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Traffic-related air pollutants (TRAP) including nitric oxide (NO), nitrogen oxide (NO

In Fall 2020, universities saw extensive transmission of SARS-CoV-2 among their populations, threatening health of the university and surrounding communities, and viability of in-person instruction. Here we report a case study at the University of Illinois at Urbana-Champaign, where a multimodal “SHIELD: Target, Test, and Tell” program, with other non-pharmaceutical interventions, was employed to keep classrooms and laboratories open. The program included epidemiological modeling and surveillance, fast/frequent testing using a novel low-cost and scalable saliva-based RT-qPCR assay for SARS-CoV-2 that bypasses RNA extraction, called covidSHIELD, and digital tools for communication and compliance. In Fall 2020, we performed >1,000,000 covidSHIELD tests, positivity rates remained low, we had zero COVID-19-related hospitalizations or deaths amongst our university community, and mortality in the surrounding Champaign County was reduced more than 4-fold relative to expected. This case study shows that fast/frequent testing and other interventions mitigated transmission of SARS-CoV-2 at a large public university.

In the Fall of 2020, many universities saw extensive transmission of SARS-CoV-2 among their populations, threatening the health of students, faculty and staff, the viability of in-person instruction, and the health of surrounding communities.1, 2 Here we report that a multimodal “SHIELD: Target, Test, and Tell” program mitigated the spread of SARS-CoV-2 at a large public university, prevented community transmission, and allowed continuation of in-person classes amidst the pandemic. The program combines epidemiological modelling and surveillance (Target); fast and frequent testing using a novel and FDA Emergency Use Authorized low-cost and scalable saliva-based RT-qPCR assay for SARS-CoV-2 that bypasses RNA extraction, called covidSHIELD (Test); and digital tools that communicate test results, notify of potential exposures, and promote compliance with public health mandates (Tell). These elements were combined with masks, social distancing, and robust education efforts. In Fall 2020, we performed more than 1,000,000 covidSHIELD tests while keeping classrooms, laboratories, and many other university activities open. Generally, our case positivity rates remained less than 0.5%, we prevented transmission from our students to our faculty and staff, and data indicate that we had no spread in our classrooms or research laboratories. During this fall semester, we had zero COVID-19-related hospitalizations or deaths amongst our university community. We also prevented transmission from our university community to the surrounding Champaign County community. Our experience demonstrates that multimodal transmission mitigation programs can enable university communities to achieve such outcomes until widespread vaccination against COVID-19 is achieved, and provides a roadmap for how future pandemics can be addressed.

Accurate, continuous long-term measurements of aromatic volatile organic compounds with known health impacts are needed for comprehensive assessments of air quality in the vicinity of industrial and vehicular emission sources. Historically, evacuated canister sampling and on-line gas chromatography (GC) have been the most popular approaches applied by government institutions in North America to measure benzene, toluene, ethylbenzene and xylenes (BTEX) in ambient air. Canister sampling is labour-intensive and typically does not provide the continuous data needed for epidemiological studies, while on-line GCs are costly and require shelter and power. In this work, the accuracy and suitability of three techniques for generating long-term ambient BTEX datasets are assessed. The first is a passive sampling method involving sorbent-packed thermal desorption tubes, the second is an on-line miniature gas chromatograph (miniGC) coupled with a photoionization detector (PID) and the third is a more traditional on-line gas chromatograph coupled with a flame ionization detector (GC-FID). These three techniques were deployed at an air quality monitoring station located adjacent to a busy highway for six weeks in summer 2018 to compare method performance and accuracy. Ambient mean concentrations of BTEX determined from the three methods for the entire study period were found to agree within 7% for benzene and within 30% for the other species. Interestingly, a temperature dependent positive bias previously identified for 14-day passive tube sampling for ethylbenzene and xylenes under cold wintertime conditions was found to be negligible under summertime conditions.

The contribution of traffic-related particulate matter (PM2.5, particles smaller than 2.5 μm in diameter) sources can vary temporally and spatially, which may disproportionately contribute to health outcomes. Furthermore, non-exhaust emissions are a growing concern due to the high concentrations of redox active metals that can be present. The temporal and spatial variabilities of traffic-related PM2.5 sources were investigated in this study by comparing source contributions between two near-road sites. In order to identify local PM2.5 sources with greater temporal and spatial resolution, receptor modeling was performed for hourly-resolved organics, inorganic ions, trace elements, and black carbon in PM2.5 simultaneously measured at downtown and highway sites located within 15 m of a major roadway and highway, respectively, in Toronto. The source apportionment study revealed that traffic-related PM2.5 sources were mainly from exhaust emissions (9%–19% of PM2.5) and non-exhaust emissions including brake wear (2%–6%) and resuspension of road dust (3%–4%). The traffic-related sources exhibited strong diurnal and spatial variabilities, whereas no spatial and temporal differences were observed for the largest PM2.5 contributors, oxidized organic aerosol and secondary sulphate. During morning rush hours, the overall contribution of traffic exhaust and non-exhaust emissions were elevated up to 35%–48% of total PM2.5 mass, which was found to be the largest PM2.5 source at the highway site and the second largest contributor in the downtown area. Furthermore, the contribution of traffic-related sources at the highway site was higher than at the downtown site by a factor of 2–3, suggesting that exposure to traffic-related emissions varies greatly in space and time. Nearly one-third of the traffic-related source contributions were associated with non-exhaust emissions from brake wear and road dust resuspension in the urban environment. Elevated levels of non-exhaust sources were correlated with the number of heavy-duty vehicles, rather than total traffic volume. Although the contribution of brake wear and road dust sources to total PM2.5 mass was relatively low, non-exhaust emissions contributed a substantial fraction of trace elements, especially for Ba (74–79%), Cu (66–71%), and Mn (53–65%) in the urban atmosphere.

International audience; Industrial metalworking facilities emit a variety of air toxics including volatile organic compounds, polycyclic aromatic hydrocarbons (PAHs) and heavy metals. In order to investigate these emissions, a 1-month multi-instrument field campaign was undertaken at an industrial site in Grande-Synthe, Dunkirk (France), in May and June 2012. One of the main objectives of the study was to provide new information on the chemical composition of particulate matter with aerodynamic diameters smaller than 2.5 μm (PM2.5) in the vicinity of metalworking facilities. An aerosol time-of-flight mass spectrometer (ATOFMS) was deployed to provide size-resolved chemical mixing state measurements of ambient single particles at high temporal resolution. This mixing state information was then used to apportion PM2.5 to local metalworking facilities influencing the receptor site. Periods when the site was influenced by metalworking sources were characterised by a pronounced increase in particles containing toxic metals (manganese, iron, lead) and polycyclic aromatic hydrocarbons (PAHs) with a variety of chemical mixing states. The association of specific particle classes with a nearby ferromanganese alloy manufacturing plant was confirmed through comparison with previous analysis of raw materials (ores) and chimney filter particle samples collected at the facility. Particles associated with emissions from a nearby steelworks were also identified. The contribution of local metalworking activities to PM2.5 at the receptor site for the period when the ATOFMS was deployed ranged from 1 to 65% with an average contribution of 17%, while the remaining mass was attributed to other local and regional sources. These findings demonstrate the impact of metalworking facilities on air quality downwind and provide useful single particle signatures for future source apportionment studies in communities impacted by metalworking emissions.

