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Atmospheric pressure flow reactor / aerosol mass spectrometer studies of tropospheric aerosol nucleat and growth kinetics. Final report, June, 2001

Description: The objective of this program was to determine the mechanisms and rates of growth and transformation and growth processes that control secondary aerosol particles in both the clear and polluted troposphere. The experimental plan coupled an aerosol mass spectrometer (AMS) with a chemical ionization mass spectrometer to provide simultaneous measurement of condensed and particle phases. The first task investigated the kinetics of tropospheric particle growth and transformation by measuring vapor accretion to particles (uptake coefficients, including mass accommodation coefficients and heterogeneous reaction rate coefficients). Other work initiated investigation of aerosol nucleation processes by monitoring the appearance of submicron particles with the AMS as a function of precursor gas concentrations. Three projects were investigated during the program: (1) Ozonolysis of oleic acid aerosols as model of chemical reactivity of secondary organic aerosol; (2) Activation of soot particles by measurement deliquescence in the presence of sulfuric acid and water vapor; (3) Controlled nucleation and growth of sulfuric acid aerosols.
Date: June 1, 2001
Creator: Worsnop, Douglas R.
Partner: UNT Libraries Government Documents Department

A combined droplet train and ambient pressure photoemission spectrometer for the investigation of liquid/vapor interfaces

Description: We describe a combined ambient pressure photoelectron spectroscopy/droplet train apparatus for investigating the nature and heterogeneous chemistry of liquid/vapor interfaces. In this instrument a liquid droplet train with typical droplet diameters from 50...150 {micro}m is produced by a vibrating orifice aerosol generator (VOAG). The droplets are irradiated by soft X-rays (100...1500 eV) in front of the entrance aperture of a differentially pumped electrostatic lens system that transfers the emitted electrons into a conventional hemispherical electron analyzer. The photoemission experiments are performed at background pressures of up to several Torr, which allows the study of environmentally important liquid/vapor interfaces, in particular aqueous solutions, under equilibrium conditions. The exposure time of the droplet surface to the background gases prior to the XPS measurement can be varied, which will allow future kinetic measurements of gas uptake on liquid surfaces. As an example, a measurement of the surface composition of a {chi} = 0.21 aqueous methanol solution is presented. The concentration of methanol at the vapor/liquid interface is enhanced by a factor of about 3 over the bulk value, while the expected bulk value is recovered at depths larger than about 1.5 nm.
Date: May 1, 2008
Creator: Starr, David E.; Wong, Ed K.; Worsnop, Douglas R.; Wilson, Kevin R. & Bluhm, Hendrik
Partner: UNT Libraries Government Documents Department

Measurement of fragmentation and functionalization pathways in the multistep heterogeneous oxidation of organic aerosol

Description: The competition between the addition of polar, oxygen-containing functional groups (functionalization) and the cleavage of C-C bonds (fragmentation) has a governing influence on the change in volatility of organic species upon atmospheric oxidation, and hence on the loading of tropospheric organic aerosol. However the branching between these two channels is generally poorly constrained for oxidized organics. Here we determine functionalization/fragmentation branching ratios for organics spanning a range of oxidation levels, using the heterogeneous oxidation of squalane (C30H62) as a model system. Squalane particles are exposed to high concentrations of OH in a flow reactor, and measurements of particle mass and elemental ratios enable the determination of absolute elemental composition (number of oxygen, carbon, and hydrogen atoms) of the oxidized particles. At low OH exposures, the oxygen content of the organics increases, indicating that functionalization dominates, whereas at higher exposures the amount of carbon in the particles decreases, indicating the increasing importance of fragmentation processes. Once the organics are moderately oxidized (O/C~;;0.4), fragmentation completely dominates, and the increase in O/C ratio upon further oxidation is due to the loss of carbon rather than the addition of oxygen. These results suggest that fragmentation reactions may be key steps in the atmospheric formation and evolution of oxygenated organic aerosol (OOA).
Date: March 10, 2009
Creator: Kroll, Jesse H.; Smith, Jared D.; Che, Dung L.; Kessler, Sean H.; Worsnop, Douglas R. & Wilson, Kevin R.
Partner: UNT Libraries Government Documents Department

