrometer combined with a suite of micrometeorological instruments to identify and quantify a range of air pollutants. Results were compared with simultaneous in situ observations at a roadside monitoring station, and with output from a special version of the operational Canadian air quality forecast model (GEM-MACH). Elevated mixing ratios of ammonia (0–23 ppb) were observed, of which 76 % were associated with traffic emissions. Hydrogen cyanide was identified at mixing ratios between 0 and 4 ppb. Using a simple dispersion model, an integrated emission factor of on average 2.6 g km−1 carbon monoxide was calculated for this defined section of Highway 401, which agreed well with estimates based on vehicular emission factors and observed traffic volumes. Based on the same dispersion calculations, vehicular average emission factors of 0.04, 0.36, and 0.15 g km−1 were calculated for ammonia, nitrogen oxide, and methanol, respectively.

Reported sulfur dioxide (SO2) emissions from US and Canadian sources have declined dramatically since the 1990s as a result of emission control measures. Observations from the Ozone Monitoring Instrument (OMI) on NASA's Aura satellite and ground-based in situ measurements are examined to verify whether the observed changes from SO2 abundance measurements are quantitatively consistent with the reported changes in emissions. To make this connection, a new method to link SO2 emissions and satellite SO2 measurements was developed. The method is based on fitting satellite SO2 vertical column densities (VCDs) to a set of functions of OMI pixel coordinates and wind speeds, where each function represents a statistical model of a plume from a single point source. The concept is first demonstrated using sources in North America and then applied to Europe. The correlation coefficient between OMI-measured VCDs (with a local bias removed) and SO2 VCDs derived here using reported emissions for 1° by 1° gridded data is 0.91 and the best-fit line has a slope near unity, confirming a very good agreement between observed SO2 VCDs and reported emissions. Having demonstrated their consistency, seasonal and annual mean SO2 VCD distributions are calculated, based on reported point-source emissions for the period 1980–2015, as would have been seen by OMI. This consistency is further substantiated as the emission-derived VCDs also show a high correlation with annual mean SO2 surface concentrations at 50 regional monitoring stations.

SnTe is a topological crystalline insulator that exhibits crystal symmetry protected topological surface states (SS), which are useful for the development of novel devices, such as low-dissipation transistors. However, major obstacles remain to probe the SS and realize the application of SnTe and other topological insulators. Due to unintentional doping by Sn vacancies, bulk conduction may overwhelm the transport through SS in SnTe. Synthesis of SnTe films thin enough to suppress bulk conduction has proven difficult due to the formation of discontinuous domain structures. By introducing a novel deposition method that builds upon molecular beam epitaxy, we achieve ultrathin continuous films of single-orientation SnTe (001) on SrTiO3 (STO) (001) substrates. We separate the carrier concentrations in the bulk and in the SS and discover that conduction through the SS dominates (a majority of hole carriers occupy the SS) in films thinner than 40 unit cells, with a large temperature independent hole density of SS nS = 5 × 1014 cm−2. Unlike the depletion of SS carriers observed at the vacuum/SnTe interface that inhibits topological behavior, we show that SS carriers are buried and protected from depletion at the SnTe/STO interface, which is enabled by the relatively large bandgap of STO and its favorable band alignment with SnTe. This work provides an important pathway for probing and realizing SS transport in SnTe and other TIs even when bulk conduction coexists.

Sulfur dioxide (SO2) measurements from the Ozone Monitoring Instrument (OMI) satellite sensor processed with the new principal component analysis (PCA) algorithm were used to detect large point emission sources or clusters of sources. The total of 491 continuously emitting point sources releasing from about 30 kt yr−1 to more than 4000 kt yr−1 of SO2 per year have been identified and grouped by country and by primary source origin: volcanoes (76 sources); power plants (297); smelters (53); and sources related to the oil and gas industry (65). The sources were identified using different methods, including through OMI measurements themselves applied to a new emission detection algorithm, and their evolution during the 2005–2014 period was traced by estimating annual emissions from each source. For volcanic sources, the study focused on continuous degassing, and emissions from explosive eruptions were excluded. Emissions from degassing volcanic sources were measured, many for the first time, and collectively they account for about 30 % of total SO2 emissions estimated from OMI measurements, but that fraction has increased in recent years given that cumulative global emissions from power plants and smelters are declining while emissions from oil and gas industry remained nearly constant. Anthropogenic emissions from the USA declined by 80 % over the 2005–2014 period as did emissions from western and central Europe, whereas emissions from India nearly doubled, and emissions from other large SO2-emitting regions (South Africa, Russia, Mexico, and the Middle East) remained fairly constant. In total, OMI-based estimates account for about a half of total reported anthropogenic SO2 emissions; the remaining half is likely related to sources emitting less than 30 kt yr−1 and not detected by OMI.

