P. F. DeCarlo

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.

Particle Morphology and Density Characterization by Combined Mobility and Aerodynamic Diameter Measurements. Part 1: Theory

Different on-line submicron particle sizing techniques report different “equivalent diameters.” For example, differential mobility analyzers (DMAs) report electrical mobility diameter (dm ), while a number of recently developed instruments (such as the Aerodyne aerosol mass spectrometer, or AMS) measure vacuum aerodynamic diameter (dva ). Particle density and physical morphology (shape) have important effects on diameter measurements. Here a framework is presented for combining the information content of different equivalent diameter measurements into a single coherent mathematical description of the particles. We first present a review of the mathematical formulations used in the literature and their relationships. We then show that combining dm and dva measurements for the same particle population allows the placing of constraints on particle density, dynamic shape factor (x), and fraction of internal void space. The amount of information that can be deduced from the combination of dm and dm measurements for various particle types is shown. With additional measurements and/or some assumptions, all relevant parameters can be determined. Specifically, particle mass can be determined from dm and dva measurements if the particle density is known and an assumption about x is made. Even if x and density are not known, particle mass can be estimated within about a factor of 2 from dm and dva measurements alone. The mass of a fractal particle can also be estimated under certain conditions. The meaning of various definitions of “effective density” used in the literature is placed in the context of the theory. This theoretical framework is applied to measurements of fractal (soot-like) particles by using experimental results from the literature as additional constraints.

A New Time-of-Flight Aerosol Mass Spectrometer (TOF-AMS)—Instrument Description and First Field Deployment

We report the development and first field deployment of a new version of the Aerosol Mass Spectrometer (AMS), which is capable of measuring non-refractory aerosol mass concentrations, chemically speciated mass distributions and single particle information. The instrument was constructed by interfacing the well-characterized Aerodyne AMS vacuum system, particle focusing, sizing, and evaporation/ionization components, with a compact TOFWERK orthogonal acceleration reflectron time-of-flight mass spectrometer. In this time-of-flight aerosol mass spectrometer (TOF-AMS) aerosol particles are focused by an aerodynamic lens assembly as a narrow beam into the vacuum chamber. Non-refractory particle components flash-vaporize after impaction onto the vaporizer and are ionized by electron impact. The ions are continuously guided into the source region of the time-of-flight mass spectrometer, where ions are extracted into the TOF section at a repetition rate of 83.3 kHz. Each extraction generates a complete mass spectrum, which is processed by a fast (sampling rate 1 Gs/s) data acquisition board and a PC. Particle size information is obtained by chopping the particle beam followed by time-resolved detection of the particle evaporation events. Due to the capability of the time-of-flight mass spectrometer of measuring complete mass spectra for every extraction, complete single particle mass spectra can be collected. This mode provides quantitative information on single particle composition. The TOF-AMS allows a direct measurement of internal and external mixture of non-refractory particle components as well as sensitive ensemble average particle composition and chemically resolved size distribution measurements. Here we describe for the first time the TOF-AMS and its operation as well as results from its first field deployment during the PM 2.5 Technology Assessment and Characterization Study—New York (PMTACS-NY) Winter Intensive in January 2004 in Queens, New York. These results show the capability of the TOF-AMS to measure quantitative aerosol composition and chemically resolved size distributions of the ambient aerosol. In addition it is shown that the single particle information collected with the instrument gives direct information about internal and external mixture of particle components.

Pollutant Emissions and Energy Efficiency under Controlled Conditions for Household Biomass Cookstoves and Implications for Metrics Useful in Setting International Test Standards

Realistic metrics and methods for testing household biomass cookstoves are required to develop standards needed by international policy makers, donors, and investors. Application of consistent test practices allows emissions and energy efficiency performance to be benchmarked and enables meaningful comparisons among traditional and advanced stove types. In this study, 22 cookstoves burning six fuel types (wood, charcoal, pellets, corn cobs, rice hulls, and plant oil) at two fuel moisture levels were examined under laboratory-controlled operating conditions as outlined in the Water Boiling Test (WBT) protocol, Version 4. Pollutant emissions (carbon dioxide, carbon monoxide, methane, total hydrocarbons, and ultrafine particles) were continuously monitored. Fine particle mass was measured gravimetrically for each WBT phase. Additional measurements included cookstove power, energy efficiency, and fuel use. Emission factors are given on the basis of fuel energy, cooking energy, fuel mass, time, and cooking task or activity. The lowest PM(2.5) emissions were 74 mg MJ(delivered)(-1) from a technologically advanced cookstove compared with 700-1400 mg MJ(delivered)(-1) from the base-case open 3-stone cookfire. The highest thermal efficiency was 53% compared with 14-15% for the 3-stone cookfire. Based on these laboratory-controlled test results and observations, recommendations for developing potentially useful metrics for setting international standards are suggested.

