Shang Liu

Elucidating secondary organic aerosol from diesel and gasoline vehicles through detailed characterization of organic carbon emissions

Emissions from gasoline and diesel vehicles are predominant anthropogenic sources of reactive gas-phase organic carbon and key precursors to secondary organic aerosol (SOA) in urban areas. Their relative importance for aerosol formation is a controversial issue with implications for air quality control policy and public health. We characterize the chemical composition, mass distribution, and organic aerosol formation potential of emissions from gasoline and diesel vehicles, and find diesel exhaust is seven times more efficient at forming aerosol than gasoline exhaust. However, both sources are important for air quality; depending on a region’s fuel use, diesel is responsible for 65% to 90% of vehicular-derived SOA, with substantial contributions from aromatic and aliphatic hydrocarbons. Including these insights on source characterization and SOA formation will improve regional pollution control policies, fuel regulations, and methodologies for future measurement, laboratory, and modeling studies.

Effect of anthropogenic aerosols on biologically active ultraviolet radiation

Aerosols from anthropogenic sources contribute significantly to the scattering of solar radiation in the atmosphere over most populated areas. By using observed values of visual range we estimate that in non-urban areas of the industrialized countries the amount of biologically active solar radiation (UVB, 280 to 315 nm) reaching the surface has decreased by a range of 5 to 18% since the industrial revolution, primarily due to aerosols formed from emissions of sulfur dioxide (SO2). The UVB reduction in the industrialized countries may have offset partly or fully the UVB increases associated with current stratospheric ozone depletion at NH continental mid-latitudes. However, this offset is not expected to continue because the SO2 emissions are leveling off in the industrialized countries.

Evidence for NOx Control over Nighttime SOA Formation

Nighttime Sources Organic aerosols account for about half of the total mass of small (submicrometer) particles in the troposphere, and most of them are believed to form through the oxidation of volatile molecules, rather than being emitted directly from specific sources. These particles have important roles in many atmospheric processes, and therefore a better understanding of their complex composition and chemistry is desirable. Rollins et al. (p. 1210) report on measurements of particulate organic nitrates, an important class of organic aerosols that form at night. However, they also found that high concentrations of organic molecules can suppress the growth of organic nitrate particles. These observations should help improve efforts to reduce organic aerosol pollution. The growth of particulate organic nitrates can account for much of the nighttime increase in organic aerosol mass. Laboratory studies have established a number of chemical pathways by which nitrogen oxides (NOx) affect atmospheric organic aerosol (OA) production. However, these effects have not been directly observed in ambient OA. We report measurements of particulate organic nitrates in Bakersfield, California, the nighttime formation of which increases with NOx and is suppressed by high concentrations of organic molecules that rapidly react with nitrate radical (NO3)—evidence that multigenerational chemistry is responsible for organic nitrate aerosol production. This class of molecules represents about a third of the nighttime increase in OA, suggesting that most nighttime secondary OA is due to the NO3 product of anthropogenic NOx emissions. Consequently, reductions in NOx emissions should reduce the concentration of organic aerosol in Bakersfield and the surrounding region.

Mixing state of elemental carbon and non-light-absorbing aerosol components derived from in situ particle optical properties at Xinken in Pearl River Delta of China

Received 29 November 2005; revised 28 April 2006; accepted 5 June 2006; published 21 October 2006. [1] The aerosol mixing state was investigated with an optical closure study at Xinken, Pearl River Delta of China in 2004. On the basis of in situ aerosol microphysical and chemical measurements and a two-component aerosol optical model an internal consistency algorithm was developed to model the mass ratio (r) of externally mixed elemental carbon (EC) to total EC, which minimized the discrepancies between measured and calculated optical properties. The rest of EC was assumed to be internally mixed. A time series of r was retrieved. Good agreement between model and observation was found, on the order of ±15% for total/back scattering coefficients and ±10% for absorption coefficient. The EC mixing state was strongly dependent on the local wind patterns. When north/northeasterly winds prevailed, the air came from the urban and industrial areas of mainland China, and EC was mainly externally mixed with an average r of 85 ± 12%. When the airflow was controlled by a weak local wind system, the mixing state showed a pronounced diurnal variation. During daytime the wind speed was nearly zero. This favored the increase of local pollution, and the average r was about 95%. However, during nighttime the EC mixing state transformed to be internally mixed apparently with an average r of 53 ± 15%, which can be explained by a more aged air mass. The south/ southeasterlywindscomingfromtheseawerefoundtohavethemostimportanteffectonthe transformation of EC mixing state in the night, but fairly rapid local aging processing was also observed. The uncertainties of the model were explored by a Monte Carlo simulation.

Enhanced light absorption by mixed source black and brown carbon particles in UK winter

Black carbon (BC) and light-absorbing organic carbon (brown carbon, BrC) play key roles in warming the atmosphere, but the magnitude of their effects remains highly uncertain. Theoretical modelling and laboratory experiments demonstrate that coatings on BC can enhance BCs light absorption, therefore many climate models simply assume enhanced BC absorption by a factor of ∼1.5. However, recent field observations show negligible absorption enhancement, implying models may overestimate BCs warming. Here we report direct evidence of substantial field-measured BC absorption enhancement, with the magnitude strongly depending on BC coating amount. Increases in BC coating result from a combination of changing sources and photochemical aging processes. When the influence of BrC is accounted for, observationally constrained model calculations of the BC absorption enhancement can be reconciled with the observations. We conclude that the influence of coatings on BC absorption should be treated as a source and regionally specific parameter in climate models.