A parameter called the scavenging coefficient Λ is widely used in aerosol chemical transport models (CTMs) to describe below-cloud scavenging of aerosol particles by rain and snow. However, uncertainties associated with available size-resolved theoretical formulations for Λ span one to two orders of magnitude for rain scavenging and nearly three orders of magnitude for snow scavenging. Two recent reviews of below-cloud scavenging of size-resolved particles recommended that the upper range of the available theoretical formulations for Λ should be used in CTMs based on uncertainty analyses and comparison with limited field experiments. Following this recommended approach, a new semi-empirical parameterization for size-resolved Λ has been developed for below-cloud scavenging of atmospheric aerosol particles by both rain (Λrain) and snow (Λsnow). The new parameterization is based on the 90th percentile of Λ values from an ensemble data set calculated using all possible "realizations" of available theoretical Λ formulas and covering a large range of aerosol particle sizes and precipitation intensities (R). For any aerosol particle size of diameter d, a strong linear relationship between the 90th-percentile log10 (Λ) and log10 (R), which is equivalent to a power-law relationship between Λ and R, is identified. The log-linear relationship, which is characterized by two parameters (slope and y intercept), is then further parameterized by fitting these two parameters as polynomial functions of aerosol size d. A comparison of the new parameterization with limited measurements in the literature in terms of the magnitude of Λ and the relative magnitudes of Λrain and Λsnow suggests that it is a reasonable approximation. Advantages of this new semi-empirical parameterization compared to traditional theoretical formulations for Λ include its applicability to below-cloud scavenging by both rain and snow over a wide range of particle sizes and precipitation intensities, ease of implementation in any CTM with a representation of size-distributed particulate matter, and a known representativeness, based on the consideration in its development, of all available theoretical formulations and field-derived estimates for Λ (d) and their associated uncertainties.

The balance between turbulent transport and emissions is a key issue in understanding the formation of O3 and particulate matter with diameters less than 2.5 μm (PM2.5). Discrepancies between observed and simulated concentrations for these species have, in the past, been ascribed to insufficient turbulent mixing, particularly for atmospherically stable environments. This assumption may be simplistic – turbulent mixing deficiencies may explain only part of these discrepancies, and as turbulence parameterizations are improved, the timing of primary PM2.5 emissions may play a much more significant role in the further reduction of model error. In a study of these issues, two regional air-quality models, the Community Multi-scale Air Quality model (CMAQ, version 4.6) and A Unified Regional Air-quality Modelling System (AURAMS, version 1.4.2), were compared to observations for a domain in north-western North America. The air-quality models made use of the same emissions inventory, emissions processing system, meteorological driving model, and model domain, map projection and horizontal grid, eliminating these factors as potential sources of discrepancies between model predictions. The initial statistical comparison between the models and monitoring network data showed that AURAMS' O3 simulations outperformed those of this version of CMAQ4.6, while CMAQ4.6 outperformed AURAMS for most PM2.5 statistical measures. A process analysis of the models revealed that many of the differences between the models' results could be attributed to the strength of turbulent diffusion, via the choice of an a priori lower limit in the magnitude of vertical diffusion coefficients, with AURAMS using 0.1 m2 s−1 and CMAQ4.6 using 1.0 m2 s−1. The use of the larger CMAQ4.6 value for the lower limit of vertical diffusivity within AURAMS resulted in a similar performance for the two models (with AURAMS also showing improved PM2.5, yet degraded O3, and a similar time series as CMAQ4.6). The differences between model results were most noticeable at night, when the higher minimum turbulent diffusivity resulted in an erroneous secondary peak in predicted night-time O3. A spatially invariant and relatively high lower limit in diffusivity could not reduce errors in both O3 and PM2.5 fields, implying that other factors aside from the strength of turbulence might be responsible for the PM2.5 over-predictions. Further investigation showed that the magnitude, timing and spatial allocation of area source emissions could result in improvements to PM2.5 performance with minimal O3 performance degradation. AURAMS was then used to investigate a land-use-dependant lower limit in diffusivity of 1.0 m2 s−1 in urban regions, linearly scaling to 0.01 m2s−1 in rural areas, as employed in CMAQ5.0.1. This strategy was found to significantly improve mean statistics for PM2.5 throughout the day and mean O3 statistics at night, while significantly degrading (halving) midday PM2.5 correlation coefficients and slope of observed to model simulations. Time series of domain-wide model error statistics aggregated by local hour were shown to be a useful tool for performance analysis, with significant variations in performance occurring at different hours of the day. The use of the land-use-dependant lower limit in diffusivity was also shown to reduce the model's sensitivity to the temporal allocation of its emissions inputs. The modelling scenarios suggest that while turbulence plays a key role in O3 and PM2.5 formation in urban regions, and in their downwind transport, the spatial and temporal allocation of primary PM2.5 emissions also has a potentially significant impact on PM2.5 concentration levels. The results show the complex nature of the interactions between turbulence and emissions, and the potential of the strength of the former to mask the impact of changes in the latter.