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, NOx, and particle number EFs (R2:0.50–0.75), with lower model performance for CO and black carbon (BC) EFs (R2:0.28–0.4...

Temporal variations of vehicle emissions are affected by various compounding factors in the real world. The focus of this study is to determine the effects of ambient conditions and post-tailpipe changes on traffic emissions measured in the near-road region. Emission factors allowed for the isolation of the traffic signal and accounted for effects of local meteorology and dilution. Five month-long measurement campaigns were conducted at an urban near-road site that exhibited a broad range of ambient conditions with temperatures ranging between −18 and +30 °C. Particle number emission factors were 2.0× higher in the winter relative to the summer, which was attributed to changes in particles post-tailpipe. Conversely, toluene emissions were 2.5× higher in the summer relative to the winter, attributed to changes in fuel composition. Diurnal trends of emission factors showed substantial increases in emissions during the morning rush hour for black carbon (1.9×), particle number (2.4×), and particle-bound polycyclic aromatic hydrocarbons (3.0×), affected by fleet make-up. In contrast, particle number emission factors were highest midday with mean values 3.7× higher than at night. This midday increase was attributed to particle formation or growth from local traffic emissions and showed different wind direction dependence than regional events.

Real-time analysis of volatile organic compounds (VOCs) in air is useful both for source identification and emissions compliance applications. In this work, two complementary triple quadrupole mass spectrometers, fitted with an atmospheric pressure chemical ionization (APCI) and a low pressure chemical ionization (LPCI) source, respectively, were deployed simultaneously to investigate emissions of VOCs associated with an Ontario-based chemical waste disposal facility. Mobile measurements performed upwind and downwind of the facility enabled selection of the best locations for stationary sampling. Seven separate field studies were undertaken between 2000 and 2016 to assess how emissions of VOCs have changed at the site as a function of time. Up to twenty-nine VOCs were successfully identified and quantified using MS/MS in each study. Simultaneous deployment of the two mass spectrometers enabled the detection of polar VOCs including alcohols, esters, amines and ketones as well as non-polar aromatic VOCs including benzene and naphthalene in real time. Concentrations of VOCs were found to decrease significantly in the vicinity of the facility over the sixteen year period, in particular since 2007. Concentration values for each year are compared with odour thresholds and provincial guidelines and implications of future expansion of on-site solid waste landfill volumes are also discussed.

The differences in PM2.5 concentrations between two relatively close stations, one situated near a major highway and the other much more distant were used to develop a protocol for determining the impact of highway traffic on particulate matter concentrations at the roadside. The roadside station was ≳ 50%. Of interest was the variation of multi-time factors based on ME2 analyses of the speciation data from the roadside station during these imbalance events. Of the 7 mass-contributing ME2 factors, a black carbon factor was determined to be the major cause of the PM2.5 imbalance and was especially dominant for the case when PM2.5 concentrations at the roadside station were greater than the farther-station PM2.5. The black carbon concentrations observed during these specific events were further regressed against other traffic-related and meteorological parameters with two nonlinear optimization algorithms (generalized reduced gradient and rules ensemble) in our attempts to model any potential relationships. It was observed that the traffic counts of heavy duty vehicles (predominantly diesel-powered) dominated the relationship with black carbon while contributions from light duty vehicles were negligible during these [PM2.5]Roadside > [PM2.5]Farther events at the roadside station. This work details the most critical ways that highway traffic can contribute to local ambient PM2.5 concentrations that commuters are exposed to and will be important in informing policies and strategies for particulate matter pollution reduction.

The province of Alberta, Canada, is home to three oil sands regions which, combined, contain the third largest deposit of oil in the world. Of these, the Athabasca oil sands region is the largest. As part of Environment and Climate Change Canada's program in support of the Joint Canada-Alberta Implementation Plan for Oil Sands Monitoring program, concentrations of trace elements in PM2. 5 (particulate matter smaller than 2.5 µm in diameter) were measured through two campaigns that involved different methodologies: a long-term filter campaign and a short-term intensive campaign. In the long-term campaign, 24 h filter samples were collected once every 6 days over a 2-year period (December 2010–November 2012) at three air monitoring stations in the regional municipality of Wood Buffalo. For the intensive campaign (August 2013), hourly measurements were made with an online instrument at one air monitoring station; daily filter samples were also collected. The hourly and 24 h filter data were analyzed individually using positive matrix factorization. Seven emission sources of PM2. 5 trace elements were thereby identified: two types of upgrader emissions, soil, haul road dust, biomass burning, and two sources of mixed origin. The upgrader emissions, soil, and haul road dust sources were identified through both the methodologies and both methodologies identified a mixed source, but these exhibited more differences than similarities. The second upgrader emissions and biomass burning sources were only resolved by the hourly and filter methodologies, respectively. The similarity of the receptor modeling results from the two methodologies provided reassurance as to the identity of the sources. Overall, much of the PM2. 5-related trace elements were found to be anthropogenic, or at least to be aerosolized through anthropogenic activities. These emissions may in part explain the previously reported higher levels of trace elements in snow, water, and biota samples collected near the oil sands operations.

Black carbon (BC) is of significant interest from a human exposure perspective but also due to its impacts as a short-lived climate pollutant. In this study, sources of BC influencing air quality in Ontario, Canada were investigated using nine concurrent Aethalometer datasets collected between June 2015 and May 2016. The sampling sites represent a mix of background and near-road locations. An optical model was used to estimate the relative contributions of fossil fuel combustion and biomass burning to ambient concentrations of BC at every site. The highest annual mean BC concentration was observed at a Toronto highway site, where vehicular traffic was found to be the dominant source. Fossil fuel combustion was the dominant contributor to ambient BC at all sites in every season, while the highest seasonal biomass burning mass contribution (35%) was observed in the winter at a background site with minimal traffic contributions. The mass absorption cross-section of BC was also investigated at two sites, where concurrent thermal/optical elemental carbon data were available, and was found to be similar at both locations. These results are expected to be useful for comparing the optical properties of BC at other near-road environments globally. A strong seasonal dependence was observed for fossil fuel BC at every Ontario site, with mean summer mass concentrations higher than their respective mean winter mass concentrations by up to a factor of two. An increased influence from transboundary fossil fuel BC emissions originating in Michigan, Ohio, Pennsylvania and New York was identified for the summer months. The findings reported here indicate that BC should not be considered as an exclusively local pollutant in future air quality policy decisions. The highest seasonal difference was observed at the highway site, however, suggesting that changes in fuel composition may also play an important role in the seasonality of BC mass concentrations in the near-road environment. This finding has implications for future policies aiming to improve air quality in urban environments where fuel composition changes as a function of season.

