Dan G. Imre

Evaporation kinetics and phase of laboratory and ambient secondary organic aerosol

Field measurements of secondary organic aerosol (SOA) find significantly higher mass loads than predicted by models, sparking intense effort focused on finding additional SOA sources but leaving the fundamental assumptions used by models unchallenged. Current air-quality models use absorptive partitioning theory assuming SOA particles are liquid droplets, forming instantaneous reversible equilibrium with gas phase. Further, they ignore the effects of adsorption of spectator organic species during SOA formation on SOA properties and fate. Using accurate and highly sensitive experimental approach for studying evaporation kinetics of size-selected single SOA particles, we characterized room-temperature evaporation kinetics of laboratory-generated α-pinene SOA and ambient atmospheric SOA. We found that even when gas phase organics are removed, it takes ∼24 h for pure α-pinene SOA particles to evaporate 75% of their mass, which is in sharp contrast to the ∼10 min time scale predicted by current kinetic models. Adsorption of “spectator” organic vapors during SOA formation, and aging of these coated SOA particles, dramatically reduced the evaporation rate, and in some cases nearly stopped it. Ambient SOA was found to exhibit evaporation behavior very similar to that of laboratory-generated coated and aged SOA. For all cases studied in this work, SOA evaporation behavior is nearly size-independent and does not follow the evaporation kinetics of liquid droplets, in sharp contrast with model assumptions. The findings about SOA phase, evaporation rates, and the importance of spectator gases and aging all indicate that there is need to reformulate the way SOA formation and evaporation are treated by models.

Nonequilibrium atmospheric secondary organic aerosol formation and growth

Airborne particles play critical roles in air quality, health effects, visibility, and climate. Secondary organic aerosols (SOA) formed from oxidation of organic gases such as α-pinene account for a significant portion of total airborne particle mass. Current atmospheric models typically incorporate the assumption that SOA mass is a liquid into which semivolatile organic compounds undergo instantaneous equilibrium partitioning to grow the particles into the size range important for light scattering and cloud condensation nuclei activity. We report studies of particles from the oxidation of α-pinene by ozone and NO3 radicals at room temperature. SOA is primarily formed from low-volatility ozonolysis products, with a small contribution from higher volatility organic nitrates from the NO3 reaction. Contrary to expectations, the particulate nitrate concentration is not consistent with equilibrium partitioning between the gas phase and a liquid particle. Rather the fraction of organic nitrates in the particles is only explained by irreversible, kinetically determined uptake of the nitrates on existing particles, with an uptake coefficient that is 1.6% of that for the ozonolysis products. If the nonequilibrium particle formation and growth observed in this atmospherically important system is a general phenomenon in the atmosphere, aerosol models may need to be reformulated. The reformulation of aerosol models could impact the predicted evolution of SOA in the atmosphere both outdoors and indoors, its role in heterogeneous chemistry, its projected impacts on air quality, visibility, and climate, and hence the development of reliable control strategies.

Ozone production rate and hydrocarbon reactivity in 5 urban areas: A cause of high ozone concentration in Houston

[1]xa0Observations of ozone (O3) and O3 precursors taken from aircraft flights over Houston, TX, Nashville, TN; New York, NY; Phoenix, AZ, and Philadelphia, PA show that high concentrations of reactive volatile organic compounds (VOCs) in the Houston atmosphere lead to calculated O3 production rates that are 2 to 5 times higher than in the other 4 cities even though NOx concentrations are comparable. Within the Houston metropolitan area, concentrations of VOCs and O3 production rates are highest in the Ship Channel region; the location of one of the largest petrochemical complexes in the world. As a consequence the concentration of O3 in the Houston metropolitan area has recently exceeded 250 ppb, the highest value observed in the U.S within the past 5 years.

From Agglomerates of Spheres to Irregularly Shaped Particles: Determination of Dynamic Shape Factors from Measurements of Mobility and Vacuum Aerodynamic Diameters

With the advent of advanced real-time aerosol instrumentation, it has become possible to simultaneously measure individual particle mobility and vacuum aerodynamic diameters. This paper presents an experimental exploration of the effect of particle shape on the relationship between mobility and vacuum aerodynamic diameters. We make measurements on systems of three types: (1) Agglomerates of spheres, for which the density and the volume are known; (2) Ammonium sulfate, sodium chloride, succinic acid and lauric acid irregularly shaped particles of known density; and (3) Internally mixed particles, containing organics and ammonium sulfate, of unknown density and shape. For agglomerates of spheres we observe and quantify alignment effects in the Differential Mobility Analyzer (DMA), an important consequence of which is that mobility diameter of aspherical particles can be a function of DMA operating voltages. We report the first measurements of the dynamic shape factors (DSFs) in free molecular regime. We report the first experimental determination of DSF for ammonium sulfate particles, for which we find DSF to increase from 1.03 to 1.07 as particle mobility diameter increases from 160 nm to 500 nm. Three types of NaCl particles were generated and characterized: nearly spherical particles with DSF of ∼ 1.02; cubic with DSF that increases from 1.06 to 1.17 as particle mobility diameter increases; and compact agglomerates with DSF 1.3–1.4. Organic particles were found to be nearly spherical. The data suggest that addition of organics to ammonium sulfate particles lowers their DSF.