A bidirectional air–surface exchange scheme for atmospheric ammonia was incorporated into the Stochastic Time-Inverted Lagrangian Transport air quality model (STILT-Chem v0.8). STILT-Chem v0.8 was then applied to simulate atmospheric ammonia concentrations at 53 measurement sites in the province of Ontario, Canada for a six-month period from 1 June to 30 November 2006. In addition to the bidirectional scheme, two unidirectional dry deposition schemes were tested. Comparisons of modeled ammonia concentrations against observations show that all three schemes can reasonably predict observations. For sites with low observed ammonia concentrations, the bidirectional scheme clearly overestimated ammonia concentrations during crop-growing season. Although all three schemes tended to underestimate ammonia concentrations after mid-October and for sites with elevated observed concentrations, mainly due to underestimated NH3 emission inventory after mid-October and/or underestimated emission potentials for those sites, the bidirectional scheme performed better because of its introduction of compensation points into the flux calculation parameterization. In addition to uncertainties in the emission inventory, the results of additional sensitivity tests suggest that uncertainties in the input values of emission potentials in the bidirectional scheme greatly affect the accuracy of modeled ammonia concentrations. The use of much larger emission potentials in the bidirectional scheme and larger anthropogenic NH3 emission after mid-October than provided in the model emissions files is needed for accurate prediction of elevated ammonia concentrations at intensive agricultural locations.

The offline Eulerian AURAMS (A Unified Regional Air quality Modelling System) chemical transport model was adapted to simulate airborne concentrations of seven PAHs (polycyclic aromatic hydrocarbons): phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene + triphenylene, and benzo[a]pyrene. The model was then run for the year 2002 with hourly output on a grid covering southern Canada and the continental USA with 42 km horizontal grid spacing. Model predictions were compared to ~5000 24 h-average PAH measurements from 45 sites, most of which were located in urban or industrial areas. Eight of the measurement sites also provided data on particle/gas partitioning which had been modelled using two alternative schemes. This is the first known regional modelling study for PAHs over a North American domain and the first modelling study at any scale to compare alternative particle/gas partitioning schemes against paired field measurements. The goal of the study was to provide output concentration maps of use to assessing human inhalation exposure to PAHs in ambient air. Annual average modelled total (gas + particle) concentrations were statistically indistinguishable from measured values for fluoranthene, pyrene and benz[a]anthracene whereas the model underestimated concentrations of phenanthrene, anthracene and chrysene + triphenylene. Significance for benzo[a]pyrene performance was close to the statistical threshold and depended on the particle/gas partitioning scheme employed. On a day-to-day basis, the model simulated total PAH concentrations to the correct order of magnitude the majority of the time. The model showed seasonal differences in prediction quality for volatile species which suggests that a missing emission source such as air–surface exchange should be included in future versions. Model performance differed substantially between measurement locations and the limited available evidence suggests that the model's spatial resolution was too coarse to capture the distribution of concentrations in densely populated areas. A more detailed analysis of the factors influencing modelled particle/gas partitioning is warranted based on the findings in this study.

