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

Biomass burning aerosols in most climate models are too absorbing

Uncertainty in the representation of biomass burning (BB) aerosol composition and optical properties in climate models contributes to a range in modeled aerosol effects on incoming solar radiation. Depending on the model, the top-of-the-atmosphere BB aerosol effect can range from cooling to warming. By relating aerosol absorption relative to extinction and carbonaceous aerosol composition from observational datasets to nine state-of-the-art Earth System Models/Chemical Transport Models,we identify varying degrees of overestimation in BB aerosol absorptivity by these models. Modifications to BB aerosol refractive index, size, and mixing state improve the Community Atmosphere Model version 5 (CAM5) agreement with observations, leading to a global change in BB direct radiative effect of -0.07 W m-2,and regional changes of -2 W m-2(Africa) and -0.5 W m-2(South America/Temperate). Our findings suggest that current modeled BB contributes less to warming than previously thought, largely due to treatments of aerosol mixing state

Aerosol mass spectrometer constraint on the global secondary organic aerosol budget

The budget of atmospheric secondary organic aerosol (SOA) is very uncertain, with recent estimates suggesting a global source of between 12 and 1820 Tg (SOA) a−1. We used a dataset of aerosol mass spectrometer (AMS) observations from 34 different surface locations to evaluate the GLOMAP global chemical transport model. The standard model simulation (which included SOA from monoterpenes only) underpredicted organic aerosol (OA) observed by the AMS and had little skill reproducing the variability in the dataset. We simulated SOA formation from biogenic (monoterpenes and isoprene), lumped anthropogenic and lumped biomass burning volatile organic compounds (VOCs) and varied the SOA yield from each precursor source to produce the best overall match between model and observations. We assumed that SOA is essentially non-volatile and condenses irreversibly onto existing aerosol. Our best estimate of the SOA source is 140 Tg (SOA) a−1 but with a large uncertainty range which we estimate to be 50–380 Tg (SOA) a−1. We found the minimum in normalised mean error (NME) between model and the AMS dataset when we assumed a large SOA source (100 Tg (SOA) a−1) from sources that spatially matched anthropogenic pollution (which we term antropogenically controlled SOA). We used organic carbon observations compiled by Bahadur et al. (2009) to evaluate our estimated SOA sources. We found that the model with a large anthropogenic SOA source was the most consistent with these observations, however improvement over the model with a large biogenic SOA source (250 Tg (SOA) a−1) was small. We used a dataset of 14C observations from rural locations to evaluate our estimated SOA sources. We estimated a maximum of 10 Tg (SOA) a−1 (10 %) of the anthropogenically controlled SOA source could be from fossil (urban/industrial) sources. We suggest that an additional anthropogenic source is most likely due to an anthropogenic pollution enhancement of SOA formation from biogenic VOCs. Such an anthropogenically controlled SOA source would result in substantial climate forcing. We estimated a global mean aerosol direct effect of −0.26 ± 0.15 Wm−2 and indirect (cloud albedo) effect of −0.6+0.24−0.14 Wm−2 from anthropogenically controlled SOA. The biogenic and biomass SOA sources are not well constrained with this analysis due to the limited number of OA observations in regions and periods strongly impacted by these sources. To further improve the constraints by this method, additional OA observations are needed in the tropics and the Southern Hemisphere

Spatially and seasonally resolved estimate of the ratio of organic mass to organic carbon

