Robert M. Healy

The use of polar organic compounds to estimate the contribution of domestic solid fuel combustion and biogenic sources to ambient levels of organic carbon and PM2.5 in Cork Harbour, Ireland

PM(2.5) 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 PM(2.5) 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 PM(2.5) 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.

Light-absorbing properties of ambient black carbon and brown carbon from fossil fuel and biomass burning sources

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.

Local and regional components of aerosol in a heavily trafficked street canyon in central London derived from PMF and cluster analysis of single-particle ATOFMS spectra

Positive matrix factorization (PMF) has been applied to single particle ATOFMS spectra collected on a six lane heavily trafficked road in central London (Marylebone Road), which well represents an urban street canyon. PMF analysis successfully extracted 11 factors from mass spectra of about 700,000 particles as a complement to information on particle types (from K-means cluster analysis). The factors were associated with specific sources and represent the contribution of different traffic related components (i.e., lubricating oils, fresh elemental carbon, organonitrogen and aromatic compounds), secondary aerosol locally produced (i.e., nitrate, oxidized organic aerosol and oxidized organonitrogen compounds), urban background together with regional transport (aged elemental carbon and ammonium) and fresh sea spray. An important result from this study is the evidence that rapid chemical processes occur in the street canyon with production of secondary particles from road traffic emissions. These locally generated particles, together with aging processes, dramatically affected aerosol composition producing internally mixed particles. These processes may become important with stagnant air conditions and in countries where gasoline vehicles are predominant and need to be considered when quantifying the impact of traffic emissions.

Rapid formation of secondary organic aerosol from the photolysis of 1-nitronaphthalene: role of naphthoxy radical self-reaction.

The chemical composition of secondary organic aerosol (SOA) formed from the photolysis of 1-nitronaphthalene in a series of simulation chamber experiments has been investigated using an aerosol time-of-flight mass spectrometer (ATOFMS). The resulting SOA is characterized by the presence of a dimer (286 Da) proposed to be formed through the self-reaction of naphthoxy radicals along with the expected product nitronaphthol. The molecular formulas of the SOA products were confirmed by collecting filter samples and analyzing the extracts using ultrahigh resolution mass spectrometry. Further evidence for the radical self-reaction mechanism was obtained by photolyzing 1-nitronaphthalene in the presence of excess nitrobenzene, where it was shown that the resulting SOA contained a product consistent with the cross-reaction of phenoxy and naphthoxy radicals. The naphthoxy dimer was formed from the photolysis of 1-nitronaphthalene under a variety of different experimental conditions including the presence of excess butyl ether as an OH scavenger and the presence of ambient air and particles. However, formation of the dimer was suppressed when 1-nitronaphthalene was photolyzed in the presence of excess NO and nitronaphthol was instead found to be the dominant particle-phase product indicating that the yield of the dimer is dependent upon the concentration of pre-existing NO(x). The results of this work suggest that photolysis of 1-nitronaphthalene represents a previously unidentified pathway to SOA formation in the troposphere. Analogous mechanisms may also be important for other nitrated polycyclic aromatic hydrocarbons.

Field Measurements of Gasoline Direct Injection Emission Factors: Spatial and Seasonal Variability.

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.

Predicting hygroscopic growth using single particle chemical composition estimates

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.

The atmospheric photolysis of o-tolualdehyde.

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.

Kinetics of the gas-phase reactions of chlorine atoms with naphthalene, acenaphthene, and acenaphthylene.

Reactions of polycyclic aromatic hydrocarbons (PAHs) with chlorine atoms may occur in specific areas such as coastal regions and the marine boundary layer. In this work, rate constants for the gas-phase reactions of naphthalene, acenaphthene, and acenaphthylene with chlorine atoms have been measured using the relative rate technique. Experiments were performed at room temperature (293 ± 2 K) and atmospheric pressure in an atmospheric simulation chamber using a proton-transfer reaction mass spectrometer (PTR-MS) to monitor the concentrations of PAHs and the reference compounds (acetone, methanol, 1,3,5-trimethylbenzene, and isoprene) as a function of time. The rate constants obtained in this work were (in units of cm(3) molecule(-1) s(-1)) (4.22 ± 0.46) × 10(-12), (3.01 ± 0.82) × 10(-10), and (4.69 ± 0.82) × 10(-10) for naphthalene, acenaphthene, and acenaphthylene, respectively. These are the first measurements of the rate constants for gas-phase reactions of Cl atoms with acenaphthene and acenaphthylene. The rate constant determined in this study for the reaction of naphthalene with Cl atoms is not in agreement with the only other previously reported value in the literature. The results are used to assess the potential role of chlorine atom reactions in the atmospheric oxidation of PAHs.

Rapid physical and chemical transformation of traffic-related atmospheric particles near a highway

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.

Real-World Emission of Particles from Vehicles: Volatility and the Effects of Ambient Temperature

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 (<0 °C), the volatile fraction of particles was 94%, but decreased to 85% during warmer periods (>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 findings demonstrate that significant differences exist between particles in thermally treated vehicle exhaust as compared to in real-world vehicle plumes to which populations in near-road environments are actually exposed. Furthermore, the magnitude of these differences are dependent upon season and may be more extreme in colder climates.