Particle morphology and density characterization by combined mobility and aerodynamic diameter measurements. Part 2: Application to combustion-generated soot aerosols as a function of fuel equivalence ratio

Composition, shape factor, size, and fractal dimension of soot aerosol particles generated in a propane/O2, flame were determined as a function of the fuel equivalence ratio (φ). Soot particles were first size-selected by a differential mobility analyzer (DMA) and then analyzed by an Aerodyne aerosol mass spectrometer (AMS). The DMA provides particles of known mobility diameter (dm ). The AMS quantitatively measures the mass spectrum of the nonrefractory components of the particles and also provides the vacuum aerodynamic diam eter (dva ) corresponding to the particles of known mobility diameter. The measured dm, dva , and nonrefractory composition are used in a system of equations based on the formulation presented in the companion article to estimate the particle dynamic shape factor, total mass, and black carbon (BC) content. Fractal dimension was estimated based on the mass-mobility relationship. Two types of soot particles were observed depending on the fuel equivalence ratio. Type 1: for φ < 4 (lower propane/O2), dva ; was nearly constant and independent of dm . The value of dva increased with increasing φ. Analysis of the governing equations showed that these particles were highly irregular (likely fractal aggregates), with a dynamic shape factor that increased with dm and φ. The fractal dimension of these particles was approximately 1.7. These particles were composed mostly of BC, with the organic carbon content increasing as φ increased. At φ = 1.85, the particles were about 90% BC, 5% PAH, and 5% aliphatic hydrocarbon (particle density = 1.80 g/cm3). Type 2: for φ > 4 (high propane/O2), dva was linearly proportional to dm . Analysis of the governing equations showed that these particles were nearly spherical (likely compact aggregates), with a dynamic shape factor of 1.1 (versus 1 for a sphere) and a fr actal dimension of 2.95 (3 for a sphere). These particles were composed of about 50% PAH, 45% BC, and 5% aliphatic hydrocarbons (particle density = 1.50 g/cm3). These results help interpret some measurement s obtained in recent field studies.

Aging of biogenic secondary organic aerosol via gas-phase OH radical reactions

The Multiple Chamber Aerosol Chemical Aging Study (MUCHACHAS) tested the hypothesis that hydroxyl radical (OH) aging significantly increases the concentration of first-generation biogenic secondary organic aerosol (SOA). OH is the dominant atmospheric oxidant, and MUCHACHAS employed environmental chambers of very different designs, using multiple OH sources to explore a range of chemical conditions and potential sources of systematic error. We isolated the effect of OH aging, confirming our hypothesis while observing corresponding changes in SOA properties. The mass increases are consistent with an existing gap between global SOA sources and those predicted in models, and can be described by a mechanism suitable for implementation in those models.

Design and Operation of a Pressure-Controlled Inlet for Airborne Sampling with an Aerodynamic Aerosol Lens

Two pressure-controlled inlets (PCI) have been designed and integrated into the Aerodyne Aerosol Mass Spectrometer (AMS) inlet system containing an aerodynamic aerosol lens system for use in airborne measurements. Laboratory experiments show that size calibration and mass flow rate into the AMS are not affected by changes in upstream pressure (P 0 ) of the PCI as long as the pressure within the PCI chamber (P PCI ) is controlled to values lower than P 0 . Numerous experiments were conducted at different P PCI , P 0 , and AMS lens pressures (P Lens ) to determine particle transmission efficiency into the AMS. Based on the results, optimum operating conditions were selected which allow for constant pressure sampling with close to 100% transmission efficiency of particles in the size range of ∼ 100–700 nm vacuum aerodynamic diameter (d va ) at altitudes up to ∼ 6.5 km. Data from an airborne field study are presented for illustration.

Changes of hygroscopicity and morphology during ageing of diesel soot

Soot particles are an important component of atmospheric aerosol and their interaction with water is important for their climate effects. The hygroscopicity of fresh and photochemically aged soot and secondary organic aerosol (SOA) from diesel passenger car emissions was studied under atmospherically relevant conditions in a smog chamber at sub-and supersaturation of water vapor. Fresh soot particles show no significant hygroscopic growth nor cloud condensation nucleus (CCN) activity. Ageing by condensation of SOA formed by photooxidation of the volatile organic carbon (VOC) emission leads to increased water uptake and CCN activity as well as to a compaction of the initially non-spherical soot particles when exposed to high relative humidity (RH). It is important to consider the latter effect for the interpretation of mobility based measurements. The vehicle with oxidation catalyst (EURO3) emits much fewer VOCs than the vehicle without after-treatment (EURO2). Consequently, more SOA is formed for the latter, resulting in more pronounced effects on particle hygroscopicity and CCN activity. Nevertheless, the aged soot particles did not reach the hygroscopicity of pure SOA particles formed from diesel VOC emissions, which are similarly hygroscopic (0.06 < κH − TDMA < 0.12 and 0.09 < κCCN < 0.14) as SOA from other precursor gases investigated in previous studies.

Modeling the Multiday Evolution and Aging of Secondary Organic Aerosol During MILAGRO 2006

In this study, we apply several recently proposed models to the evolution of secondary organic aerosols (SOA) and organic gases advected from downtown Mexico City at an altitude of ∼3.5 km during three days of aging, in a way that is directly comparable to simulations in regional and global models. We constrain the model with and compare its results to available observations. The model SOA formed from oxidation of volatile organic compounds (V-SOA) when using a non-aging SOA parameterization cannot explain the observed SOA concentrations in aged pollution, despite the increasing importance of the low-NO(x) channel. However, when using an aging SOA parameterization, V-SOA alone is similar to the regional aircraft observations, highlighting the wide diversity in current V-SOA formulations. When the SOA formed from oxidation of semivolatile and intermediate volatility organic vapors (SI-SOA) is computed following Robinson et al. (2007) the model matches the observed SOA mass, but its O/C is ∼2× too low. With the parameterization of Grieshop et al. (2009), the total SOA mass is ∼2× too high, but O/C and volatility are closer to the observations. Heating or dilution cause the evaporation of a substantial fraction of the model SOA; this fraction is reduced by aging although differently for heating vs dilution. Lifting of the airmass to the free-troposphere during dry convection substantially increases SOA by condensation of semivolatile vapors; this effect is reduced by aging.