Advanced receptor modeling of near–real–time, ambient PM2.5 and its associated components collected at an urban–industrial site in Toronto, Ontario

AbstractPM2.5 and other atmospheric pollutants were continuously monitored at high time resolution for 1 year at an urban–industrial location in Toronto, ON, Canada's largest city. The data collected for these pollutants were examined to determine seasonal trends and potential sources. Advanced receptor models including residence time weighted concentration (RTWC) and simplified quantitative transport bias analysis (sQTBA) trajectory ensemble models (TEM) and conditional probability function (CPF) were applied to these data to identify potential local and regional sources of pollution impacting this receptor site. Seasonal trends showed that concentrations of PM2.5 were more frequently high in winter than in any other season. Median concentrations of lead and arsenic were highest in fall while median levels of chromium were not significantly different over the four seasons. The black carbon–derived measurement commonly known as Delta C (i.e., BC370nm–BC880nm) had its greatest abundance in winter and lowest levels in summer. The seasonality of Delta C is indicative of the impact of residential wood combustion near the receptor site. CPF indicated that lead and iron had the most unidirectional radial plots with sectors located west–southwest of the receptor being the most likely local source regions. Winter CPF for Delta C is almost of equal strengths in all directions suggestive of near–uniform isotropic local impacts. The sQTBA model provided the most satisfactory spatial representation of impacting sources. The strongest sources of PM2.5 identified by the sQTBA model were both local and transboundary in origin. More potential source regions were found in winter and summer than in spring and fall

Source apportionment of ambient PM collected at three sites in an urban-industrial area with multi-time resolution factor analyses.

Chemical speciation data for PM10, collected for annual trend analyses of health-relevant species, at three receptor sites in a highly industrialized area (IJmond) in the Netherlands were used in a multi-time resolution receptor model (ME-2) to identify the PM10 sources in this area. Despite the available data not being optimized for receptor modelling, five-factor solutions were obtained for all sites based on independent PMF analysis on PM10 data from the three sites (IJM, WAZ and BEV). Four factors were common to all three sites: nitrate-sulphate (average percentage contributions to PM10: IJM: 35.3 %, WAZ: 37.7 %, and BEV: 36.3 %); sea salt (20.2 %, 23.7 %, 15.2 %); industrial (8.1 %, 11.0 %, 18.1 %) and brake wear/traffic (31.4 %, 21.2 %, 20.6 %). At WAZ, a local/site-specific factor containing most of the PAH measurements was found (6.4 %) while a crustal matter factor was resolved at IJM (7.6 %) and BEV (9.8 %). Additionally, sludge-drying was a potential source of the marker species in the industrial factor at WAZ. Bootstrapping (BS) and factor displacement (DISP) were applied to the factor profiles in this work for error estimation. In general, the factor profiles at all three sites had very small intervals from both BS and DISP methods. To our knowledge, this is the first time DISP was applied in a complex model such as the multi-time resolution model. Most of the measured metal and PAH concentrations found in the IJmond area during the 2017-2019 period had local sources, with significant contributions from several processes related to the steel industry. This study shows that available detailed PM10 chemical speciation data, although primarily collected for annual trend analyses of health-relevant species, could also be used in receptor modelling by applying a multi-time framework. We propose general recommendations for the optimization of the measurement strategy for source apportionment of PM in areas with similar urban-industrial land use

Source apportionment of ambient PM collected at three sites in an urban-industrial area with multi-time resolution factor analyses.