Theoretical parameterizations for the size-resolved scavenging coefficient for atmospheric aerosol particles scavenged by snow (Λsnow) need assumptions regarding (i) snow particle–aerosol particle collection efficiency E, (ii) snow-particle size distribution N(Dp), (iii) snow-particle terminal velocity VD, and (iv) snow-particle cross-sectional area A. Existing formulas for these parameters are reviewed in the present study, and uncertainties in Λsnow caused by various combinations of these parameters are assessed. Different formulations of E can cause uncertainties in Λsnow of more than one order of magnitude for all aerosol sizes for typical snowfall intensities. E is the largest source of uncertainty among all the input parameters, similar to rain scavenging of atmospheric aerosols (Λrain) as was found in a previous study by Wang et al. (2010). However, other parameters can also cause significant uncertainties in Λsnow, and the uncertainties from these parameters are much larger than for Λrain. Specifically, different N(Dp) formulations can cause one-order-of-magnitude uncertainties in Λsnow for all aerosol sizes, as is also the case for a combination of uncertainties from both VD and A. Assumptions about dominant snow-particle shape (and thus different VD and A) will cause an uncertainty of up to one order of magnitude in the calculated scavenging coefficient. In comparison, uncertainties in Λrain from N(Dp) are smaller than a factor of 5, and those from VD are smaller than a factor of 2. As expected, Λsnow estimated from empirical formulas generated from field measurements falls in the upper range of, or is higher than, the theoretically estimated values, which can be explained by additional processes/mechanisms that influence field-derived Λsnow but that are not considered in the theoretical Λsnow formulas. Predicted aerosol concentrations obtained by using upper range vs. lower range of Λsnow values (a difference of around two orders of magnitude in Λsnow) can differ by a factor of 2 for just a one-centimetre snowfall (liquid water equivalent of approximately 1 mm). Based on the median and upper range of theoretically generated Λsnow and Λsnow values, it is likely that, for typical rain and snow events, the removal of atmospheric aerosol particles by snow is more effective than removal by rain for equivalent precipitation amounts, although a firm conclusion requires much more evidence.

This study is conducted in the framework of the Air Quality Modelling Evaluation International Initiative (AQMEII) and aims at the operational evaluation of an ensemble of 12 regional-scale chemical transport models used to predict air quality over the North American (NA) and European (EU) continents for 2006. The modelled concentrations of ozone and CO, along with the meteorological fields of wind speed (WS) and direction (WD), temperature (T), and relative humidity (RH), are compared against high-quality in-flight measurements collected by instrumented commercial aircraft as part of the Measurements of OZone, water vapour, carbon monoxide and nitrogen oxides by Airbus In-service airCraft (MOZAIC) programme. The evaluation is carried out for five model domains positioned around four major airports in NA (Portland, Philadelphia, Atlanta, and Dallas) and one in Europe (Frankfurt), from the surface to 8.5 km. We compare mean vertical profiles of modelled and measured variables for all airports to compute error and variability statistics, perform analysis of altitudinal error correlation, and examine the seasonal error distribution for ozone, including an estimation of the bias introduced by the lateral boundary conditions (BCs). The results indicate that model performance is highly dependent on the variable, location, season, and height (e.g. surface, planetary boundary layer (PBL) or free troposphere) being analysed. While model performance for T is satisfactory at all sites (correlation coefficient in excess of 0.90 and fractional bias ≤ 0.01 K), WS is not replicated as well within the PBL (exhibiting a positive bias in the first 100 m and also underestimating observed variability), while above 1000 m, the model performance improves (correlation coefficient often above 0.9). The WD at NA airports is found to be biased in the PBL, primarily due to an overestimation of westerly winds. RH is modelled well within the PBL, but in the free troposphere large discrepancies among models are observed, especially in EU. CO mixing ratios show the largest range of modelled-to-observed standard deviations of all the examined species at all heights and for all airports. Correlation coefficients for CO are typically below 0.6 for all sites and heights, and large errors are present at all heights, particularly in the first 250 m. Model performance for ozone in the PBL is generally good, with both bias and error within 20%. Profiles of ozone mixing ratios depend strongly on surface processes, revealed by the sharp gradient in the first 2 km (10 to 20 ppb km−1). Modelled ozone in winter is biased low at all locations in the NA, primarily due to an underestimation of ozone from the BCs. Most of the model error in the PBL is due to surface processes (emissions, transport, photochemistry), while errors originating aloft appear to have relatively limited impact on model performance at the surface. Suggestions for future work include interpretation of the model-to-model variability and common sources of model bias, and linking CO and ozone bias to the bias in the meteorological fields. Based on the results from this study, we suggest possible in-depth, process-oriented and diagnostic investigations to be carried out next.

