Submicron aerosol particles (PM₁) were measured in-situ using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer during the summer 2009 Field Intensive Study at Queens College in New York, NY. Organic aerosol (OA) and sulfate are the two dominant species, accounting for 54% and 24%, respectively, of the total PM₁ mass. The average mass-based size distribution of OA presents a small mode peaking at ~150 nm (<i>D</i>_va) and an accumulation mode (~550 nm) that is internally mixed with sulfate, nitrate, and ammonium. The diurnal cycles of both sulfate and OA peak between 01:00–02:00 p.m. EST due to photochemical production. The average (±σ) oxygen-to-carbon (O/C), hydrogen-to-carbon (H/C), and nitrogen-to-carbon (N/C) ratios of OA in NYC are 0.36 (±0.09), 1.49 (±0.08), and 0.012 (±0.005), respectively, corresponding to an average organic mass-to-carbon (OM/OC) ratio of 1.62 (±0.11). Positive matrix factorization (PMF) of the high resolution mass spectra identified two primary OA (POA) sources, traffic and cooking, and three secondary OA (SOA) components including a highly oxidized, regional low-volatility oxygenated OA (LV-OOA; O/C = 0.63), a less oxidized, semi-volatile SV-OOA (O/C = 0.38) and a unique nitrogen-enriched OA (NOA; N/C = 0.053) characterized with prominent C_xH_{2x + 2}N⁺ peaks likely from amino compounds. Our results indicate that cooking and traffic are two distinct and mass-equivalent POA sources in NYC, together contributing ~30% of the total OA mass during this study. The OA composition is dominated by secondary species, especially during high PM events. SV-OOA and LV-OOA on average account for 34% and 30%, respectively, of the total OA mass. The chemical evolution of SOA in NYC appears to progress with a continuous oxidation from SV-OOA to LV-OOA, which is further supported by a gradual increase of O/C ratio and a simultaneous decrease of H/C ratio in total OOA. Detailed analysis of NOA (5.8% of OA) presents evidence that organic nitrogen species such as amines might have played an important role in the atmospheric processing of OA in NYC, likely involving both acid-base chemistry and photochemistry. In addition, analysis of air mass trajectories and satellite imagery of aerosol optical depth (AOD) indicates that the high potential source regions of secondary sulfate and aged OA are mainly located in regions to the west and southwest of the city

Fine particulate matters less than 2.5 µm (PM2.5) in the ambient atmosphere are strongly associated with adverse health effects. However, it is unlikely that all fine particles are equally toxic in view of their different sizes and chemical components. Toxicity of fine particles produced from various combustion sources (diesel engine, gasoline engine, biomass burning (rice straw and pine stem burning), and coal combustion) and non-combustion sources (road dust including sea spray aerosols, ammonium sulfate, ammonium nitrate, and secondary organic aerosols (SOA)), which are known major sources of PM2.5, was determined. Multiple biological and chemical endpoints were integrated for various source-specific aerosols to derive toxicity scores for particles originating from different sources. The highest toxicity score was obtained for diesel engine exhaust particles, followed by gasoline engine exhaust particles, biomass burning particles, coal combustion particles, and road dust, suggesting that traffic plays the most critical role in enhancing the toxic effects of fine particles. The toxicity ranking of fine particles produced from various sources can be used to better understand the adverse health effects caused by different fine particle types in the ambient atmosphere, and to provide practical management of fine particles beyond what can be achieved only using PM mass which is the current regulation standard.