Chemical speciation data for PM10, collected for annual trend analyses of health-relevant species, at three receptor sites in a highly industrialized area (IJmond) in the Netherlands were used in a multi-time resolution receptor model (ME-2) to identify the PM10 sources in this area. Despite the available data not being optimized for receptor modelling, five-factor solutions were obtained for all sites based on independent PMF analysis on PM10 data from the three sites (IJM, WAZ and BEV). Four factors were common to all three sites: nitrate-sulphate (average percentage contributions to PM10: IJM: 35.3 %, WAZ: 37.7 %, and BEV: 36.3 %); sea salt (20.2 %, 23.7 %, 15.2 %); industrial (8.1 %, 11.0 %, 18.1 %) and brake wear/traffic (31.4 %, 21.2 %, 20.6 %). At WAZ, a local/site-specific factor containing most of the PAH measurements was found (6.4 %) while a crustal matter factor was resolved at IJM (7.6 %) and BEV (9.8 %). Additionally, sludge-drying was a potential source of the marker species in the industrial factor at WAZ. Bootstrapping (BS) and factor displacement (DISP) were applied to the factor profiles in this work for error estimation. In general, the factor profiles at all three sites had very small intervals from both BS and DISP methods. To our knowledge, this is the first time DISP was applied in a complex model such as the multi-time resolution model. Most of the measured metal and PAH concentrations found in the IJmond area during the 2017-2019 period had local sources, with significant contributions from several processes related to the steel industry. This study shows that available detailed PM10 chemical speciation data, although primarily collected for annual trend analyses of health-relevant species, could also be used in receptor modelling by applying a multi-time framework. We propose general recommendations for the optimization of the measurement strategy for source apportionment of PM in areas with similar urban-industrial land use

Spatially Resolved Source Apportionment of Industrial VOCs Using a Mobile Monitoring Platform

Industrial emissions of volatile organic compounds (VOCs) directly impact air quality downwind of facilities and contribute to regional ozone and secondary organic aerosol production. Positive matrix factorization (PMF) is often used to apportion VOCs to their respective sources using measurement data collected at fixed sites, for example air quality monitoring stations. Here, we apply PMF analysis to high time-resolution VOC measurement data collected both while stationary and while moving using a mobile monitoring platform. The stationary monitoring periods facilitated the extraction of representative industrial VOC source profiles while the mobile monitoring periods were critical for the spatial identification of VOC hotspots. Data were collected over five days in a heavily industrialized region of southwestern Ontario containing several refineries, petrochemical production facilities and a chemical waste disposal facility. Factors associated with petroleum, chemical waste and rubber production were identified and ambient mixing ratios of selected aromatic, unsaturated and oxygenated VOCs were apportioned to local and background sources. Fugitive emissions of benzene, highly localized and predominantly associated with storage, were found to be the dominant local contributor to ambient benzene mixing ratios measured while mobile. Toluene and substituted aromatics were predominantly associated with refining and traffic, while methyl ethyl ketone was linked to chemical waste handling. The approach described here facilitates the apportionment of VOCs to their respective local industrial sources at high spatial and temporal resolution. This information can be used to identify problematic source locations and to inform VOC emission abatement strategies

Source apportionment of ambient PM in an industrialized city using dispersion-normalized, multi-time resolution factor analyses.

Ambient fine particulate matter (PM2.5) data were collected in the lower City of Hamilton, Ontario to apportion the sources of this pollutant over an 18-month period. Hamilton has complex topographical features that may result in worsened air pollution within the lower city, thus, dispersion-normalized, multi-time resolution factor analysis (DN-MT-FA) was used to identify and quantify contributions of factors in a manner that reduced the influence of local meteorology. These factors were secondary organic aerosols type 1 (SOA_1), particulate nitrate (pNO3), particulate sulphate (pSO4), primary traffic organic matter (PTOM), Steel/metal processing and vehicular road dust emissions (Steel & Mobile) and, secondary organic aerosols type 2 (SOA_2) with origins ranging from mainly regional to mainly local. Factors that were mainly local (PTOM, Steel & Mobile, SOA_2) contributed up to 17% of the average PM2.5 mass while mixed local/regional factors (pNO3, pSO4) made up 43% on average, indicating the potential for further reduction of harmful PM concentrations locally. Of particular interest from a health protection perspective, was the composition of PM2.5 on days when an exceedance of the 24-hr WHO air quality guideline for this pollutant was observed. In general, SOA_1 was found to drive summer exceedances while pNO3 dominated in the winter. During the summer period, SOA_1 was attributable to wildfires in the northern parts of Canada while local traffic sources in winter contributed to the high levels of pNO3. While local, industrial factors only had minor relative mass contributions during exceedances, they are high in highly oxidized organic species (SOA_2) and toxic metals (Steel & Mobile). Thus, they are likely to have more impacts on human health. The methods and results described in this work will be useful in understanding prevalent sources of particulate matter pollution in the ambient air in the presence of complex topography and meteorological effects