International audience; In a context where a significant fraction of the population lives near industrial areas, the main objectives of this study are to provide (a) new data on PM2.5 chemical compositions, heavy metal concentrations and trace gases released by metalworking activities and (b) new information on the nearfield evolution (up to about a thousand meters) of such industrial plumes in terms of particle chemical composition and size distribution. For that purpose, aone-month field campaign was performed in an industrial area near the city of Dunkirk (Northern France), combining measurements of atmospheric dynamics and physico-chemical characterization of air masses. Comparisons between several elemental ratios (mainly Mn/Fe), particle size distributions and volatile organic compound (VOC) concentrations at the stacks and at a near-field site suggest that plumes of a ferromanganese alloy plant were quickly mixed with pollutants emitted by other sources (mainly other industries, possibly traffic and sea spray), in particular a neighboring steelworks, before reaching the sampling site. This led to the emergence of secondary particles related to condensation and/or aggregationphenomena inside the plumes. Metalworking emissions were also identified as a source of new particle formation, formed through the emission of gaseous precursors and their fast transformation and condensation, over a timescale of minutes before reaching the near-field site 800 m downwind. Ultrafine particles emitted at the stacks also quickly agglomerated to form larger particles before reaching the near-field site. These results show that, even over short distances, the chemical composition and size distribution of metalworking plumes may evolve rapidly and the characteristics of particles at the boundary of an industrial area (especially in contiguous urban areas) may differ from those emitted directly at the stacks.

Ambient fine particulate matter (PM2.5) data of similar continuously monitored species at two air monitoring sites with different characteristics within the City of Toronto were used to gauge the intra-city variations in the PM composition over a largely concurrent period spanning two years. One location was

Road traffic emissions are an increasingly important source of particulate matter in urban and non-road environments, where non-tailpipe emissions can contribute substantially to elevated levels of metals associated with adverse health effects. Thus, better characterization and quantification of traffic-emitted metals is warranted. In this study, real-world emission factors for fine particulate metals were determined from hourly x-ray fluorescence measurements over a three-year period (2015–2018) at an urban roadway and busy highway. Inter-site differences and temporal trends in real-world emission factors for metals were explored. The emission factors at both sites were within the range of past studies, and it was found that Ti, Fe, Cu, and Ba emissions were 2.2–3.0 times higher at the highway site, consistent with the higher proportion of heavy-duty vehicles. Weekday emission factors for some metals were also higher by 2.0–3.5 times relative to Sundays for Mn, Zn, Ca, and Fe, illustrating a dependence on fleet composition and roadway activity. Metal emission factors were also inversely related to relative humidity and precipitation, due to reduced road dust resuspension under wetter conditions. Correlation analysis revealed groups of metals that were co-emitted by different traffic activities and sources. Determining emission factors enabled the isolation of traffic-related metal emissions and also revealed that human exposure to metals in ambient air can vary substantially both temporally and spatially depending on fleet composition and traffic volume.

Polycyclic aromatic hydrocarbons (PAHs) are recognized as important secondary organic aerosol (SOA) precursors in the urban atmosphere. In this work, the gas-phase ozonolysis of acenaphthylene was investigated in an atmospheric simulation chamber using a proton transfer reaction time-of-flight-mass spectrometer (PTR-TOF-MS) and an aerosol time-of-flight-mass spectrometer (ATOFMS) for on-line characterization of the oxidation products in the gas and particle phases, respectively. SOA samples were also collected on filters and analyzed by ultra performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS) and gas chromatography/electron impact ionization-mass spectrometry (GC/EI-MS). The major gas-phase products included a range of oxygenated naphthalene derivatives such as 1,8-naphthalic anhydride, naphthalene 1,8-dicarbaldehyde and naphthaldehyde, as well as a secondary ozonide. Possible reaction mechanisms are proposed for the formation of these products and favoured pathways have been suggested. Many of these products were also found in the particle phase along with a range of oligomeric compounds. The same range of gas and particle phase products was observed in the presence and absence of excess cyclohexane, an OH scavenger, indicating that OH radical production from the ozonolysis of acenaphthylene is negligible. SOA yields in the range 23–37% were determined and indicate that acenaphthylene ozonolysis may contribute to part of the SOA observed in urban areas.

Biomass burning organic aerosol (BBOA) can be emitted from natural forest fires and human activities such as agricultural burning and domestic energy generation. BBOA is strongly associated with atmospheric brown carbon (BrC) that absorbs near-ultraviolet and visible light, resulting in significant impacts on regional visibility degradation and radiative forcing. The mixing state of BBOA can play a critical role in the prediction of aerosol optical properties. In this work, single-particle measurements from a Soot-Particle Aerosol Mass Spectrometer coupled with a light scattering module (LS-SP-AMS) were performed to examine the mixing state of BBOA, refractory black carbon (rBC), and potassium (K, a tracer for biomass burning aerosol) in an air mass influenced by wildfire emissions transported from northern Québec to Toronto, representing aged biomass burning plumes. Cluster analysis of single-particle measurements identified five BBOA-related particle types. rBC accounted for 3–14 wt % of these particle types on average. Only one particle type exhibited a strong ion signal for K+, with mass spectra characterized by low molecular weight organic species. The remaining four particle types were classified based on the apparent molecular weight of the BBOA constituents. Two particle types were associated with low potassium content and significant amounts of high molecular weight (HMW) organic compounds. Our observations indicate non-uniform mixing of particles within a biomass burning plume in terms of molecular weight and illustrate that HMW BBOA can be a key contributor to low-volatility BrC observed in BBOA particles. The average mass absorption efficiency of low-volatility BBOA is about 0.8–1.1 m2 g−1 based on a theoretical closure calculation. Our estimates indicate that low-volatility BBOA contributes ∼ 33–44 % of thermo-processed particle absorption at 405 nm; and almost all of the BBOA absorption was associated with low-volatility organics.

