Robert D. McWhinney

Kinetic limitations in gas-particle reactions arising from slow diffusion in secondary organic aerosol

The potential for aerosol physical properties, such as phase, morphology and viscosity/ diffusivity, to affect particle reactivity remains highly uncertain. We report here a study of the effect of bulk diffusivity of polycyclic aromatic hydrocarbons (PAHs) in secondary organic aerosol (SOA) on the kinetics of the heterogeneous reaction of particle-borne benzo[a]pyrene (BaP) with ozone. The experiments were performed by coating BaP-ammonium sulfate particles with multilayers of SOA formed from ozonolysis of alpha-pinene, and by subsequently investigating the kinetics of BaP loss via reaction with excess ozone using an aerosol flow tube coupled to an Aerodyne Aerosol Mass Spectrometer (AMS). All reactions exhibit pseudo-first order kinetics and are empirically well described by a Langmuir-Hinshelwood (L-H) mechanism. The results show that under dry conditions (RH < 5%) diffusion through the SOA coating can lead to significant mass transfer constraints on the kinetics, with behavior between that previously observed by our group for solid and liquid organic coats. The reactivity of BaP was enhanced at -50% relative humidity (RH) suggesting that water uptake lowers the viscosity of the SOA, hence lifting the mass transfer constraint to some degree. The kinetics for -70% RH were similar to results obtained without SOA coats, indicating that the SOA had sufficiently low viscosity and was sufficiently liquid-like that reactants could rapidly diffuse through the coat. A kinetic multi-layer model for aerosol surface and bulk chemistry was applied to simulate the kinetics, yielding estimates for the diffusion coefficients (in cm2 s(-1)) for BaP in alpha-pinene SOA of 2 x 10(-14), 8 x 10(-14) and > 1 x 10(-12) for dry (RH < 5%), 50% RH and 70% RH conditions, respectively. These results clearly indicate that slow diffusion of reactants through SOA coats under specific conditions can provide shielding from gas-phase oxidants, enabling the long-range atmospheric transport of toxic trace species, such as PAHs and persistent organic pollutants.

Cytotoxic and proinflammatory effects of ambient and source-related particulate matter (PM) in relation to the production of reactive oxygen species (ROS) and cytokine adsorption by particles

The composition of airborne particulate matter (PM) varies widely depending on its source, and recent studies have suggested that particle-associated adverse health effects are related to particle composition. The objective of this study was to compare the biological/toxicological effects of different source-related PM. Specifically, we investigated the biological/toxicological effects of standard reference materials (SRMs): non-ferrous dust (PD-1, industrial), urban PM (UPM, SRM1648a), and diesel PM (DPM, SRM2975), and ambient PM2.5 (PM with an aerodynamic diameter <2.5 µm) collected at an urban site (Toronto, Canada). The dithiothreitol assay was used to measure the redox activity of the particles. Human alveolar epithelial cells (A549) were exposed to a range of concentrations (10–1000 µg/ml) of total PM, and the respective water-soluble and insoluble fractions, for 24 h. Biological responses were then evaluated in terms of cytotoxicity and interleukin (IL)-8 release, and compared with the PM composition and redox activity. We demonstrated that transition metal-enriched PD-1 exhibited the greatest cytotoxic effect (LD50 values of 100–400 µg/ml vs. >1000 µg/ml for the SRM1648a, SRM2975, and ambient PM2.5). Similarly, the PM-induced release of IL-8 was greatest for PD-1 (~6–9 ng/ml vs. ~1.5–3 ng/ml for others). These endpoints were more responsive to metals as compared with compared with secondary inorganic ions and organic compounds. Interestingly, we demonstrated a high degree of adsorption of IL-8 to the various SRMs and ambient PM2.5, and subsequently derived a new correction method to aid in interpretation of these data. These characteristics likely impart differential effects toward the toxic and immune effects of PM.

Evaluation of the effects of ozone oxidation on redox-cycling activity of two-stroke engine exhaust particles.

The effect of oxidation on the redox-cycling activity of engine exhaust particles is examined. Particles obtained from a two-stroke gasoline engine were oxidized in a flow tube with ozone on a one-minute time scale both in the presence and absence of substantial gas-phase exhaust components. Whereas ozone concentrations were high, the ozone exposures were approximately equivalent to 60 ppb ozone for 2-8 h. Oxidation led to substantial increases in redox-cycling of aqueous extracts of filtered particles, as measured using the dithiothreitol (DTT) assay. Increases in redox activity when the entire exhaust was oxidized were primarily driven by deposition of redox-active secondary organic aerosol (SOA), resulting in an upper-limit DTT activity of 8.6 ± 2.0 pmol DTT consumed per min per microgram of particles, compared to 0.73 ± 0.60 pmol min(-1) μg(-1) for fresh, unoxidized exhaust particles. Redox-cycling activity reached higher levels when VOC denuded exhaust was oxidized, with the highest DTT activity observed being 16.7 ± 1.6 pmol min(-1) μg(-1) with no upper limit reached for the range of ozone exposures used in this study. Our results provide laboratory support for the hypothesis that the toxicity of engine combustion particles due to redox-cycling may increase as they age in the atmosphere.

