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.

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.

The application of mass spectrometric techniques to the real-time measurement and characterization of aerosols represents a significant advance in the field of atmospheric science. This review focuses on the aerosol mass spectrometer (AMS), an instrument designed and developed at Aerodyne Research, Inc. (ARI) that is the most widely used thermal vaporization AMS. The AMS uses aerodynamic lens inlet technology together with thermal vaporization and electron-impact mass spectrometry to measure the real-time non-refractory (NR) chemical speciation and mass loading as a function of particle size of fine aerosol particles with aerodynamic diameters between approximately 50 and 1,000 nm. The original AMS utilizes a quadrupole mass spectrometer (Q) with electron impact (EI) ionization and produces ensemble average data of particle properties. Later versions employ time-of-flight (ToF) mass spectrometers and can produce full mass spectral data for single particles. This manuscript presents a detailed discussion of the strengths and limitations of the AMS measurement approach and reviews how the measurements are used to characterize particle properties. Results from selected laboratory experiments and field measurement campaigns are also presented to highlight the different applications of this instrument. Recent instrumental developments, such as the incorporation of softer ionization techniques (vacuum ultraviolet (VUV) photo-ionization, Li+ ion, and electron attachment) and high-resolution ToF mass spectrometers, that yield more detailed information about the organic aerosol component are also described.

[1] An extensive set of volatile organic compounds (VOCs) and particulate organic matter (POM) was measured in polluted air during the New England Air Quality Study in 2002. Using VOC ratios, the photochemical age of the sampled air masses was estimated. This approach was validated (1) by comparing the observed rates at which VOCs were removed from the atmosphere with the rates expected from OH oxidation, (2) by comparing the VOC emission ratios inferred from the data with the average composition of urban air, and (3) by the ability to describe the increase of an alkyl nitrate with time in terms of the chemical kinetics. A large part of the variability observed for oxygenated VOCs (OVOCs) and POM could be explained by a description that includes the removal of the primary anthropogenic emissions, the formation and removal of secondary anthropogenic species, and a biogenic contribution parameterized by the emissions of isoprene. The OVOC sources determined from the data are compared with the available literature, and a satisfactory agreement is obtained. The observed sub-mm POM was highly correlated with secondary anthropogenic gas-phase species, strongly suggesting that the POM was from secondary anthropogenic sources. The results are used to describe the speciation and total mass of gas-and particle-phase organic carbon as a function of the photochemical age of an urban air mass. Shortly after emission the organic carbon mass is dominated by primary VOCs, while after two days the dominant contribution is from OVOCs and sub-mm POM. The total measured organic carbon mass decreased by about 40% over the course of two days. The increase in sub-mm POM could not be explained by the removal of aromatic precursors alone, suggesting that other species must have contributed and/or that the mechanism for POM formation is more efficient than previously assumed.Citation: de Gouw, J. A., et al. (2005), Budget of organic carbon in a polluted atmosphere: Results from the New England Air

In recent years, Aerodyne aerosol mass spectrometers (AMS) have been used in many locations around the world to study the size-resolved, nonrefractory chemical composition of ambient particles. In order to obtain quantitative data, the mass or (number) of particles detected by the AMS relative to the mass (or number) of particles sampled by the AMS, i.e., the AMS collection efficiency (CE) must be known. Previous studies have proposed and used parameterizations of the AMS CE based on the aerosol composition and sampling line relative humidity. Here, we evaluate these parameterizations by comparing AMS mass concentrations with independent measurements of fine particle volume or particle-into-liquid sampler (PILS) ion chromatography measurements for 3 field campaigns with different dominant aerosol mixtures: (1) acidic sulfate particles, (2) aerosol containing a high mass fraction of ammonium nitrate, and (3) aerosol composed of primarily biomass burning emissions. The use of the default CE of 0.5 for all campaigns resulted in 81-90% of the AMS speciated and total mass concentrations comparing well with fine particle volume or PILS measurements within experimental uncertainties, with positive biases compared with a random error curve. By using composition-dependent CE values (sometimes as a function of size) which increased the CE for the above aerosol types, the fraction of data points within the measurement uncertainties increased to more than 92% and the mass concentrations decreased by ∼5-15% on an average. The CE did not appear to be significantly dependent on changes in organic mass fraction although it was substantial in the 3 campaigns (47, 30, and 55%).