The chemical composition of single particles deposited on industrial filters located in three different chimneys of an iron-manganese (Fe-Mn) alloy manufacturing plant have been compared using aerosol time-of-flight mass spectrometry (ATOFMS) and scanning electron microscopy-energy dispersive X-ray spectrometry (SEM-EDX). Very similar types of particles were observed using both analytical techniques. Calcium-containing particles dominated in the firing area of the sintering unit, Mn and/or Al-bearing particles were observed at the cooling area of the sintering unit, while Mn-containing particles were dominant at the smelting unit. SEM-EDX analysis of particles collected downstream of the industrial filters showed that the composition of the particles emitted from the chimneys is very similar to those collected on the filters. ATOFMS analysis of ore samples was also performed to identify particulate emissions that could be generated by wind erosion and manual activities. Specific particle types have been identified for each emission source (chimneys and ore piles) and can be used as tracers for source apportionment of ambient PM measured in the vicinity of the industrial site.

Traffic has a substantial impact on air pollution in many cities. As the introduction of new vehicle technologies reduces emissions of some pollutants, the role of non-tailpipe emissions is increas...

Environmental Protection Agency Method 325 was developed for continuous passive monitoring of volatile organic compounds (VOCs), particularly benzene, at petroleum refinery fencelines. In this work, a modified version of the method was evaluated at an Ontario near-road research station in winter to assess its suitability for urban air quality monitoring. Samples were collected at 24 hour and 14 day resolution to investigate accuracy for different exposure times. Tubes were analyzed by thermal desorption-gas chromatography-mass spectrometry, and 11 VOCs were quantified, including aromatic air toxics. The same VOCs were simultaneously monitored using traditional canister sampling for comparison, and a subset of four were also monitored using a novel miniature gas chromatograph. Good agreement (within 10%) was observed between the 14 day passive tube samples and the canister samples for benzene. However, field-calibrated uptake rates were required to correct passive tube concentrations for less volatile aromatics. Passive tube deployment and analysis is inexpensive; sampling does not require power, and accurate measurements of benzene are demonstrated here for an urban environment. The method is expected to be advantageous for the generation of long-term continuous benzene datasets suitable for epidemiological research with greater spatial coverage than is currently available using traditional monitoring techniques.

8 pages, 4 figures, Organic oligomers were discovered in laboratory-generated atmospheric aerosol over a decade ago. However, evidence for the presence of oligomers in ambient aerosols is scarce and mechanisms for their formation have yet to be fully elucidated. In this work, three unique aerosol particle types internally mixed with High molecular weight organic compounds (HMW-OC) species - likely oligomers - were detected in ambient air using single particle Aerosol Time-Of-Flight Mass Spectrometry (ATOFMS) in Cork (Ireland) during winter 2009. These particle types can be described as follows: (1) HMW-OCs rich in organic nitrogen - possibly containing nitrocatechols and nitroguaiacols - originating from primary emissions of biomass burning particles during evening times; (2) HMW-OCs internally mixed with nitric acid, occurring in stagnant conditions during night time; and (3) HMW-OCs internally mixed with sea salt, likely formed via photochemical reactions during day time. The study exemplifies the power of methodologies capable of monitoring the simultaneous formation of organic and inorganic particle-phase reaction products. Primary emissions and atmospheric aging of different types of HMW-OC contributes to aerosol with a range of acidity, hygroscopic and optical properties, which can have different impacts on climate and health, This work was funded by the Ireland Higher Education Authority Programme for Research in Third Level Institutes (PRTL1) – Cycle 5, and the Irish Environmental Protection Agency. Additional founding by the Spanish Ministry of Economy through projects BIO-NUC (CGL2013-49020-R), and by the EU though the FP7-PEOPLE-2013-IOF programme (Project number 624680, MANU – Marine Aerosol NUcleations) and the Ramon y Cajal fellowship (RYC-2012-11922). The National Centre for Atmospheric Science NCAS Birmingham group is funded by the UK Natural Environment Research Council

The chlorine atom (Cl)-initiated oxidation of three polycyclic aromatic hydrocarbons (PAHs; namely, naphthalene, acenaphthylene, and acenaphthene) was investigated. Experiments were performed in an atmospheric simulation chamber using a proton transfer reaction time-of-flight mass spectrometer (TOF-MS) and an aerosol TOF-MS to characterize the oxidation products in the gas and particle phases, respectively. The major products identified from the reaction of Cl atoms with naphthalene were phthalic anhydride and chloronaphthalene, indicating that H atom abstraction and Cl addition reaction pathways are both important. Acenaphthenone was the principal product arising from reaction of Cl with acenaphthene, while 1,8-naphthalic anhydride, acenaphthenone, acenaphthenequinone, and chloroacenaphthenone were all identified as products of acenaphthylene oxidation, confirming that the cylcopenta-fused ring controls the reactivity of these PAHs toward Cl atoms. Possible reaction mechanisms are proposed for the formation of these products, and favored pathways have been suggested. Large yields of secondary organic aerosol (SOA) were also observed in all experiments, and the major products were found to undergo significant partitioning to the particle-phase. This work suggests that Cl-initiated oxidation could play an important role in SOA formation from PAHs under specific atmospheric conditions where the Cl atom concentration is high, such as the marine boundary layer.

The optical properties of ambient black carbon-containing particles and the composition of their associated coatings were investigated at a downtown site in Toronto, Canada, for 2 weeks in June 2013. The objective was to assess the relationship between black carbon (BC) coating composition/thickness and absorption. The site was influenced by emissions from local vehicular traffic, wildfires in Quebec, and transboundary fossil fuel combustion emissions in the United States. Mass concentrations of BC and associated nonrefractory coatings were measured using a soot particle–aerosol mass spectrometer (SP-AMS), while aerosol absorption and scattering were measured using a photoacoustic soot spectrometer (PASS). Absorption enhancement was investigated both by comparing ambient and thermally denuded PASS absorption data and by relating absorption data to BC mass concentrations measured using the SP-AMS. Minimal absorption enhancement attributable to lensing at 781 nm was observed for BC using both approaches. However, brown carbon was detected when the site was influenced by wildfire emissions originating in Quebec. BC coating to core mass ratios were highest during this period (~7), and while direct absorption by brown carbon resulted in an absorption enhancement at 405 nm (>2.0), no enhancement attributable to lensing at 781 nm was observed. The efficiency of BC coating removal in the denuder decreased substantially when wildfire-related organics were present and may represent an obstacle for future similar studies. These findings indicate that BC absorption enhancement due to lensing is minimal for downtown Toronto, and potentially other urban locations, even when impacted by long-range transport events.