Effect of industrialization on the differences in sources and composition of ambient PM in two Southern Ontario locations.

PM2.5 was sampled over a seven-year period (2013-2019) at two locations ∼50 km apart in Southern Ontario (concurrently for five years: 2015-2019). One is a heavily industrialized site (Hamilton), while the other was a rural site (Simcoe). To assess the impact of industrialization on the composition and sources of PM affecting air quality in these two locations, positive matrix factorization coupled with dispersion normalization (DN-PMF) was used to identify six and eight factors at Simcoe and Hamilton, respectively. The Simcoe factors in order of diminishing PM mass contribution were: particulate sulphate (pSO4), secondary organic aerosol (SOA), crustal matter, particulate nitrate (pNO3), biomass burning, and vehicular emissions. At Hamilton, the effects of industrialization were observed by the ∼36% higher average ambient PM2.5 concentration for the study period as well as the presence of factors unique to metallurgy, i.e., coking and steelmaking, compared to Simcoe. The coking and steelmaking factors contributed ∼15% to the PM mass at Hamilton. Seasonal variants of appropriate nonparametric trend tests with the associated slopes (Sen's) were used to assess statistically significant changes in the factor contributions to PM2.5 over time. Specifically at Hamilton, a significant decline in PM contributions was noted for coking (-0.03 μg/m³/yr or -4.1%/yr) while steelmaking showed no statistically significant decline over the study period. Other factors at Hamilton that showed statistically significant declines over the study period were: pSO4 (-0.27 μg/m³/yr or -12.6%/yr), biomass burning (-0.05 μg/m³/yr or -9.02%/yr), crustal matter (-0.03 μg/m³/yr or -5.28%/yr). These factors mainly accounted for the significant decline in PM2.5 over the study period (-0.35 μg/m³/yr or -4.24%/yr). This work shows the importance of long-term monitoring in assessing the unique contributions and temporal changes of industrialization on air quality in Ontario and similarly affected locations

Heavy metals in the near-road environment: Results of semi-continuous monitoring of ambient particulate matter in the greater Toronto and Hamilton area

Six heavy metals - Mn, Fe, Cu, Zn, Se, and Pb among other elemental species were monitored in ambient PM2.5 at three near-road ambient air monitoring locations in the Greater Toronto and Hamilton Area (GTHA) with semi-continuous X-ray fluorescence (XRF) instrumentation over a period spanning January 1st, 2014 to June 30th, 2017. Land use in these air monitoring locations includes residential, institutional and industrial, thus, air monitoring is representative of typical urban areas. Ambient metal concentrations were found below Ontario's ambient air quality criteria. Temporal trends however indicated that high concentrations of Fe and Cu correlated with peak commuting and working hours on weekdays. To further understand the potential sources of these metals, scatterplots of metal concentrations and criteria pollutant gases were made on weekdays and weekends. These scatterplots reveal edges that are due to multiple sources of these metals. When these scatterplots are colour-coded by the hour of day, edges associated with the morning rush hour on weekdays for Fe and Cu (also Mn and Zn to a lesser extent) likely due to traffic-related emissions are more clearly-delineated from other edges arising from industrial or regional sources that were prevalent during other times of the day. Finally, an auxiliary receptor model was used to explore the potential source regions of these metals. It was observed that Mn, Fe and Cu had intense potential source regions within the GTHA on weekdays that diminished on the weekends, and in the case of Fe, the potential source regions in the GTHA were sensitive to the morning rush hour period, indicating that traffic-related emissions are a major source of Fe. Other metals, especially Zn, Se and Pb have source regions that are less sensitive to the morning rush hour period and are usually situated outside the GTHA. Keywords: Heavy metals, Near-road, Non-parametric statistics, PM2.5, sQTB

Evaluating the effectiveness of low-sulphur marine fuel regulations at improving urban ambient PM2.5 air quality: Source apportionment of PM2.5 at Canadian Atlantic and Pacific coast cities with implementation of the North American Emissions Control Area.