Particulate organic matter is of interest for air quality and climate research, but the relationship between ambient organic mass (OM) and organic carbon (OC) remains ambiguous both in measurements and in modeling. We present a simple method to derive an estimate of the spatially and seasonally resolved global, lower tropospheric, ratio between OM and OC. We assume ambient NO2 concentrations as a surrogate for fresh emission which mostly determines the continental scale OM/OC ratio. For this, we first develop a parameterization for the OM/OC ratio using the primary organic aerosol (POA) fraction of total OM estimated globally from Aerosol Mass Spectrometer (AMS) measurements, and evaluate it with high mass resolution AMS data. Second, we explore the ability of ground-level NO2 concentrations derived from the OMI satellite sensor to serve as a proxy for fresh emissions that have a high POA fraction, and apply NO2 data to derive ambient POA fraction. The combination of these two methods yields an estimate of OM/OC from NO2 measurements. Although this method has inherent deficiencies over biomass burning, free-tropospheric, and marine environments, elsewhere it offers more information than the currently used global-mean OM/OC ratios. The OMI-derived global OM/OC ratio ranges from 1.3 to 2.1 (μg/μgC), with distinct spatial variation between urban and rural regions. The seasonal OM/OC ratio has a summer maximum and a winter minimum over regions dominated by combustion emissions. This dataset serves as a tool for interpreting organic carbon measurements, and for evaluating modeling of atmospheric organics. We also develop an additional parameterization for models to estimate the ratio of primary OM to OC from simulated NOx concentrations

An Eddy-Covariance System for the Measurement of Surface/Atmosphere Exchange Fluxes of Submicron Aerosol Chemical Species—First Application Above an Urban Area

Until now, micrometeorological measurements of surface/ atmosphere exchange fluxes of submicron aerosol chemical components such as nitrate, sulfate or organics could only be made with gradient techniques. This paper describes a novel setup to measure speciated aerosol fluxes by the more direct eddy covariance technique. The system is based on the Aerodyne quadrupole-based Aerosol Mass Spectrometer (Q-AMS), providing a quantitative measurement of aerosol constituents of environmental concern at a time resolution sufficient for eddy-covariance. The Q-AMS control software was modified to maximize duty cycle and statistics and enable fast data acquisition, synchronized with that of an ultrasonic anemometer. The detection limit of the Q-AMS based system for flux measurements ranges from 0.2 for NO−3 to 15 ng m−2 s−1 for hydrocarbon-like organic aerosol (HOA), with an estimated precision of around 6 ng m−2 s−1, depending on aerosol loading. At common ambient concentrations the system is capable of resolving deposition velocity values < 1 mm s−1, sufficient for measurements of dry deposition to vegetation. First tests of the system in the urban environment (6 to 20 June 2003) in Boulder, CO, USA, reveal clear diurnal, presumably traffic related, patterns in the emission of HOA and NO−3 , with indication of fast production of moderately oxygenated organic aerosol below the measurement height, averaging about 15% of the HOA emission. The average emission factor for HOA was 0.5 g (kg fuel)−1, similar to those found in previous studies. For NO−3 an emission factor of 0.09 g (kg fuel)−1 was estimated, implying oxidation of 0.5% of the traffic derived NOx below the measurement height of 45 m. By contrast, SO2− 4 fluxes were on average downward, with deposition velocities that increase with friction velocity from 0.4 to 4 mm s−1

An eddy-covariance system for the measurement of surface/atmosphere exchange fluxes of submicron aerosol chemical species - First application above an urban area

Until now, micrometeorological measurements of surface/ atmosphere exchange fluxes of submicron aerosol chemical components such as nitrate, sulfate or organics could only be made with gradient techniques. This article describes a novel setup to measure speciated aerosol fluxes by the more direct eddy covariance technique. The system is based on the Aerodyne quadrupole-based Aerosol Mass Spectrometer (Q-AMS), providing a quantitative measurement of aerosol constituents of environmental concern at a time resolution sufficient for eddy-covariance. The Q-AMS control software was modified to maximize duty cycle and statistics and enable fast data acquisition, synchronized with that of an ultrasonic anemometer. The detection limit of the Q-AMS based system for flux measurements ranges from 0.2 for NO3- to 15 ng m-2 s-1 for hydrocarbon-like organic aerosol (HOA), with an estimated precision of around 6 ng m-2 s-1, depending on aerosol loading. At common ambient concentrations the system is capable of resolving deposition velocity values &lt; 1 mm s-1, sufficient for measurements of dry deposition to vegetation. First tests of the system in the urban environment (6 to 20 June 2003) in Boulder, CO, USA, reveal clear diurnal, presumably traffic related, patterns in the emission of HOA and NO3-, with indication of fast production of moderately oxygenated organic aerosol below the measurement height, averaging about 15% of the HOA emission. The average emission factor for HOA was 0.5 g (kg fuel)-1, similar to those found in previous studies. For NO3- an emission factor of 0.09 g (kg fuel)-1 was estimated, implying oxidation of 0.5% of the traffic derived NOx below the measurement height of 45 m. By contrast, SO42- fluxes were on average downward, with deposition velocities that increase with friction velocity from 0.4 to 4 mm s-1. Copyright © American Association for Aerosol Research

