A. Trimborn

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.

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.

Soot Particle Aerosol Mass Spectrometer: Development, Validation, and Initial Application

The Soot Particle Aerosol Mass Spectrometer (SP-AMS) was developed to measure the chemical and physical properties of particles containing refractory black carbon (rBC). The SP-AMS is an Aerodyne Aerosol Mass Spectrometer (AMS) equipped with an intracavity laser vaporizer (1064 nm) based on the Single Particle Soot Photometer (SP2) design, in addition to the resistively heated, tungsten vaporizer used in a standard AMS. The SP-AMS can be operated with the laser vaporizer alone, with both the laser and tungsten vaporizers, or with the tungsten vaporizer alone. When operating with only the laser vaporizer, the SP-AMS is selectively sensitive to laser-light absorbing particles, such as ambient rBC-containing particles as well as metal nanoparticles, and measures both the refractory and nonrefractory components. When operated with both vaporizers and modulating the laser on and off, the instrument measures the refractory components of absorbing particles and the nonrefractory particulate matter of all sampled particles. The SP-AMS design, mass spectral interpretation, calibration, and sensitivity are described. Instrument calibrations yield a sensitivity of greater than 140 carbon ions detected per picogram of rBC mass sampled, a 3σ detection limit of less than 0.1 μg·m−3 for 60 s averaging, and a mass-specific ionization efficiency relative to particulate nitrate of 0.2 ± 0.1. Sensitivities were found to vary depending upon laser-particle beam overlap. The utility of the instrument to characterize ambient rBC aerosol is demonstrated. Copyright 2012 American Association for Aerosol Research

Soot Particle Studies—Instrument Inter-Comparison—Project Overview

An inter-comparison study of instruments designed to measure the microphysical and optical properties of soot particles was completed. The following mass-based instruments were tested: Couette Centrifugal Particle Mass Analyzer (CPMA), Time-of-Flight Aerosol Mass Spectrometer—Scanning Mobility Particle Sizer (AMS-SMPS), Single Particle Soot Photometer (SP2), Soot Particle-Aerosol Mass Spectrometer (SP-AMS) and Photoelectric Aerosol Sensor (PAS2000CE). Optical instruments measured absorption (photoacoustic, interferometric, and filter-based), scattering (in situ), and extinction (light attenuation within an optical cavity). The study covered an experimental matrix consisting of 318 runs that systematically tested the performance of instruments across a range of parameters including: fuel equivalence ratio (1.8 ≤ φ ≤ 5), particle shape (mass-mobility exponent ( D fm ), 2.0 ≤ D fm ≤ 3.0), particle mobility size (30 ≤ d m ≤ 300 nm), black carbon mass (0.07 ≤ m BC ≤ 4.2 fg) and particle chemical composition. In selected runs, particles were coated with sulfuric acid or dioctyl sebacate (DOS) (0.5 ≤ Δ r ve ≤ 201 nm) where Δ r ve is the change in the volume equivalent radius due to the coating material. The effect of non-absorbing coatings on instrument response was determined. Changes in the morphology of fractal soot particles were monitored during coating and denuding processes and the effect of particle shape on instrument response was determined. The combination of optical and mass based measurements was used to determine the mass specific absorption coefficient for denuded soot particles. The single scattering albedo of the particles was also measured. An overview of the experiments and sample results are presented.

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

Identification of diesel exhaust particles at an Autobahn, urban and rural location using single-particle mass spectrometry

Abstract A single-particle mass spectrometer (LAMPAS-2) was operated at an Autobahn (high-speed highway with significant heavy-duty diesel traffic), an urban and a rural site in the vicinity of Aachen (Germany). The single-particle mass spectra could be classified into eight classes, representing different types of mineral particles, inorganic salt particles, and carbonaceous aerosol particles. At all three sites characteristic patterns of diesel exhaust particles with and without secondary compounds (ammonium sulfate/nitrate) were observed. The relative contribution of diesel soot to the number of 0.5 μm particles was 23% or 35% at the rural and the Autobahn site, respectively. The absolute number of diesel exhaust particles was three times larger at the Autobahn site. At the urban site the diesel exhaust particle contribution ranged from 10% to 35%, depending on the local operation of heavy-duty construction vehicles. Elemental carbon and carbonaceous particles made up the majority number of the 0.5 μm particles, and showed a decreasing percentage towards 2 μm particle size. As expected mineral-soil-derived particles showed the reverse size distribution. The data sets were also analyzed using a reference pattern obtained from exhaust particles of a light-duty diesel vehicle as a fingerprint. A similar trend of the contribution to the diesel-exhaust-like particle class was found, although the absolute numbers were somewhat different. On-line single-particle mass spectrometry proved to be a promising tool to identify individual particles if characteristic reference spectra were available.