The health of a substantial portion of urban populations is potentially being impacted by exposure to traffic–related atmospheric pollutants. To better understand the rapid physical and chemical transformation of these pollutants, the number size distributions of non–volatile traffic–related particles were investigated at different distances from a major highway. Particle volatility measurements were performed upwind and downwind of the highway using a fast mobility particle sizing spectrometer with a thermodenuder on a mobile laboratory. The number concentration of non–denuded ultrafine particles decreased exponentially with distance from the highway, whereas a more gradual gradient was observed for non–volatile particles. The non–volatile number concentration at 27 m was higher than that at 280 m by a factor of approximately 3, and the concentration at 280 m was still higher than that upwind of the highway. The proportion of non–volatile particles increased away from the highway, representing 36% of the total particle number at 27 m, 62% at 280 m, and 81% at the upwind site. A slight decrease in the geometric mean diameter of the non–volatile particle size distributions from approximately 35 nm to 30 nm was found between 27 m and 280 m, in contrast to the growth of non–denuded particles with increasing distance from the highway. Single particle analysis results show that the contribution of elemental carbon (EC)–rich particle types at 27 m was higher than the contribution at 280 m by a factor of approximately 2. The findings suggest that people living or spending time near major roadways could be exposed to elevated number concentrations of nucleation–mode volatile particles ( 100 nm). The impact of the highway emissions on air quality was observable up to 300 m.

Understanding the impact of atmospheric black carbon (BC)-containing particles on human health and radiative forcing requires knowledge of the mixing state of BC, including the characteristics of the materials with which it is internally mixed. In this study, we examine the mixing state of refractory BC (rBC) and other aerosol components in an urban environment (downtown Toronto) utilizing the Aerodyne soot particle aerosol mass spectrometer equipped with a light scattering module (LS-SP-AMS). k-means cluster analysis was used to classify single particle mass spectra into chemically distinct groups. One resultant particle class is dominated by rBC mass spectral signals (C1+ to C5+) while the organic signals fall into a few major particle classes identified as hydrocarbon-like organic aerosol (HOA), oxygenated organic aerosol (OOA), and cooking emission organic aerosol (COA). A gradual mixing is observed with small rBC particles only thinly coated by HOA (~ 28% by mass on average), while over 90% of the HOA-rich particles did not contain detectable amounts of rBC. Most of the particles classified into other inorganic and organic particle classes were not significantly associated with rBC. The single particle results also suggest that HOA and COA emitted from anthropogenic sources were likely major contributors to organic-rich particles with vacuum aerodynamic diameter (dva) ranging from ~ 200 to 400 nm. The similar temporal profiles and mass spectral features of the organic classes identified by cluster analysis and the factors from a positive matrix factorization (PMF) analysis of the ensemble aerosol data set validate the interpretation of the PMF results.

International audience; This work is focused on the gas-phase oxidation of acenaphthylene and acenaphthene by OH radicals and associated secondary organic aerosol (SOA) formation under low and high-NOx conditions. Experiments were carried out in an atmospheric simulation chamber using a proton transfer reaction time-of-flight-mass spectrometer (PTR-TOF-MS) and an aerosol time-of-flight-mass spectrometer (ATOFMS) to chemically characterize the gas- and particle-phase products, respectively. Due to the structures of these two aromatic compounds, the proposed chemical mechanisms exhibit some differences. In the case of acenaphthene, H-atom abstraction from the saturated cyclopenta-fused ring was found to be competitive with the OH-addition to the aromatic rings. During the photooxidation of acenaphthene using nitrous acid (HONO), aromatic ring-opening products such as indanone and indanone carbaldehyde, generated through OH addition to the aromatic ring, were formed in higher yields compared to low-NOx conditions. In the case of acenaphthylene, OH addition to the unsaturated cyclopenta-fused ring was strongly favored. Hence, ring-retaining species such as acenaphthenone and acenaphthenequinone, were identified as the main reaction products in both gas- and particle-phases, especially under high-NOx conditions. Subsequent SOA formation was observed in all experiments and SOA yields were determined under low/high-NOx conditions to be 0.61/0.46 and 0.68/0.55 from the OH-initiated oxidation of acenaphthylene and acenaphthene, respectively.

A majority of the ultrafine particles observed in real-world conditions are systematically excluded from many measurements that help to guide regulation of vehicle emissions. To investigate the impact of this exclusion, coincident near-road particle number (PN) emission factors were quantified up- and downstream of a thermodenuder during two seasonal month-long campaigns with wide-ranging ambient temperatures (−19 to +30 °C) to determine the volatile fraction of particles. During colder temperatures ( 20 °C). Additionally, mean PN emission factors were a factor of 3.8 higher during cold compared to warm periods. On the basis of 130 000 vehicle plumes including three additional campaigns, fleet mean emission factors were calculated for PN (8.5 × 1014 kg-fuel–1), black carbon (37 mg kg-fuel–1), organic aerosol (51 mg kg-fuel–1), and particle-bound polycyclic aromatic hydrocarbons (0.7 mg kg-fuel–1). These finding...

The province of Alberta, Canada is home to three oil sands regions which, combined, contain the third largest deposit of oil in the world. Of these, the Athabasca Oil Sands Region is the largest. As part of Environment and Climate Change Canada's program in support of the Joint Canada-Alberta Implementation Plan for Oil Sands Monitoring program, concentrations of trace metals in PM2.5 were measured through two campaigns that involved different methodologies: a long-term filter campaign and a short term intensive campaign. In the long-term campaign, 24-hr filter samples were collected one-in-six days over a two-year period (Dec. 2010–Nov. 2012) at three air monitoring stations in the Regional Municipality of Wood Buffalo. For the intensive campaign (Aug. 2013), hourly measurements were made with an on-line instrument at one air monitoring station; daily filter samples were also collected. The hourly and 24-h filter data were analysed individually using positive matrix factorization. Seven emission sources of PM2.5 were thereby identified: two types of Upgrader Emissions, Soil, Haul Road Dust, Biomass Burning, and two sources of mixed origin. The Upgrader Emissions, Soil, and Haul Road Dust sources were identified through both the methodologies and both methodologies identified a mixed source, but these exhibited more differences than similarities. The second Upgrader Emissions and Biomass Burning sources were only resolved by the hourly and filter methodologies, respectively. The similarity of the receptor modeling results from the two methodologies provided reassurance as to the identity of the sources. Overall much of the PM2.5 related metal was found to be anthropogenic, or at least to be aerosolized through anthropogenic activities. These emissions may in part explain the previously reported higher levels of metals in snow, water, and biota samples collected near the oil sands operations.