The combined effects of physicochemical properties of size-fractionated ambient particulate matter on in vitro toxicity in human A549 lung epithelial cells

Epidemiological and toxicological studies have suggested that the health effects associated with exposure to particulate matter (PM) are related to the different physicochemical properties of PM. These effects occur through the initiation of differential cellular responses including: the induction of antioxidant defenses, proinflammatory responses, and ultimately cell death. The main objective of this study was to investigate the effects of size-fractionated ambient PM on epithelial cells in relation to their physicochemical properties. Concentrated ambient PM was collected on filters for three size fractions: coarse (aerodynamic diameter [AD] 2.5–10 μm), fine (0.15–2.5 μm), and quasi-ultrafine (<0.2 μm), near a busy street in Toronto, Ontario, Canada. Filters were extracted and analyzed for chemical composition and redox activity. Chemical analyses showed that the coarse, fine, and quasi-ultrafine particles were comprised primarily of metals, water-soluble species, and organic compounds, respectively. The highest redox activity was observed for fine PM. After exposure of A549 cells to PM (10–100 μg/ml) for 4 h, activation of antioxidant, proinflammatory and cytotoxic responses were assessed by determining the expression of heme oxygenase (HMOX-1, mRNA), interleukin-8 (IL-8, mRNA), and metabolic activity of the cells, respectively. All three size fractions induced mass-dependent antioxidant, proinflammatory, and cytotoxic responses to different degrees. Quasi-ultrafine PM caused significant induction of HMOX-1 at the lowest exposure dose. Correlation analyses with chemical components suggested that the biological responses correlated mainly with transition metals and organic compounds for coarse and fine PM and with organic compounds for quasi-ultrafine PM. Overall, the observed biological responses appeared to be related to the combined effects of size and chemical composition and thus both of these physicochemical properties should be considered when explaining PM toxicity.

Physical Characterization of the University of Toronto Coarse, Fine, and Ultrafine High-Volume Particle Concentrator Systems

Particle concentrators allow exposure to controlled levels of concentrated ambient particulate matter (PM) over a broad range of concentrations. The performance of these systems can be influenced by the physicochemical characteristics of PM and so it is vital to characterize the concentrators at a given site. The quasi-ultrafine PM (<0.2 μm), fine PM (0.15–2.5 μm), and coarse PM (2.5–10 μm) concentrators at the Southern Ontario Center for Atmospheric Aerosol Research (SOCAAR), University of Toronto, were characterized as a part of the “Health Effects of Aerosols in Toronto (HEAT)” campaign held during February–March, 2010. The full size distributions of ambient and concentrated particles were simultaneously measured in terms of number, surface area, and volume using high time-resolution instruments. Examination of the complete size distribution, including the unconcentrated particles beyond the cutpoints of the concentrator systems, revealed that particles in the unconcentrated size ranges made significant contributions to the particle number and surface area present in the concentrated airstreams of fine and coarse concentrators. Further transients in the ambient ultrafine particle concentrations were evident as dampened signals in these concentrated airstreams. The ultrafine concentrator exhibited a significant size shift when the ambient particle size distribution had a mode ≤30 nm. Overall the fine and coarse concentrators provided a reasonable concentrated reproduction of the ambient PM mass while questions remain regarding the representativeness of the ultrafine concentrator. Copyright 2012 American Association for Aerosol Research

Characterization of the University of Toronto Concentrated Aerosol Particle Exposure Facility (CAPEF)—Effects on Fine and Ultrafine Nonrefractory Aerosol Composition

Virtual impactor-based particle concentrators have been developed to enable the study of biological mechanisms and dose-response relationships of particulate matter (PM) inhalation. The Concentrated Aerosol Particle Exposure Facility (CAPEF) at the University of Toronto houses the Harvard School of Public Health designed coarse, fine, and quasi-ultrafine particle concentrators for such studies. Characterization of the concentration of the nonrefractory components of ambient particles was carried out in the winter of 2010. The fine concentrator shows higher mass concentration factors for ambient sulfate than for semi-volatile components, as measured using an Aerodyne aerosol mass spectrometer (AMS). The change in composition is based on the relative size distributions of particulate sulfate, which, compared to particulate organic and nitrate, is more dominant in larger particles more efficiently concentrated due to the physical characteristics of the virtual impactors. The ultrafine concentrator, which requires aqueous condensational growth of particles prior to concentration, shows a large enhancement in organic mass both for ambient particles and for laboratory-generated ammonium sulfate and ammonium nitrate particles added to filtered outdoor air. As suggested previously, changes in the organic mass spectrum and size distributions are consistent with addition of organic mass through reactions of water-soluble volatile organic compounds. Coagulation of particles or droplet coalescence may also account for some of the observed increase in organic mass and nitrate may be lost due to volatilization. While such effects are unlikely to affect refractory species, increased attention should be given to the effect of condensational growth on the composition of concentrated ultrafine particles. Copyright 2012 American Association for Aerosol Research