Yele Sun

Evolution of Organic Aerosols in the Atmosphere

Framework for Change Organic aerosols make up 20 to 90% of the particulate mass of the troposphere and are important factors in both climate and human heath. However, their sources and removal pathways are very uncertain, and their atmospheric evolution is poorly characterized. Jimenez et al. (p. 1525; see the Perspective by Andreae) present an integrated framework of organic aerosol compositional evolution in the atmosphere, based on model results and field and laboratory data that simulate the dynamic aging behavior of organic aerosols. Particles become more oxidized, more hygroscopic, and less volatile with age, as they become oxygenated organic aerosols. These results should lead to better predictions of climate and air quality. Organic aerosols are not compositionally static, but they evolve dramatically within hours to days of their formation. Organic aerosol (OA) particles affect climate forcing and human health, but their sources and evolution remain poorly characterized. We present a unifying model framework describing the atmospheric evolution of OA that is constrained by high–time-resolution measurements of its composition, volatility, and oxidation state. OA and OA precursor gases evolve by becoming increasingly oxidized, less volatile, and more hygroscopic, leading to the formation of oxygenated organic aerosol (OOA), with concentrations comparable to those of sulfate aerosol throughout the Northern Hemisphere. Our model framework captures the dynamic aging behavior observed in both the atmosphere and laboratory: It can serve as a basis for improving parameterizations in regional and global models.

Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically-influenced Northern Hemisphere midlatitudes

[1] Organic aerosol (OA) data acquired by the Aerosol Mass Spectrometer (AMS) in 37 field campaigns were deconvolved into hydrocarbon-like OA (HOA) and several types of oxygenated OA (OOA) components. HOA has been linked to primary combustion emissions (mainly from fossil fuel) and other primary sources such as meat cooking. OOA is ubiquitous in various atmospheric environments, on average accounting for 64%, 83% and 95% of the total OA in urban, urban downwind, and rural/remote sites, respectively. A case study analysis of a rural site shows that the OOA concentration is much greater than the advected HOA, indicating that HOA oxidation is not an important source of OOA, and that OOA increases are mainly due to SOA. Most global models lack an explicit representation of SOA which may lead to significant biases in the magnitude, spatial and temporal distributions of OA, and in aerosol hygroscopic properties.

Understanding atmospheric organic aerosols via factor analysis of aerosol mass spectrometry: a review.

Organic species are an important but poorly characterized constituent of airborne particulate matter. A quantitative understanding of the organic fraction of particles (organic aerosol, OA) is necessary to reduce some of the largest uncertainties that confound the assessment of the radiative forcing of climate and air quality management policies. In recent years, aerosol mass spectrometry has been increasingly relied upon for highly time-resolved characterization of OA chemistry and for elucidation of aerosol sources and lifecycle processes. Aerodyne aerosol mass spectrometers (AMS) are particularly widely used, because of their ability to quantitatively characterize the size-resolved composition of submicron particles (PM1). AMS report the bulk composition and temporal variations of OA in the form of ensemble mass spectra (MS) acquired over short time intervals. Because each MS represents the linear superposition of the spectra of individual components weighed by their concentrations, multivariate factor analysis of the MS matrix has proved effective at retrieving OA factors that offer a quantitative and simplified description of the thousands of individual organic species. The sum of the factors accounts for nearly 100% of the OA mass and each individual factor typically corresponds to a large group of OA constituents with similar chemical composition and temporal behavior that are characteristic of different sources and/or atmospheric processes. The application of this technique in aerosol mass spectrometry has grown rapidly in the last six years. Here we review multivariate factor analysis techniques applied to AMS and other aerosol mass spectrometers, and summarize key findings from field observations. Results that provide valuable information about aerosol sources and, in particular, secondary OA evolution on regional and global scales are highlighted. Advanced methods, for example a-priori constraints on factor mass spectra and the application of factor analysis to combined aerosol and gas phase data are discussed. Integrated analysis of worldwide OA factors is used to present a holistic regional and global description of OA. Finally, different ways in which OA factors can constrain global and regional models are discussed.