In situ concentration of semi-volatile aerosol using water-condensation technology

The effect of concentrating semi-volatile aerosols using a water-condensation technology was investigated using the Versatile Aerosol Concentration Enrichment System (VACES) and the Aerodyne Aerosol Mass Spectrometer (AMS) during measurements of ambient aerosol in Pittsburgh, PA. It was found that the shape of the sulfate mass-weighed size distribution was approximately preserved during passage through the concentrator for all the experiments performed, with a mass enhancement factor of about 10-20 depending on the experiment. The size distributions of organics, ammonium and nitrate were preserved on a relatively clean day (sulfate concentration around 7μg/m3), while during more polluted conditions the concentration of these compounds, especially nitrate, was increased at small sizes after passage through the concentrator. The amount of the extra material, however, is rather small in these experiments: between 2.4% and 7.5% of the final concentrated PM mass is due to "artifact" condensation. An analysis of thermodynamic processes in the concentrator indicates that the extra particle material detected can be explained by redistribution of gas-phase material to the aerosol phase in the concentrator. The analysis shows that the condensation of extra material is expected to be larger for water-soluble semi-volatile material, such as nitrate, which agrees with the observations. The analysis also shows that artifact formation of nitrate will be more pronounced in ammonia-limited conditions and virtually undetectable in ammonia-rich conditions. © 2004 Elsevier Ltd. All rights reserved

Secondary organic aerosol yields of 12-carbon alkanes

Secondary organic aerosol (SOA) yields were measured for cyclododecane, hexylcyclohexane, n-dodecane, and 2-methylundecane under high-NOx conditions, in which alkyl proxy radicals (RO2) react primarily with NO, and under low-NOx conditions, in which RO2 reacts primarily with HO2. Experiments were run until 95-100% of the initial alkane had reacted. Particle wall loss was evaluated as two limiting cases using a new approach that requires only suspended particle number-size distribution data and accounts for size-dependent particle wall losses and condensation. SOA yield differed by a factor of 2 between the two limiting cases, but the same trends among alkane precursors were observed for both limiting cases. Vapor-phase wall losses were addressed through a modeling study and increased SOA yield uncertainty by approximately 30%. SOA yields were highest from cyclododecane under both NOx conditions. SOA yields ranged from 3.3% (dodecane, low-NOx conditions) to 160% (cyclododecane, high-NOx conditions). Under high-NOx conditions, SOA yields increased from 2-methylundecane &lt; dodecane ∼ hexylcyclohexane &lt; cyclododecane, consistent with previous studies. Under low-NOx conditions, SOA yields increased from 2-methylundecane ∼ dodecane &lt; hexylcyclohexane &lt; cyclododecane. The presence of cyclization in the parent alkane structure increased SOA yields, whereas the presence of branch points decreased SOA yields due to increased vapor-phase fragmentation. Vapor-phase fragmentation was found to be more prevalent under high-NOx conditions than under low-NOx conditions. For different initial mixing ratios of the same alkane and same NOx conditions, SOA yield did not correlate with SOA mass throughout SOA growth, suggesting kinetically limited SOA growth for these systems. © 2014 Author(s)