A new chemistry module that simulates atmospheric ammonia (NH3) and ammonium (NH+4) was incorporated into a backward-in-time stochastic Lagrangian air quality model (STILT-Chem) that was originally developed to simulate the concentrations of a variety of gas-phase species at receptors. STILT-Chem simulates the transport of air parcels backward in time using ensembles of fictitious particles with stochastic motions, while accounting for emissions, deposition and chemical transformation forward in time along trajectories identified by the backward-in-time simulations. The incorporation of the new chemistry module allows the model to simulate not only gaseous species, but also multi-phase species involving NH3 and NH+4. The model was applied to simulate concentrations of NH3 and particulate NH+4 at six sites in the Canadian province of Ontario for a six-month period in 2006. The model-predicted concentrations of NH3 and particulate NH+4 were compared with observations, which show broad agreement between simulated concentrations and observations. Since the model is based on back trajectories, the influence of each major process such as emission, deposition and chemical conversion on the concentration of a modeled species at a receptor can be determined for every upstream location at each time step. This makes it possible to quantitatively investigate the upstream processes affecting receptor concentrations. The modeled results suggest that the concentrations of NH3 at those sites were significantly and frequently affected by Ohio, Iowa, Minnesota, Michigan, Wisconsin, southwestern Ontario and nearby areas. NH3 is mainly contributed by emission sources whereas particulate NH+4 is mainly contributed by the gas-to-aerosol chemical conversion of NH3. Dry deposition is the largest removal process for both NH3 and particulate NH+4. This study revealed the contrast between agricultural versus forest sites. Not only were emissions of NH3 higher, but removal mechanisms (especially chemical loss for NH3 and dry deposition for NH+4) were less efficient for agricultural sites. This combination explains the significantly higher concentrations of NH3 and particulate NH+4 observed at agricultural sites.

Observations from the 2007 Border Air Quality and Meteorology Study (BAQS-Met 2007) in Southern Ontario, Canada, were used to evaluate predictions of primary organic aerosol (POA) and two other carbonaceous species, black carbon (BC) and carbon monoxide (CO), made for this summertime period by Environment Canada's AURAMS regional chemical transport model. Particle component-based factor analysis was applied to aerosol mass spectrometer measurements made at one urban site (Windsor, ON) and two rural sites (Harrow and Bear Creek, ON) to derive hydrocarbon-like organic aerosol (HOA) factors. A novel diagnostic model evaluation was performed by investigating model POA bias as a function of HOA mass concentration and indicator ratios (e.g. BC/HOA). Eight case studies were selected based on factor analysis and back trajectories to help classify model bias for certain POA source types. By considering model POA bias in relation to co-located BC and CO biases, a plausible story is developed that explains the model biases for all three species. At the rural sites, daytime mean PM1 POA mass concentrations were under-predicted compared to observed HOA concentrations. POA under-predictions were accentuated when the transport arriving at the rural sites was from the Detroit/Windsor urban complex and for short-term periods of biomass burning influence. Interestingly, the daytime CO concentrations were only slightly under-predicted at both rural sites, whereas CO was over-predicted at the urban Windsor site with a normalized mean bias of 134%, while good agreement was observed at Windsor for the comparison of daytime PM1 POA and HOA mean values, 1.1 μg m−3 and 1.2 μg m−3, respectively. Biases in model POA predictions also trended from positive to negative with increasing HOA values. Periods of POA over-prediction were most evident at the urban site on calm nights due to an overly-stable model surface layer. This model behaviour can be explained by a combination of model under-estimation of vertical mixing at the urban location, under-representation of PM emissions for on-road traffic exhaust along major urban roads and highways, and a more structured allocation of area POA sources such as food cooking and dust emissions to urban locations. A downward trend in POA bias was also observed at the urban site as a function of the BC/HOA indicator ratio, suggesting a possible association of POA under-prediction with under-representation of diesel combustion sources. An investigation of the emission inventories for the province of Ontario and the nearby US state of Indiana also suggested that the top POA area emission sources (food cooking, organic-bound to dust, waste disposal burning) dominated over mobile and point sources, again consistent with a mobile under-estimation. We conclude that more effort should be placed at reducing uncertainties in the treatment of several large POA emission sources, in particular food cooking, fugitive dust, waste disposal burning, and on-road traffic sources, and especially their spatial surrogates and temporal profiles. This includes using higher spatial resolution model grids to better resolve the urban road network and urban food cooking locations. We also recommend that additional sources of urban-scale vertical mixing in the model, such as a stronger urban heat island effect and vehicle-induced turbulence, would help model predictions at urban locations, especially at night time.