Submicron aerosol particles (PM₁) were measured in-situ using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) during the summer 2009 Field Intensive Study at Queens College in New York City. Organic aerosol (OA) and sulfate are the two dominant species, accounting for 54% and 24%, respectively, of total PM₁ mass on average. The average mass size distribution of OA presents a small mode peaking at ~150 nm (<i>D</i>_va) in addition to an accumulation mode (~550 nm) that is internally mixed with sulfate, nitrate, and ammonium. The diurnal cycles of sulfate and OA both show pronounced peaks between 01:00–02:00 p.m. EST due to photochemical production. The average (&plusmn;1&sigma;) oxygen-to-carbon (O/C), hydrogen-to-carbon (H/C), and nitrogen-to-carbon (N/C) ratios of OA in NYC are 0.36 (&plusmn;0.09), 1.49 (&plusmn;0.08), and 0.012(&plusmn;0.005), respectively, corresponding to an average organic mass-to-carbon (OM/OC) ratio of 1.62(&plusmn;0.11). Positive matrix factorization (PMF) of the high resolution mass spectra identified five OA components: a hydrocarbon-like OA (HOA), two types of oxygenated OA (OOA) including a low-volatility OOA (LV-OOA) and a semi-volatile OOA (SV-OOA), a cooking-emission related OA (COA), and a unique nitrogen-enriched OA (NOA). HOA appears to represent primary OA (POA) from urban traffic emissions. It comprises primarily of reduced species (H/C=1.83; O/C=0.06) and shows a mass spectral pattern very similar to those of POA from fossil fuel combustion, and correlates tightly with traffic emission tracers including elemental carbon and NO_x. LV-OOA, which is highly oxidized (O/C=0.63) and correlates well with sulfate, appears to be representative for regional, aged secondary OA (SOA). SV-OOA, which is less oxidized (O/C=0.38) and correlates well with non-refractory chloride, likely represents less photo-chemically aged, semi-volatile SOA. COA shows a similar spectral pattern to the reference spectra of POA from cooking emissions and a distinct diurnal pattern peaking around local lunch and dinner times. In addition, NOA is characterized with prominent C_xH_2x+2N⁺ peaks likely from amine compounds. Our results indicate that cooking-related activities are a major source of POA in NYC, releasing comparable amounts of POA as traffic emissions. POA=HOA+COA) on average accounts for ~30% of the total OA mass during this study while SOA dominates the OA composition with SV-OOA and LV-OOA on average accounting for 34% and 30%, respectively, of the total OA mass. The chemical evolution of SOA in NYC involves a~continuous oxidation from SV-OOA to LV-OOA, which is further supported by a gradual increase of O/C ratio and a simultaneous decrease of H/C ratio in total OOA. Detailed analysis of NOA (5.8% of OA) presents evidence that nitrogen-containing orga...

Knowledge of the variations of mass concentration, chemical composition and size distributions of submicron aerosols near roadways is of importance for reducing exposure assessment uncertainties in health effects studies. The goal of this study is to deploy and evaluate an Atmospheric Sciences Research Center-Mobile Laboratory (ASRC-ML), equipped with a suite of rapid response instruments for characterization of traffic plumes, adjacent to the Long Island Expressway (LIE) &ndash; a high-traffic highway in the New York City Metropolitan Area. In total, four measurement periods, two in the morning and two in the evening were conducted at a location approximately 30 m south of the LIE. The mass concentrations and size distributions of non-refractory submicron aerosol (NR-PM₁) species were measured in situ at a time resolution of 1 min by an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer, along with rapid measurements (down to 1 Hz) of gaseous pollutants (e.g. HCHO, NO₂, NO, O₃, and CO₂, etc.), black carbon (BC), and particle number concentrations and size distributions. Particulate organics varied dramatically during periods with high traffic influences from the nearby roadway. The variations were mainly observed in the hydrocarbon-like organic aerosol (HOA), a surrogate for primary OA from vehicle emissions. The inorganic species (sulfate, ammonium, and nitrate) and oxygenated OA (OOA) showed much smoother variations indicating minor impacts from traffic emissions. The concentration and chemical composition of NR-PM₁ also varied differently on different days depending on meteorology, traffic intensity and vehicle types. Overall, organics dominated the traffic-related NR-PM₁ composition (>60%) with HOA accounting for a major fraction of OA. The traffic-influenced organics showed two distinct modes in mass-weighted size distributions, peaking at &sim;120 nm and 500 nm (vacuum aerodynamic diameter, <i>D</i>_va), respectively. OOA and inorganic species appear to be internally mixed in the accumulation mode peaking at &sim;500&ndash;600 nm. The enhancement of organics in traffic emissions mainly occurred at ultrafine mode dominated by HOA, with little relation to the OOA-dominated accumulation mode. From Fast Mobility Particle Sizer (FMPS) measurements, a large increase in number concentration at &sim;10 nm (mobility number mean diameter, <i>D</i>_m) was also found due to traffic influence; though these particles typically contribute a minor fraction of total particle mass. The observed rapid variations of aerosol chemistry and microphysics may have significant implications for near-highway air pollution characterization and exposure assessments