An Aerosol Chemical Speciation Monitor (ACSM) for Routine Monitoring of the Composition and Mass Concentrations of Ambient Aerosol

We present a new instrument, the Aerosol Chemical Speciation Monitor (ACSM), which routinely characterizes and monitors the mass and chemical composition of non-refractory submicron particulate matter in real time. Under ambient conditions, mass concentrations of particulate organics, sulfate, nitrate, ammonium, and chloride are obtained with a detection limit <0.2 μg/m3 for 30 min of signal averaging. The ACSM is built upon the same technology as the widely used Aerodyne Aerosol Mass Spectrometer (AMS), in which an aerodynamic particle focusing lens is combined with high vacuum thermal particle vaporization, electron impact ionization, and mass spectrometry. Modifications in the ACSM design, however, allow it to be smaller, lower cost, and simpler to operate than the AMS. The ACSM is also capable of routine stable operation for long periods of time (months). Results from a field measurement campaign in Queens, NY where the ACSM operated unattended and continuously for 8 weeks, are presented. ACSM data is analyzed with the same well-developed techniques that are used for the AMS. Trends in the ACSM mass concentrations observed during the Queens, NY study compare well with those from co-located instruments. Positive Matrix Factorization (PMF) of the ACSM organic aerosol spectra extracts two components: hydrocarbon-like organic aerosol (HOA) and oxygenated organic aerosol (OOA). The mass spectra and time trends of both components correlate well with PMF results obtained from a co-located high resolution time-of-flight AMS instrument.

Investigation of the sources and evolution processes of severe haze pollution in Beijing in January 2013

China experienced severe haze pollution in January 2013. Here we have a detailed characterization of the sources and evolution mechanisms of this haze pollution with a focus on four haze episodes that occurred during 10–14 January in Beijing. The main source of data analyzed is from submicron aerosol measurements by an Aerodyne Aerosol Chemical Speciation Monitor. The average PM1 mass concentration during the four haze episodes ranged from 144 to 300 µg m−3, which was more than 10 times higher than that observed during clean periods. All submicron aerosol species showed substantial increases during haze episodes with sulfate being the largest. Secondary inorganic species played enhanced roles in the haze formation as suggested by their elevated contributions during haze episodes. Positive matrix factorization analysis resolved six organic aerosol (OA) factors including three primary OA (POA) factors from traffic, cooking, and coal combustion emissions, respectively, and three secondary OA (SOA) factors. Overall, SOA contributed 41–59% of OA with the rest being POA. Coal combustion OA (CCOA) was the largest primary source, on average accounting for 20–32% of OA, and showed the most significant enhancement during haze episodes. A regional SOA (RSOA) was resolved for the first time which showed a pronounced peak only during the record-breaking haze episode (Ep3) on 12–13 January. The regional contributions estimated based on the steep evolution of air pollutants were found to play dominant roles for the formation of Ep3, on average accounting for 66% of PM1 during the peak of Ep3 with sulfate, CCOA, and RSOA being the largest fractions (> ~ 75%). Our results suggest that stagnant meteorological conditions, coal combustion, secondary production, and regional transport are four main factors driving the formation and evolution of haze pollution in Beijing during wintertime.

Primary and secondary organic aerosols in Fresno, California during wintertime: Results from high resolution aerosol mass spectrometry

of 7.9 m gm � 3 and a nominal formula of C1H1.59N0.014O0.27S0.00008, which corresponds to an average organic mass-to-carbon ratio of 1.50. Three primary OA (POA) factors and one oxygenated OA factor (OOA) representative of secondary OA (SOA) were identified via Positive Matrix Factorization of the high-resolution mass spectra. The three POA factors, which include a traffic-related hydrocarbon-like OA (HOA), a cooking OA (COA), and a biomass burning OA (BBOA) released from residential heating, accounted for an average 57% of the OA mass and up to 80% between 6 – 9 P.M., during which enhanced emissions from evening rush hour traffic, dinner cooking, and residential wood burning were exacerbated by low mixed layer height. The mass-based size distributions of the OA factors were estimated based on multilinear analysis of the size-resolved mass spectra of organics. Both HOA and BBOA peaked at � 140 nm in vacuum aerodynamic diameter (Dva) while OOA peaked at an accumulation mode of � 460 nm. COA exhibited a unique size distribution with two size modes centering at � 200 nm and 450 nm respectively. This study highlights the leading roles played by anthropogenic POA emissions, primarily from traffic, cooking and residential heating, in aerosol pollution in Fresno in wintertime.

Pollution Gradients and Chemical Characterization of Particulate Matter from Vehicular Traffic near Major Roadways: Results from the 2009 Queens College Air Quality Study in NYC

We present measurements of traffic-related pollutants made near the Long Island Expressway (LIE, I-495), in Queens, New York. The Aerodyne Research Inc. (ARI) mobile laboratory (AML) was deployed to map spatial and temporal gradients of gas-phase species and particulate matter (PM) associated with vehicular exhaust in the residential areas near the LIE. We observe that pollutant levels build up during the early morning hours under stable boundary layer conditions yet fall off quickly within 150 m downwind of the highway. An ARI soot particle aerosol mass spectrometer (SP-AMS) provided measurements of the size-resolved chemical composition of refractory black carbon (rBC) and the associated coating species. The average size distribution of the traffic related PM is characterized by a rBC mode centered at ∼100 nm in vacuum aerodynamic diameter, D va (rBC mass fraction ∼50%). A second rBC mode (rBC mass fraction ∼5%) more heavily coated with organic material is also observed at D va ∼500 nm. Positive matrix factorization (PMF) analyses of the traffic-related PM indicates that rBC is mostly associated with hydrocarbon-like organic (HOA) PM. These results are discussed in the context of chemically resolved size distributions and PMF analysis results performed on the SP-AMS stationary data collected at the Queens College site. Finally, we report emission indices (EI) for both fleet-average conditions and single vehicles, including several New York City Metropolitan Transit Authority (MTA) buses, sampled by the AML in “chase” mode during the study. Copyright 2012 American Association for Aerosol Research