An aerosol time-of-flight mass spectrometer (ATOFMS) was employed to provide real-time single particle mixing state and thereby source information for aerosols impacting the western Mediterranean basin during the ChArMEx-ADRIMED and SAF-MED campaigns in summer 2013. The ATOFMS measurements were made at a ground-based remote site on the northern tip of Corsica Island. 27 distinct ATOFMS particle classes were identified and subsequently grouped into 8 general categories: EC-rich (elemental carbon), K-rich, Na-rich, Amines, OC-rich (organic carbon), V-rich, Fe-rich and Ca-rich. Mass concentrations were reconstructed for the ATOFMS particle classes and found to be in good agreement with other co-located quantitative measurements (PM1, black carbon (BC), organic carbon, sulfate mass and ammonium mass). Total ATOFMS reconstructed mass (PM2.5) accounted for 70–90 % of measured PM10 mass and was comprised of regionally transported fossil fuel (EC-rich) and biomass burning (K-rich) particles. The accumulation of these transported particles was favoured by repeated and extended periods of air mass stagnation over the western Mediterranean during the sampling campaigns. The single particle mass spectra proved to be valuable source markers, allowing the identification of fossil fuel and biomass burning combustion sources, and therefore highly complementary to quantitative measurements made by particle-into-liquid sampler ion chromatography (PILS-IC) and an aerosol chemical speciation monitor (ACSM), which have demonstrated that PM1 and PM10 were comprised predominantly of sulfate, ammonium and OC. Good temporal agreement was observed between ATOFMS EC-rich and K-rich particle mass concentrations and combined mass concentrations of BC, sulfate, ammonium and low volatility oxygenated organic aerosol (LV-OOA). This combined information suggests that combustion of fossil fuels and biomass produced primary EC- and OC-containing particles, which then accumulated ammonium, sulfate and alkylamines during regional transport. Three other sources were also identified: local biomass burning, marine and shipping. Local combustion particles (emitted in Corsica) contributed little to PM2.5 particle number and mass concentrations but were easily distinguished from regional combustion particles. Marine emissions comprised fresh and aged sea salt; the former detected mostly during one 5-day event during which it accounted for 50–80 % of sea salt aerosol mass, while the latter detected throughout the sampling period. Dust was not efficiently detected by the ATOFMS, and support measurements showed that it was mainly in the PM2.5–10 fraction. Shipping particles, identified using markers for heavy fuel oil combustion, were associated with regional emissions, and represented only a small fraction of PM2.5 particle number and mass concentration at the site.

International audience; An aerosol time-of-flight mass spectrometer (ATOFMS) was employed to provide real-time single particle mixing state and thereby source information for aerosols impacting the western Mediterranean basin during the ChArMEx-ADRIMED and SAF-MED campaigns in summer 2013. The ATOFMS measurements were made at a ground-based remote site on the northern tip of Corsica. Twenty-seven distinct ATOFMS particle classes were identified and subsequently grouped into eight general categories: EC-rich (elemental carbon), K-rich, Na-rich, amines, OC-rich (organic carbon), V-rich, Fe-rich and Ca-rich particles. Mass concentrations were reconstructed for the ATOFMS particle classes and found to be in good agreement with other co-located quantitative measurements (PM 1 , black carbon (BC), organic carbon, sulfate mass and am-monium mass). Total ATOFMS reconstructed mass (PM 2.5) accounted for 70–90 % of measured PM 10 mass and was comprised of regionally transported fossil fuel (EC-rich) and biomass burning (K-rich) particles. The accumulation of these transported particles was favoured by repeated and extended periods of air mass stagnation over the western Mediterranean during the sampling campaigns. The single particle mass spectra proved to be valuable source markers, allowing the identification of fossil fuel and biomass burning combustion sources, and was therefore highly complementary to quantitative measurements made by Particle into Liquid Sampler ion chromatography (PILS-IC) and an aerosol chemical speciation monitor (ACSM), which have demonstrated that PM 1 and PM 10 were comprised predominantly of sulfate, ammonium and OC. Good temporal agreement was observed between ATOFMS EC-rich and K-rich particle mass concentrations and combined mass concentrations of BC, sulfate, ammonium and low volatility oxygenated organic aerosol (LV-OOA). This combined information suggests that combustion of fossil fuels and biomass produced primary EC-and OC-containing particles, which then accumulated ammonium, sulfate and alkylamines during regional transport. Three other sources were also identified: local biomass burning, marine and shipping. Local combustion particles Published by Copernicus Publications on behalf of the European Geosciences Union. 6976 J. Arndt et al.: Sources and mixing state of summertime background aerosol (emitted in Corsica) contributed little to PM 2.5 particle number and mass concentrations but were easily distinguished from regional combustion particles. Marine emissions comprised fresh and aged sea salt: the former was detected mostly during a 5-day event during which it accounted for 50–80 % of sea salt aerosol mass, while the latter was detected throughout the sampling period. Dust was not efficiently detected by the ATOFMS, and support measurements showed that it was mainly in the PM 2.5–10 fraction. Shipping particles, identified using markers for heavy fuel oil combustion , were associated with regional emissions and represented only a small fraction of PM 2.5 particle number and mass concentration at the site.

Alkylamines are associated with both natural and anthropogenic sources and have been detected in ambient aerosol in a variety of environments. However, little is known about the ubiquity or relative abundance of these species in Europe. In this work, ambient single-particle mass spectra collected at five sampling sites across Europe have been analysed for their alkylamine content. The aerosol time-of-flight mass spectrometer (ATOFMS) data used were collected in Ireland (Cork), France (Paris, Dunkirk and Corsica) and Switzerland (Zurich) between 2008 and 2013. Each dataset was queried for mass spectral marker ions associated with the following ambient alkylamines: dimethylamine (DMA), trimethylamine (TMA), diethylamine (DEA), triethylamine (TEA), dipropylamine (DPA) and tripropylamine (TPA). The fraction of ambient particles that contained detectable alkylamines ranged from 1 to 17 % depending on location, with the highest fractions observed in Paris and Zurich in the winter months. The lowest fractions were observed at coastal sites, where the influence of animal husbandry-related alkylamine emissions is also expected to be lowest. TMA was the most ubiquitous particle phase alkylamine detected and was observed at all locations. Alkylamines were found to be internally mixed with both sulphate and nitrate for each dataset, suggesting that aminium salt formation may be important at all sites investigated. Interestingly, in Corsica, all alkylamine particles detected were also found to be internally mixed with methanesulphonic acid (MSA), indicating that aminium methanesulphonate salts may represent a component of marine ambient aerosol in the summer months. Internal mixing of alkylamines with sea salt was not observed, however. Alkylamine-containing particle composition was found to be reasonably homogeneous at each location, with the exception of the Corsica and Dunkirk sites, where two and four distinct mixing states were observed, respectively.