OH-initiated heterogeneous aging of highly oxidized organic aerosol

Description: The oxidative evolution (“aging”) of organic species in the atmosphere is thought to have a major influence on the composition and properties of organic particulate matter, but remains poorly understood, particularly for the most oxidized fraction of the aerosol. Here we measure the kinetics and products of the heterogeneous oxidation of highly oxidized organic aerosol, with an aim of better constraining such atmospheric aging processes. Submicron particles composed of model oxidized organics—1,2,3,4-butanetetracarboxylic acid (C{sub 8}H{sub 10}O{sub 8}), citric acid (C{sub 6}H{sub 8}O{sub 7}), tartaric acid (C{sub 4}H{sub 6}O{sub 6}), and Suwannee River fulvic acid—were oxidized by gas-phase OH in a flow reactor, and the masses and elemental composition of the particles were monitored as a function of OH exposure. In contrast to our previous studies of less-oxidized model systems (squalane, erythritol, and levoglucosan), particle mass did not decrease significantly with heterogeneous oxidation. Carbon content of the aerosol always decreased somewhat, but this mass loss was approximately balanced by an increase in oxygen content. The estimated reactive uptake coefficients of the reactions range from 0.37 to 0.51 and indicate that such transformations occur at rates corresponding to 1-2 weeks in the atmosphere, suggesting their importance in the atmospheric lifecycle of organic particulate matter.
Date: December 5, 2011
Creator: Kessler, Sean H.; Nah, Theodora; Daumit, Kelly E.; Smith, Jared D.; Leone, Stephen R.; Kolb, Charles E. et al.
Partner: UNT Libraries Government Documents Department

Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol

Description: A detailed understanding of the sources, transformations, and fates of organic species in the environment is crucial because of the central roles that organics play in human health, biogeochemical cycles, and Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state (OSC), a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of OSC , using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number (nC).
Date: November 5, 2010
Creator: Technology, Massachusetts Institute of; Kroll, Jesse H.; Donahue, Neil M.; Jimenez, Jose L.; Kessler, Sean H.; Canagaratna, Manjula R. et al.
Partner: UNT Libraries Government Documents Department

Sampling Artifacts from Conductive Silicone Tubing

Description: We report evidence that carbon impregnated conductive silicone tubing used in aerosol sampling systems can introduce two types of experimental artifacts: 1) silicon tubing dynamically absorbs carbon dioxide gas, requiring greater than 5 minutes to reach equilibrium and 2) silicone tubing emits organic contaminants containing siloxane that adsorb onto particles traveling through it and onto downstream quartz fiber filters. The consequence can be substantial for engine exhaust measurements as both artifacts directly impact calculations of particulate mass-based emission indices. The emission of contaminants from the silicone tubing can result in overestimation of organic particle mass concentrations based on real-time aerosol mass spectrometry and the off-line thermal analysis of quartz filters. The adsorption of siloxane contaminants can affect the surface properties of aerosol particles; we observed a marked reduction in the water-affinity of soot particles passed through conductive silicone tubing. These combined observations suggest that the silicone tubing artifacts may have wide consequence for the aerosol community and should, therefore, be used with caution. Gentle heating, physical and chemical properties of the particle carriers, exposure to solvents, and tubing age may influence siloxane uptake. The amount of contamination is expected to increase as the tubing surface area increases and as the particle surface area increases. The effect is observed at ambient temperature and enhanced by mild heating (<100 oC). Further evaluation is warranted.
Date: May 15, 2009
Creator: Timko, Michael T.; Yu, Zhenhong; Kroll, Jesse; Jayne, John T.; Worsnop, Douglas R.; Miake-Lye, Richard C. et al.
Partner: UNT Libraries Government Documents Department