“APEC Blue”: Secondary Aerosol Reductions from Emission Controls in Beijing

China implemented strict emission control measures in Beijing and surrounding regions to ensure good air quality during the 2014 Asia-Pacific Economic Cooperation (APEC) summit. We conducted synchronous aerosol particle measurements with two aerosol mass spectrometers at different heights on a meteorological tower in urban Beijing to investigate the variations in particulate composition, sources and size distributions in response to emission controls. Our results show consistently large reductions in secondary inorganic aerosol (SIA) of 61–67% and 51–57%, and in secondary organic aerosol (SOA) of 55% and 37%, at 260 m and ground level, respectively, during the APEC summit. These changes were mainly caused by large reductions in accumulation mode particles and by suppression of the growth of SIA and SOA by a factor of 2–3, which led to blue sky days during APEC commonly referred to as “APEC Blue”. We propose a conceptual framework for the evolution of primary and secondary species and highlight the importance of regional atmospheric transport in the formation of severe pollution episodes in Beijing. Our results indicate that reducing the precursors of secondary aerosol over regional scales is crucial and effective in suppressing the formation of secondary particulates and mitigating PM pollution.

Characterization and Source Apportionment of Water-Soluble Organic Matter in Atmospheric Fine Particles (PM2.5) with High-Resolution Aerosol Mass Spectrometry and GC–MS

Water-soluble organic matter (WSOM) in fine particles (PM(2.5)) collected at one rural and three urban sites from the Southeastern Aerosol Research and Characterization network were characterized with a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). These samples were also analyzed for a suite of molecular markers by Gas Chromatography-Mass Spectrometry (GC-MS) to assist in the interpretation of WSOM sources. The HR-ToF-AMS measurements allow a direct determination of the organic mass-to-carbon ratios (average ± 1σ = 1.93 ± 0.12) and hence the quantification of WSOM on the same filters used to close the aerosol mass budget. WSOM constitutes a major fraction of total PM(2.5) mass (26-42%) and organic mass (50-90%) at all sites. The concentrations of WSOM are substantially higher in summer, mainly due to enhanced production of biogenic secondary organic aerosol (SOA). WSOM is composed mainly of oxygenated species with average oxygen-to-carbon (O/C) ratio of 0.56 (± 0.08). Positive matrix factorization (PMF) of the high resolution mass spectra of WSOM identifies a less oxidized component (denoted as lOOA, O/C = 0.50) associated with biogenic SOA and a more oxidized component (denoted as mOOA, O/C = 0.60) associated with WSOM contributed by wood combustion. On average, lOOA accounts for 75 (± 13) % of WSOM in summer while mOOA accounts for 78 (± 21) % in winter, suggesting that WSOM in the southeastern U.S. is primarily contributed by SOA production from biogenic species in summer and by wood burning emissions in winter. This work also demonstrates the utility of HR-ToF-AMS for investigating the bulk chemical composition of WSOM as well as for evaluating its source contributions.

Rapid formation and evolution of an extreme haze episode in Northern China during winter 2015.

We investigate the rapid formation and evolutionary mechanisms of an extremely severe and persistent haze episode that occurred in northern China during winter 2015 using comprehensive ground and vertical measurements, along with receptor and dispersion model analysis. Our results indicate that the life cycle of a severe winter haze episode typically consists of four stages: (1) rapid formation initiated by sudden changes in meteorological parameters and synchronous increases in most aerosol species, (2) persistent evolution with relatively constant variations in secondary inorganic aerosols and secondary organic aerosols, (3) further evolution associated with fog processing and significantly enhanced sulfate levels, and (4) clearing due to dry, cold north-northwesterly winds. Aerosol composition showed substantial changes during the formation and evolution of the haze episode but was generally dominated by regional secondary aerosols (53–67%). Our results demonstrate the important role of regional transport, largely from the southwest but also from the east, and of coal combustion emissions for winter haze formation in Beijing. Also, we observed an important downward mixing pathway during the severe haze in 2015 that can lead to rapid increases in certain aerosol species.