Single particle mass spectral data, collected in Paris, France, have been used to predict hygroscopic growth at the single particle level. The mass fractions of black carbon, organic aerosol, ammonium, nitrate, and sulphate present in each particle were estimated using a combination of single particle mass spectrometer and bulk aerosol chemical composition measurements. The Zdanovskii-Stokes-Robinson (ZSR) approach was then applied to predict hygroscopic growth factors based on these mass fraction estimates. Smaller particles with high black carbon mass fractions and low inorganic ion mass fractions exhibited the lowest predicted growth factors, while larger particles with high inorganic ion mass fractions exhibited the highest growth factors. Growth factors were calculated for subsaturated relative humidity (90%) to enable comparison with hygroscopic tandem differential mobility analyzer measurements. Mean predicted and measured hygroscopic growth factors for 110, 165, and 265 nm particles were found to agree within 6%. Single particle-based ZSR hygroscopicity estimates offer an advantage over bulk aerosol composition-based hygroscopicity estimates by providing additional chemical mixing state information. External mixing can be determined for particles of a given diameter through examination of the predicted hygroscopic growth factor distributions. Using this approach, 110 nm and 265 nm particles were found to be predominantly internally mixed; however, external mixing of 165 nm particles was observed periodically when thinly coated and thickly coated black carbon particles were simultaneously detected. Single particle-resolved chemical information will be useful for modeling efforts aimed at constraining cloud condensation nuclei activity and hygroscopic growth.

Receptor modeling was performed on quadrupole unit mass resolution aerosol mass spectrometer (Q-AMS) sub-micron particulate matter (PM) chemical speciation measurements from Windsor, Ontario, an industrial city situated across the Detroit River from Detroit, Michigan. Aerosol and trace gas measurements were collected on board Environment Canada's Canadian Regional and Urban Investigation System for Environmental Research (CRUISER) mobile laboratory. Positive matrix factorization (PMF) was performed on the AMS full particle-phase mass spectrum (PMFFull MS) encompassing both organic and inorganic components. This approach compared to the more common method of analyzing only the organic mass spectra (PMFOrg MS). PMF of the full mass spectrum revealed that variability in the non-refractory sub-micron aerosol concentration and composition was best explained by six factors: an amine-containing factor (Amine); an ammonium sulfate- and oxygenated organic aerosol-containing factor (Sulfate-OA); an ammonium nitrate- and oxygenated organic aerosol-containing factor (Nitrate-OA); an ammonium chloride-containing factor (Chloride); a hydrocarbon-like organic aerosol (HOA) factor; and a moderately oxygenated organic aerosol factor (OOA). PMF of the organic mass spectrum revealed three factors of similar composition to some of those revealed through PMFFull MS: Amine, HOA and OOA. Including both the inorganic and organic mass proved to be a beneficial approach to analyzing the unit mass resolution AMS data for several reasons. First, it provided a method for potentially calculating more accurate sub-micron PM mass concentrations, particularly when unusual factors are present, in this case the Amine factor. As this method does not rely on a priori knowledge of chemical species, it circumvents the need for any adjustments to the traditional AMS species fragmentation patterns to account for atypical species, and can thus lead to more complete factor profiles. It is expected that this method would be even more useful for HR–ToF–AMS data, due to the ability to understand better the chemical nature of atypical factors from high-resolution mass spectra. Second, utilizing PMF to extract factors containing inorganic species allowed for the determination of the extent of neutralization, which could have implications for aerosol parameterization. Third, subtler differences in organic aerosol components were resolved through the incorporation of inorganic mass into the PMF matrix. The additional temporal features provided by the inorganic aerosol components allowed for the resolution of more types of oxygenated organic aerosol than could be reliably resolved from PMF of organics alone. Comparison of findings from the PMFFull MS and PMFOrg MS methods showed that for the Windsor airshed, the PMFFull MS method enabled additional conclusions to be drawn in terms of aerosol sources and chemical processes. While performing PMFOrg MS can provide important distinctions between types of organic aerosol, it is shown that including inorganic species in the PMF analysis can permit further apportionment of organics for unit mass resolution AMS mass spectra.

Exposure to wildfire smoke is a public health issue of increasing prominence in North America, particularly in western states and provinces. In this study, Aethalometer data collected at six sites in the Lower Fraser Valley (LFV), British Columbia, from September 2016 through August 2017 were analyzed to investigate the relative importance of fossil fuel and biomass burning contributions to black carbon (BC) in the region. Annual mean BC mass concentrations were in the range 0.3–0.8 μg m−3, and BC was apportioned to fossil fuel and biomass burning sources at hourly resolution using the dual-wavelength Aethalometer model, applying a typical a priori assumed biomass burning Absorption Angstrom Exponent (AAE) value close to 2. However, this approach was found to underestimate biomass contributions to BC mass by up to a factor of three during wildfire events that impacted air quality throughout the region in July and August 2017. Hourly resolution PM2.5 concentrations in excess of 100 μg m−3 were recorded at multiple sites and mean ambient PM2.5 concentrations for the wildfire smoke periods were up to nine times higher than mean concentrations for the remainder of the summer. A background extraction approach was applied to optimize BC source apportionment during these events and to enable the calculation of wildfire aerosol AAE, with similar values for the latter determined across all six sites (1.35 ± 0.09). The relatively low AAE values observed suggest that evaporation and/or photobleaching of brown carbon occurred during transport of wildfire aerosol to the receptor sites. From an exposure perspective, for the sites investigated, up to 69 ± 20% (±1σ) of ambient BC is attributed to wildfires during these events. On an annual scale, however, fossil fuel combustion and residential/agricultural biomass burning are estimated to be more important contributors to ambient BC mass concentrations at every site.