Demonstration of a VUV Lamp Photoionization Source for Improved Organic Speciation in an Aerosol Mass Spectrometer

In recent years, the Aerodyne Aerosol Mass Spectrometer (AMS) has become a widely used tool for determining aerosol size distributions and chemical composition for non-refractory inorganic and organic aerosols. All AMSs to date have used a combination of flash thermal vaporization and 70 eV electron impact (EI) ionization. However, EI causes extensive fragmentation and mass spectra of organic aerosols are difficult to deconvolve because they are composites of the overlapping fragmentation patterns of a multitude of species. In this manuscript we present an approach to gain more information about organic aerosol composition by employing the softer technique of vacuum ultraviolet (VUV) ionization in a Time-of-Flight AMS (ToF-AMS). Our novel design allows for alternation between photoionization (PI) and EI within the same instrument on a timescale of minutes. Thus, the EI-based quantification capability of the AMS is retained while improved spectral interpretation is made possible by combined analysis of the complementary VUV and EI spectra. PI and EI spectra are compared for several compounds and mixtures in multiple dimensions including size distributions and size-segregated mass spectra. In general, VUV spectra contain much less fragmentation than EI spectra and for many compounds the parent ion is the base peak in the VUV spectrum. Results for oleic acid are compared to experiments conducted using tunable VUV radiation from a synchrotron source and were shown to be comparable under similar conditions of photon energy and vaporizer temperature. Future technical modifications for improvements in sensitivity and its potential for ambient measurements will be discussed.

Chemical classes of atmospheric aerosol particles at a rural site in Central Europe during winter

Ambient atmospheric particles were studied at an ecosystem research site in the Fichtelgebirge mountains in Central Europe by single-particle analysis and bulk impactor measurements. Fuzzy clustering analysis of mass spectra ofindividual aerosol particles allowed chemical classi7cation ofthe atmospheric aerosol. During the campaign, inorganic salts, mineral particles, and carbonaceous particles, with varying degrees ofsecondary components, were identi7ed. These chemical classes exhibited preferential size ranges leading to a characteristic pattern ofrelative abundances with respect to particle size. A more detailed analysis revealed that 65 –80% of all particles were assigned almost exclusively to one chemical class. These particle populations are assumed to be externally mixed with respect to the identi7ed chemical classes. The temporal variations ofthe ratio ofnitrate to ammonium (ranging between 0.37 and 0.81) determined by both impactor measurements and single-particle analyses were in good agreement. Through Monte-Carlo-type simulations, con7dence intervals ofthe mean NO − =NH + ratio were calculated for sub-samples of the total particle population. ? 2002 Elsevier

Towards direct measurement of turbulent vertical fluxes of compounds in atmospheric aerosol particles

] Vertical fluxes of gaseous and particulate compoundsin the planetary boundary layer are mainly establishedthrough turbulence. To date, it is a challenge to measurevertical fluxes of particles and, even more, the fluxes ofcompounds in particulates. The combination of disjuncteddy sampling and time-of-flight MS single particleanalysis bears the potential to directly measure theturbulent particle flux together with the chemical particlecomposition. Several obstacles must be overcome beforethis goal may be achieved. In this paper, we present astatistical procedure, using Monte-Carlo-type simulations,to obtain the flux direction of particulate compounds suchas nitrate. A first experimental application of this methodyielded emission of particulate NO

Investigations of SP-AMS Carbon Ion Distributions as a Function of Refractory Black Carbon Particle Type

The soot particle aerosol mass spectrometer (SP-AMS) instrument combines continuous wave laser vaporization with electron ionization aerosol mass spectrometry to characterize airborne, refractory black carbon (rBC) particles. The laser selectively vaporizes absorbing rBC-containing particles, allowing the SP-AMS to provide direct chemical information on the refractory and non-refractory chemical components, providing the potential to fingerprint various rBC particle types. In this study, SP-AMS mass spectra were measured for 12 types of rBC particles produced by industrial and combustion processes to explore differences in the carbon cluster (Cn+) mass spectra. The Cn+ mass spectra were classified into three categories based on their ion distributions, which varied with rBC particle type. The carbon ion distributions were investigated as a function of laser power, electron ionization (on/off), and ion charge (positive or negative). Results indicate that the dominant positive ion-formation mechanism is likely the vaporization of small, neutral carbon clusters followed by electron ionization (C1+ to C5+). Significant ion signal from larger carbon cluster ions (and their fragment ions in the small carbon cluster range), including mid carbon (C6+ to C29+) and fullerene (greater than C30+) ions, were observed in soot produced under incomplete combustion conditions, including biomass burning, as well as in fullerene-enriched materials. Fullerene ions were also observed at high laser power with electron ionization turned off, formed via an additional ionization mechanism. We expect this SP-AMS technique to find application in the identification of the source and atmospheric history of airborne ambient rBC particles. Copyright 2015 American Association for Aerosol Research