Ambient fine size fraction particulate matter (PM2.5) sources were resolved by positive matrix factorization at two Canadian cities on the Atlantic and Pacific coast over the 2010-2016 period, corresponding to implementation of the North American Emissions Control Area (NA ECA) low-sulphur marine fuel regulations. Source types contributing to local PM2.5 concentrations were: ECA regulation-related (residual oil, anthropogenic sulphate), urban transportation and residential (gasoline, diesel, secondary nitrate, biomass burning, road dust/soil), industry (refinery, Pb-enriched), and largely natural (biogenic sulphate, sea salt). Anthropogenic sources accounted for approximately 80 % of PM2.5 mass over 2010-2016. Anthropogenic and biogenic sources of PM2.5-sulphate were separated and apportioned. Anthropogenic PM2.5-sulphate was approximately 2-3 times higher than biogenic PM2.5-sulphate prior to implementation of the NA ECA low-S marine fuel regulations, decreasing to 1-2 times higher after regulation implementation. Non-marine anthropogenic sources (gasoline, road dust, local industry factors) were shown to together contribute 38 % - 45 % of urban PM2.5. At both coastal cities, the residual oil and anthropogenic sulphate factors clearly reflected the effects of the low-S fuel regulations at reducing primary and secondary sulphur-related PM2.5 emissions. Comparing a pre-regulation and post-regulation period, residual oil combustion PM2.5 decreased by 0.24-0.25 μg/m3 (94%-95 % decrease) in both cities and anthropogenic sulphate PM2.5 decreased by 0.78 μg/m3 in Halifax (47 % decrease) and 0.71 μg/m3 in Burnaby (58 % decrease). Regulation-related PM2.5 across these factors decreased by approximately 1 μg/m3 after regulation implementation, providing a quantified lower estimate of the beneficial influence of the regulations on urban ambient PM2.5 concentrations. Further reductions in coastal city ambient PM2.5 may best consider air quality strategies that include multiple sources, including marine shipping and non-marine anthropogenic source types given this analysis found that marine vessel emissions remain an important source of urban ambient PM2.5

Near-Road Air Pollutant Measurements: Accounting for Inter-Site Variability Using Emission Factors

A daily integrated emission factor (EF) method was applied to data from three near-road monitoring sites to identify variables that impact traffic related pollutant concentrations in the near-road environment. The sites were operated for 20 months in 2015–2017, with each site differing in terms of design, local meteorology, and fleet compositions. Measurement distance from the roadway and local meteorology were found to affect pollutant concentrations irrespective of background subtraction. However, using emission factors mostly accounted for the effects of dilution and dispersion, allowing intersite differences in emissions to be resolved. A multiple linear regression model that included predictor variables such as fraction of larger vehicles (>7.6 m in length; i.e., heavy-duty vehicles), vehicle speed, and ambient temperature accounted for intersite variability of the fleet average NO, NO_<i>x</i>, and particle number EFs (R²:0.50–0.75), with lower model performance for CO and black carbon (BC) EFs (R²:0.28–0.46). NO_<i>x</i> and BC EFs were affected more than CO and particle number EFs by the fraction of larger vehicles, which also resulted in measurable weekday/weekend differences. Pollutant EFs also varied with ambient temperature and because there were little seasonal changes in fleet composition, this was attributed to changes in fuel composition and/or post-tailpipe transformation of pollutants