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, sQTBA

The climatic impacts of black carbon (BC) aerosol, an important absorber of solar radiation in the atmosphere, remain poorly constrained and are intimately related to its particle-scale physical and chemical properties. Using particle-resolved modelling informed by quantitative measurements from a soot-particle aerosol mass spectrometer, we confirm that the mixing state (the distribution of co-emitted aerosol amongst fresh BC-containing particles) at the time of emission significantly affects BC-aerosol optical properties even after a day of atmospheric processing. Both single particle and ensemble aerosol mass spectrometry observations indicate that BC near the point of emission co-exists with hydrocarbon-like organic aerosol (HOA) in two distinct particle types: HOA-rich and BC-rich particles. The average mass fraction of black carbon in HOA-rich and BC-rich particle classes was

Four field campaigns were conducted between February 2014 and January 2015 to measure emissions from light-duty gasoline direct injection (GDI) vehicles (2013 Ford Focus) in an urban near-road environment in Toronto, Canada. Measurements of CO2, CO, NOx, black carbon (BC), benzene, toluene, ethylbenzene-xylenes (BTEX), and size-resolved particle number (PN) were recorded 15 m from the roadway and converted to fuel-based emission factors (EFs). Other than for NOx and CO, the GDI engine had elevated emissions compared to the Toronto fleet, with BC EFs in the 73rd percentile, BTEX EFs in the 80-90th percentile, and PN EFs in the 75th percentile during wintertime measurements. Additionally, for three campaigns, a second platform for measuring PN and CO2 was placed 1.5-3 m from the roadway to quantify changes in PN with distance from point of emission. GDI vehicle PN EFs were found to increase by up to 240% with increasing distance from the roadway, predominantly due to an increasing fraction of sub-40 nm particles. PN and BC EFs from the same engine technology were also measured in the laboratory. BC EFs agreed within 20% between the laboratory and real-world measurements; however, laboratory PN EFs were an order of magnitude lower due to exhaust conditioning.

Air quality models are used to simulate and forecast pollutant concentrations, from continental scales to regional and urban scales. These models usually assume that particles are internally mixed, i.e. particles of the same size have the same chemical composition, which may vary in space and time. Although this assumption may be realistic for continental-scale simulations, where particles originating from different sources have undergone sufficient mixing to achieve a common chemical composition for a given model grid cell and time, it may not be valid for urban-scale simulations, where particles from different sources interact on shorter time scales. To investigate the role of the mixing state assumption on the formation of particles, a size-composition resolved aerosol model (SCRAM) was developed and coupled to the Polyphemus air quality platform. Two simulations, one with the internal mixing hypothesis and another with the external mixing hypothesis, have been carried out for the period 15 January to 11 February 2010, when the MEGAPOLI winter field measurement campaign took place in Paris. The simulated bulk concentrations of chemical species and the concentrations of individual particle classes are compared with the observations of Healy et al. (Atmos. Chem. Phys., 2013, 13, 9479–9496) for the same period. The single particle diversity and the mixing-state index are computed based on the approach developed by Riemer et al. (Atmos. Chem. Phys., 2013, 13, 11423–11439), and they are compared to the measurement-based analyses of Healy et al. (Atmos. Chem. Phys., 2014, 14, 6289–6299). The average value of the single particle diversity, which represents the average number of species within each particle, is consistent between simulation and measurement (2.91 and 2.79 respectively). Furthermore, the average value of the mixing-state index is also well represented in the simulation (69% against 59% from the measurements). The spatial distribution of the mixing-state index shows that the particles are not mixed in urban areas, while they are well mixed in rural areas. This indicates that the assumption of internal mixing traditionally used in transport chemistry models is well suited to rural areas, but this assumption is less realistic for urban areas close to emission sources.

The photolysis of o-tolualdehyde by natural sunlight has been investigated at the large outdoor European Photoreactor (EUPHORE) in Valencia, Spain. The photolysis rate coefficient was measured directly under different solar flux levels, with values in the range j(o-tolualdehyde) = (1.62-2.15) × 10(-4) s(-1) observed, yielding an average value of j(o-tolualdehyde)/j(NO(2)) = (2.53 ± 0.25) × 10(-2). The estimated photolysis lifetime is 1-2 h, confirming that direct photolysis by sunlight is the major atmospheric degradation pathway for o-tolualdehyde. Published UV absorption cross-section data were used to derive an effective quantum yield (290-400 nm) close to unity, within experimental error. Possible reaction pathways for the formation of the major photolysis products, benzocyclobutenol (tentatively identified) and o-phthalaldehyde, are proposed. Appreciable yields (5-13%) of secondary organic aerosol (SOA) were observed at EUPHORE and also during supplementary experiments performed in an indoor chamber using an artificial light source. Off-line analysis by gas chromatography-mass spectrometry allowed identification of o-phthalaldehyde, phthalide, phthalic anhydride, o-toluic acid, and phthalaldehydic acid in the particle phase.

PM2.5 samples collected at Cork Harbour, Ireland during summer, autumn, late autumn and winter, 2008–2009 were analyzed for polar organic compounds that are useful markers for aerosol source characterization. The determined compounds include tracers for biomass burning primary particles, fungal spores, markers for secondary organic aerosol (SOA) from isoprene, α-/β-pinene, and d -limonene. Seasonal and temporal variations and other characteristic features of the detected tracers are discussed in terms of aerosol sources and processes. The biogenic species were detected only during the summer period where the contributions of isoprene SOA and fungal spores to the PM2.5 organic carbon (OC) were estimated to be 1.6% and 1% respectively. The biomass burning markers, and in particular levoglucosan, were present in all samples and attributed to the combustion of cellulose-containing fuels including wood, peat, bituminous and smokeless coal. The contribution of domestic solid fuel (DSF) burning to the measured OC mass concentration was estimated at 10.8, 50, 66.4 and 74.9% for summer, autumn, late autumn and winter periods, respectively, based on factors derived from a series of burning experiments on locally available fuels. Application of an alternative approach, namely principal component analysis–multiple linear regression (PCA–MLR), to the measured concentrations of the polar organic marker compounds used in conjunction with real-time air quality data provided similar trends and estimates for DSF combustion during all seasons except summer. This study clearly demonstrates that, despite the ban on the sale of bituminous coal in Cork and other large urban areas in Ireland, DSF combustion is still the major source of OC during autumn and winter periods and also makes a significant contribution to PM2.5 levels. The developed marker approach for estimating the contribution of DSF combustion to ambient OC concentrations can, in principle, also be applied to other locations.

Emissions from shipping traffic may impact severely upon air quality in port cities. In this study, the size and composition of freshly emitted individual ship exhaust particles has been investigated using an aerosol time-of-flight mass spectrometer (ATOFMS) co-located with a suite of real-time instrumentation at a site in the Port of Cork, Ireland. The collected spectra were clustered using the K-means algorithm and a unique ship exhaust class containing internally mixed elemental and organic carbon, sodium, calcium, iron, vanadium, nickel and sulfate was identified. Over twenty sharp emission events were observed for this particle type during the three week measurement period in August 2008. Coincident increases in mass concentrations of sulfate, elemental carbon and particles below 2.5 μm in diameter (PM2.5) were also observed during these events. Simultaneous scanning mobility particle sizer (SMPS) measurements indicate that the vast majority of freshly emitted ship exhaust particles lie in the ultrafine mode (