Hydrolysis of Organonitrate Functional Groups in Aerosol Particles

Organonitrate (ON) groups are thought to be important substituents in secondary organic aerosols (SOAs). Model simulations and laboratory studies indicate a large fraction of ON groups in aerosol particles, but much lower quantities are observed in the atmosphere. Hydrolysis of ON groups in aerosol particles has been proposed recently to account for this discrepancy. To test this hypothesis, we simulated formation of ON molecules in a reaction chamber under a wide range of relative humidity (RH) (0 to 90%). The mass fraction of ON groups (5 to 20% for high-NOx experiments) consistently decreased with increasing RH, which was best explained by hydrolysis of ON groups at a rate of 4 day−1 (lifetime of 6 h) for reactions under RH greater than 20%. In addition, we found that secondary nitrogen-containing molecules absorb light, with greater absorption under dry and high-NOx conditions. This work provides the first evidence for particle-phase hydrolysis of ON groups, a process that could substantially reduce ON group concentration in atmospheric SOAs. Copyright 2012 American Association for Aerosol Research

Coatings and clusters of carboxylic acids in carbon-containing atmospheric particles from spectromicroscopy and their implications for cloud-nucleating and optical properties

Particle shape and distribution of chemical compounds within individual particles are implied in the parameterizations used in air quality and climate models for radiative transfer, volatility, and mass transfer. In this study we employ Scanning Transmission X-Ray Microscopy with Near-Edge X-Ray Absorption Fine Structure Spectroscopy with image analysis and pattern recognition techniques to characterize the chemical structure of 636 particles collected on six field campaigns in the western hemisphere between 2004 and 2008. Many of the particles were chemically heterogeneous. A few observed types include black carbon particles covered by aqueous-phase components (n = 90), dust particles with organic clumps (106), organic particles enriched in carboxylic acid at the surface (54), and inorganic cores encapsulated by organic shells (10). The 90 particles in the first category collectively contained 95 regions showing a strong black-carbon spectral signature associated with the aqueous-phase components, of which 78 were between 0.1 and 1 mm. Organic mass fraction of the organic dust particles varied significantly (mean and standard deviation of 0.3 +/- 0.2), and over half of these dust particles were found to be nearly spherical. Thickness of acid-enriched coatings and carbon on inorganic cores were less than 0.6 mu m in most cases, but accounted for < 0.01 to 0.98 of the particle volume fraction. More than half of the identified organic particles (359) were found to be chemically heterogeneous, and 32 particles were observed as agglomerations or inclusions but did not meet one or more of the criteria of the categories described here. The acidic coatings on black carbon are calculated to have a significant impact on the critical supersaturation of these particles. The measured distribution of aspect ratios of dust and other particles in our samples ranged nonuniformly between 1.0 and 4.6 with a mean of 1.4, which can affect assessment of extinction-to-backscatter ratios over the case where spherical geometry is assumed.

Aerosol single scattering albedo dependence on biomass combustion efficiency: Laboratory and field studies

Single scattering albedo (ω) of fresh biomass burning (BB) aerosols produced from 92 controlled laboratory combustion experiments of 20 different woods and grasses was analyzed to determine the factors that control the variability in ω. Results show that ω varies strongly with fire-integrated modified combustion efficiency (MCEFI)—higher MCEFI results in lower ω values and greater spectral dependence of ω. A parameterization of ω as a function of MCEFI for fresh BB aerosols is derived from the laboratory data and is evaluated by field observations from two wildfires. The parameterization suggests that MCEFI explains 60% of the variability in ω, while the 40% unexplained variability could be accounted for by other parameters such as fuel type. Our parameterization provides a promising framework that requires further validation and is amenable for refinements to predict ω with greater confidence, which is critical for estimating the radiative forcing of BB aerosols.

Formation and growth of ultrafine particles from secondary sources in Bakersfield, California

carbon (EC) and the AMS tracer C4H9 for hydrocarbon-like organic aerosol (HOA) peaked in the early morning during rush hour, indicative of primary emissions. The fact that the particle number concentration peaked in the afternoon, when EC was at minimum, indicates that the midday increase in number concentration was likely due to new particle formation. The potential importance of solar radiation, the condensation sink of vapor on existing particles, concentrations of OH, O3 ,S O2 ,N H3, and VOCs for both condensational growth and new particle formation is evaluated based on the covariation of these parameters with ultrafine mass. The results suggest that the ultrafine particles are from secondary sources that are co-emitted or co-produced with glyoxal and formaldehyde.

Insights into Secondary Organic Aerosol Formation Mechanisms from Measured Gas/Particle Partitioning of Specific Organic Tracer Compounds

In situ measurements of organic compounds in both gas and particle phases were made with a thermal desorption aerosol gas chromatography (TAG) instrument. The gas/particle partitioning of phthalic acid, pinonaldehyde, and 6,10,14-trimethyl-2-pentadecanone is discussed in detail to explore secondary organic aerosol (SOA) formation mechanisms. Measured fractions in the particle phase (f(part)) of 6,10,14-trimethyl-2-pentadecanone were similar to those expected from the absorptive gas/particle partitioning theory, suggesting that its partitioning is dominated by absorption processes. However, f(part) of phthalic acid and pinonaldehyde were substantially higher than predicted. The formation of low-volatility products from reactions of phthalic acid with ammonia is proposed as one possible mechanism to explain the high f(part) of phthalic acid. The observations of particle-phase pinonaldehyde when inorganic acids were fully neutralized indicate that inorganic acids are not required for the occurrence of reactive uptake of pinonaldehyde on particles. The observed relationship between f(part) of pinonaldehyde and relative humidity suggests that the aerosol water plays a significant role in the formation of particle-phase pinonaldehyde. Our results clearly show it is necessary to include multiple gas/particle partitioning pathways in models to predict SOA and multiple SOA tracers in source apportionment models to reconstruct SOA.