A new global real-time Lagrangian diagnostic system for stratosphere-troposphere exchange (STE) developed for Environment Canada (EC) has been delivering daily archived data since July 2010. The STE calculations are performed following the Lagrangian approach proposed in Bourqui (2006) using medium-range, high-resolution operational global weather forecasts. Following every weather forecast, trajectories are started from a dense three-dimensional grid covering the globe, and are calculated forward in time for six days of the forecast. All trajectories crossing either the dynamical tropopause (±2 PVU) or the 380 K isentrope and having a residence time greater than 12 h are archived, and also used to calculate several diagnostics. This system provides daily global STE forecasts that can be used to guide field campaigns, among other applications. The archived data set offers unique high-resolution information on transport across the tropopause for both extra-tropical hemispheres and the tropics. This will be useful for improving our understanding of STE globally, and as a reference for the evaluation of lower-resolution models. This new data set is evaluated here against measurements taken during a balloon sonde campaign with daily launches from three stations in eastern Canada (Montreal, Egbert, and Walsingham) for the period 12 July to 4 August 2010. The campaign found an unexpectedly high number of observed stratospheric intrusions: 79% (38%) of the profiles appear to show the presence of stratospheric air below than 500 hPa (700 hPa). An objective identification algorithm developed for this study is used to identify layers in the balloon-sonde profiles affected by stratospheric air and to evaluate the Lagrangian STE forecasts. We find that the predictive skill for the overall intrusion depth is very good for intrusions penetrating down to 300 and 500 hPa, while it becomes negligible for intrusions penetrating below 700 hPa. Nevertheless, the statistical representation of these deep intrusions is reasonable, with an average bias of 24%. Evaluation of the skill at representing the detailed structures of the stratospheric intrusions shows good predictive skill down to 500 hPa, reduced predictive skill between 500 and 700 hPa, and none below. A significant low statistical bias of about 30% is found in the layer between 500 to 700 hPa. However, analysis of missed events at one site, Montreal, shows that 70% of them coincide with candidate clusters of trajectories that pass through Montreal, but that are too dispersed to be detected in the close neighbourhood of the station. Within the limits of this study, this allows us to expect a negligible bias throughout the troposphere in the spatially averaged STE frequency derived from this data set, for example in climatological maps of STE mass fluxes. This first evaluation is limited to eastern Canada in one summer month with a high frequency of stratospheric intrusions, and further work is needed to evaluate this STE data set in other months and locations.

Existing theoretical formulations for the size-resolved scavenging coefficient Λ(d) for atmospheric aerosol particles scavenged by rain predict values lower by one to two orders of magnitude than those estimated from field measurements of particle-concentration changes for particles smaller than 3 μm in diameter. Vertical turbulence is not accounted for in the theoretical formulations of Λ(d) but does contribute to the field-derived estimates of Λ(d) due to its influence on the overall concentration changes of aerosol particles in the layers undergoing impaction scavenging. A detailed one-dimensional cloud microphysics model has been used to simulate rain production and below-cloud particle scavenging, and to quantify the contribution of turbulent diffusion to the overall Λ(d) values calculated from particle concentration changes. The relative contribution of vertical diffusion to below-cloud scavenging is found to be largest for submicron particles under weak precipitation conditions. The discrepancies between theoretical and field-derived Λ(d) values can largely be explained by the contribution of vertical diffusion to below-cloud particle scavenging for all particles larger than 0.01 μm in diameter for which field data are available. The results presented here suggest that the current theoretical framework for Λ(d) can provide a reasonable approximation of below-cloud aerosol particle scavenging by rain in size-resolved aerosol transport models if vertical diffusion is also considered by the models.