Formation and evolution of secondary organic aerosols derived from urban-lifestyle sources: vehicle exhaust and cooking emissions

Vehicle exhaust and cooking emissions are closely related to the daily life of city dwellers. Here, we defined the secondary organic aerosols (SOAs) derived from vehicle exhaust and cooking emissions as “urban-lifestyle SOAs” and simulated their formation using a Gothenburg potential aerosol mass reactor (Go:PAM). The vehicle exhaust and cooking emissions were separately simulated, and their samples were defined as “vehicle group” and “cooking group”, respectively. After samples had been aged under 0.3–5.5 d of equivalent photochemical age, these two urban-lifestyle SOAs showed markedly distinct features in the SOA mass growth potential, oxidation pathways, and mass spectra. The SOA/POA (primary organic aerosol) mass ratios of vehicle groups (107) were 44 times larger than those of cooking groups (2.38) at about 2 d of equivalent photochemical age, according to the measurement of scanning mobility particle sizer (SMPS). A high-resolution time-of-flight aerosol mass spectrometer was used to perform a deeper analysis. It revealed that organics from the vehicle may undergo the alcohol and/or peroxide and carboxylic acid oxidation pathway to produce abundant less and more oxidized oxygenated OAs (LO-OOAs and MO-OOAs), and only a few primary hydrocarbon-like organic aerosols (HOAs) remain unaged. In contrast, organics from cooking may undergo the alcohol and/or peroxide oxidation pathway to produce moderate LO-OOAs, and comparable primary cooking organic aerosols (COAs) remain unaged. Our findings provide an insight into atmospheric contributions and chemical evolutions for urban-lifestyle SOAs, which could greatly influence the air quality and health risk assessments in urban areas.

Formation and Evolution of Secondary Organic Aerosol Derived from Urban Lifestyle Sources: Vehicle Exhaust and Cooking Emission

Both vehicle exhaust and cooking emission are closely related to the daily life of city dwellers, which are considered as major sources of urban secondary organic aerosol (SOA). Here, we defined the SOA derived from vehicle exhaust and cooking emission as Urban Lifestyle SOA, and simulated their formation using a Gothenburg potential aerosol mass reactor (Go: PAM). After samples had been aged under 0.3–5.5 days of equivalent photochemical age, these two urban lifestyle SOA showed markedly distinct features in SOA mass growth potentials, oxidation pathways and mass spectra. The SOA / POA mass ratios of vehicle groups (107) were 44 times larger than those of cooking groups (2.38) at about 2 days of equivalent photochemical age. It reveals that organics from vehicle may undergo the alcohol/peroxide and carboxylic acid oxidation pathway to produce abundant less/more oxidized oxygenated OA (LO-OOA and MO-OOA), and only a few primary hydrocarbon-like organic aerosol (HOA) remains unaged. In contrast, organics from cooking may undergo the alcohol/peroxide oxidation pathway to produce moderate LO-OOA, and comparable primary cooking organic aerosol (COA) remains unaged. Our findings provide an insight into atmospheric contributions and chemical evolutions for urban lifestyle SOA, which would greatly influence the air quality and health risk assessments in urban areas.

Understanding the optical properties of ambient sub- and supermicron particulate matter: results from the CARES 2010 field study in northern California

Measurements of the optical properties (absorption, scattering and extinction) of PM1, PM2.5 and PM10 made at two sites around Sacramento, CA, during the June 2010 Carbonaceous Aerosols and Radiative Effects Study (CARES) are reported. These observations are used to establish relationships between various intensive optical properties and to derive information about the dependence of the optical properties on photochemical aging and sources. Supermicron particles contributed substantially to the total light scattering at both sites, about 50 % on average. A strong, linear relationship is observed between the scattering Ångström exponent for PM10 and the fraction of the scattering that is contributed by submicron particles (fsca, PM1) at both sites and with similar slopes and intercepts (for a given pair of wavelengths), suggesting that the derived relationship may be generally applicable for understanding variations in particle size distributions from remote sensing measurements. At the more urban T0 site, the fsca, PM1 increased with photochemical age, whereas at the downwind, more rural T1 site the fsca, PM1 decreased slightly with photochemical age. This difference in behavior reflects differences in transport, local production and local emission of supermicron particles between the sites. Light absorption is dominated by submicron particles, but there is some absorption by supermicron particles ( ∼ 15 % of the total). The supermicron absorption derives from a combination of black carbon that has penetrated into the supermicron mode and from dust, and there is a clear increase in the mass absorption coefficient of just the supermicron particles with increasing average particle size. The mass scattering coefficient (MSC) for the supermicron particles was directly observed to vary inversely with the average particle size, demonstrating that MSC cannot always be treated as a constant in estimating mass concentrations from scattering measurements, or vice versa. The total particle backscatter fraction exhibited some dependence upon the relative abundance of sub- versus supermicron particles; however this was modulated by variations in the median size of particles within a given size range; variations in the submicron size distribution had a particularly large influence on the observed backscatter efficiency and an approximate method to account for this variability is introduced. The relationship between the absorption and scattering Ångström exponents is examined and used to update a previously suggested particle classification scheme. Differences in composition led to differences in the sensitivity of PM2.5 to heating in a thermodenuder to the average particle size, with more extensive evaporation (observed as a larger decrease in the PM2.5 extinction coefficient) corresponding to smaller particles; i.e., submicron particles were generally more susceptible to heating than the supermicron particles. The influence of heating on the particle hygroscopicity varied with the effective particle size, with larger changes observed when the PM2.5 distribution was dominated by smaller particles.

Photochemical age of air pollutants, ozone, and secondary organic aerosol in transboundary air observed on Fukue Island, Nagasaki, Japan

To better understand the secondary air pollution in transboundary air over westernmost Japan, ground-based field measurements of the chemical composition of fine particulate matter ( ≤ 1 µm), mixing ratios of trace gas species (CO, O3, NOx, NOy, i-pentane, toluene, and ethyne), and meteorological elements were conducted with a suite of instrumentation. The CO mixing ratio dependence on wind direction showed that there was no significant influence from primary emission sources near the monitoring site, indicating long- and/or mid-range transport of the measured chemical species. Despite the considerably different atmospheric lifetimes of NOy and CO, these mixing ratios were correlated (r2 = 0.67). The photochemical age of the pollutants, t[OH] (the reaction time × the mean concentration of OH radical during the atmospheric transport), was calculated from both the NOx ∕ NOy concentration ratio (NOx ∕ NOy clock) and the toluene ∕ ethyne concentration ratio (hydrocarbon clock). It was found that the toluene / ethyne concentration ratio was significantly influenced by dilution with background air containing 0.16 ppbv of ethyne, causing significant bias in the estimation of t[OH]. In contrast, the influence of the reaction of NOx with O3, a potentially biasing reaction channel on [NOx] / [NOy], was small. The t[OH] values obtained with the NOx ∕ NOy clock ranged from 2.9 × 105 to 1.3 × 108 h molecule cm−3 and were compared with the fractional contribution of the m∕z 44 signal to the total signal in the organic aerosol mass spectra (f44, a quantitative oxidation indicator of carboxylic acids) and O3 mixing ratio. The comparison of t[OH] with f44 showed evidence for a systematic increase of f44 as t[OH] increased, an indication of secondary organic aerosol (SOA) formation. To a first approximation, the f44 increase rate was (1.05 ± 0.03) × 10−9 × [OH] h−1, which is comparable to the background-corrected increase rate observed during the New England Air Quality Study in summer 2002. The similarity may imply the production of similar SOA component, possibly humic-like substances. Meanwhile, the comparison of t[OH] with O3 mixing ratio showed that there was a strong proportional relationship between O3 mixing ratio and t[OH]. A first approximation gave the increasing rate and background mixing ratio of ozone as (3.48 ± 0.06) × 10−7 × [OH] ppbv h−1 and 30.7 ppbv, respectively. The information given here can be used for prediction of secondary pollution magnitude in the outflow from the Asian continent.

Understanding the Optical Properties of Ambient Sub- and Supermicron Particulate Matter: Results from the CARES 2010 Field Study in Northern California

Measurements of the optical properties (absorption, scattering and extinction) of PM1, PM2.5 and PM10 made at two sites around Sacramento, CA during the June 2010 Carbonaceous Aerosols and Radiative Effects Study (CARES) are reported. These observations are used to establish relationships between various intensive optical properties and to derive information about the dependence of the optical properties on photochemical ageing and sources. Supermicron particles contributed substantially to the total light scattering at both sites, about 50 % on average. A strong, linear relationship is observed between the scattering Ångstrom exponent for PM10 and the fraction of the scattering that is contributed by submicron particles (fsca,PM1) at both sites and with similar slopes and intercepts (for a given pair of wavelengths), suggesting that the derived relationship may be generally applicable for under standing variations in particle size distributions from remote sensing measurements. At the more urban T0 site, the fsca,PM1 increased with photochemical age whereas at the downwind, more rural T1 site the fsca,PM1 decreased slightly with photochemical age. This difference in behavior reflects differences in transport, local production and local emission of supermicron particles between the sites. Light absorption is dominated by submicron particles, but the there is some absorption by supermicron particles (~15 % of the total). The supermicron absorption derives from a combination of black carbon that has penetrated into the supermicron mode and from dust, and there is a clear increase in the mass absorption coefficient of just the supermicron particles with increasing average particle size. The mass scattering coefficient (MSC) for the supermicron particles was directly observed to vary inversely with the average particle size, demonstrating that MSC cannot always be treated as a constant in estimating mass concentrations from scattering measurements, or vice versa. The total particle backscatter fraction exhibited some dependence upon the relative abundance of sub-versus supermicron particles, however this was modulated by variations in the median size of particles within a given size range; variations in the submicron size distribution had a particularly large influence on the observed backscatter efficiency and an approximate method to account for this variability is introduced. The relationship between the absorption and scattering Ångstrom exponents is examined and used to update a previously suggested particle classification scheme. Differences in composition led to differences in the sensitivity of PM2.5 to heating in a thermodenuder to the average particle size, with more extensive evaporation (observed as a larger decrease in the PM2.5 extinction coefficient) corresponding to smaller particles, i.e. submicron particles were generally more susceptible to heating than the supermicron particles. The influence of heating on the particle hygroscopicity varied with the effective particle size, with larger changes observed when the PM2.5 distribution was dominated by smaller particles.