Single Particle Laser Ablation Time-of-Flight Mass Spectrometer: An Introduction to SPLAT

We present our single particle mass spectrometer we call SPLAT. SPLAT was designed to make possible the detection and characterization of particles down to 100 nm, generate reproducible single particle mass spectra, and collect data at a high rate. The final instrument presented here is capable of characterizing individual particles down to 50 nm at the rate of 20 particles per second. In SPLAT mass spectra are generated by a two-step process, thet uses a pulsed infrared laser to heat the particle and a time delayed pulsed UV laser to create ions. We describe a mode of operation that makes it possible to take advantage of the gas phase ionization of the semivolatile components of the particle, while also generating mass spectral signatures of the nonvolatile fraction, thereby proividing complete particle mass spectra. We present some sample results from two field deployments of SPLAT.

Phase Transformation and Metastability of Hygroscopic Microparticles

The hydration and crystallization of inorganic salt particles are investigated in an electrodynamic balance, in which a levitated single microparticle is undergoing phase transformation and growth under controlled humidity conditions. Laser Raman and Mie scattering techniques are used to probe the chemical and physical state of the microparticle before and after phase transformation. Here, we report first spectroscopic evidence that new metastable solid states form in hygroscopic aerosol particles. Because of the high degree of supersaturation at which a solution droplet solidifies, a metastable crystalline or amorphous state often results. The formation of such state is not predicted from bulk-phase thermodynamics and, in some cases, the resulting metastable state is entirely unknown heretofore. We also document new solid-solution and solid-solid phase transitions which occur exclusively in microparticles. Results are presented for particles composed of (NH4)2SO4, Na2SO4, LiClO4, Sr(NO3)2, KHSO4, RbHSO4 ...

MODELS OVERESTIMATE DIFFUSE CLEAR-SKY SURFACE IRRADIANCE: A CASE FOR EXCESS ATMOSPHERIC ABSORPTION

Radiative transfer models consistently overestimate surface diffuse downward irradiance in cloud-free atmospheres by 9 to 40% at two low altitude sites while correctly calculating direct-normal Solar irradiance. For known systematic and random measurement errors and for realistic aerosol optical properties, the discrepancy can be resolved by a reduction in the vertical aerosol optical thickness (AOT) inferred from sunphotometric measurements by an average 0.02 ± 0.01 for 32 cases examined, together with a compensating increase in a continuum-like atmospheric absorptance over the solar spectrum of ∼5.0% ± 3.0%. This phenomenon is absent at two high altitude sites, where models and measurements agree to within their mutual uncertainties. Examination of apparent AOT at several locations around the globe also indicates presence of such excess atmospheric absorption. The proposed absorption and corresponding reduction in AOT would have important consequences for climate prediction and remote sensing.

Ozone production in the New York City urban plume

In the summer of 1996 the Department of Energy G-1 aircraft was deployed in the New York City metropolitan area as part of the North American Research Strategy for Tropospheric Ozone-Northeast effort to determine the causes of elevated O3 levels in the northeastern United States. Measurements of O3, O3 precursors, and other photochemically active trace gases were made upwind and downwind of New York City with the objective of characterizing the O3 formation process and its dependence on ambient levels of NOx and volatile organic compounds (VOCs). Four flights are discussed in detail. On two of these flights, winds were from the W-SW, which is the typical direction for an O3 episode. On the other two flights, winds were from the NW, which puts a cleaner area upwind of the city. The data presented include plume and background values of O3, CO, NOx, and NOy concentration and VOC reactivity. On the W-SW flow days O3 reached 110 ppb. According to surface observations the G-1 intercepted the plume close to the region where maximum O3 occurred. At this point the ratio NOx/NOy was 20–30%, indicating an aged plume. Plume values of CO/NOy agree to within 20% with emission estimates from the core of the New York City metropolitan area. Steady state photochemical calculations were performed using observed or estimated trace gas concentrations as constraints. According to these calculations the local rate of O3 production P(O3) in all four plumes is VOC sensitive, sometimes strongly so. The local sensitivity calculations show that a specified fractional decrease in VOC concentration yields a similar magnitude fractional decrease in P(O3). Imposing a decrease in NOx, however, causes P(O3) to increase. The question of primary interest from a regulatory point of view is the sensitivity of O3 concentration to changes in emissions of NOx and VOCs. A qualitative argument is given that suggests that the total O3 formed in the plume, which depends on the entire time evolution of the plume, is also VOC sensitive. Indicator ratios O3/NOz and H2O2/NOz mainly support the conclusion that plume O3 is VOC sensitive.

Morphology of mixed primary and secondary organic particles and the adsorption of spectator organic gases during aerosol formation

Primary organic aerosol (POA) and associated vapors can play an important role in determining the formation and properties of secondary organic aerosol (SOA). If SOA and POA are miscible, POA will significantly enhance SOA formation and some POA vapor will incorporate into SOA particles. When the two are not miscible, condensation of SOA on POA particles forms particles with complex morphology. In addition, POA vapor can adsorb to the surface of SOA particles increasing their mass and affecting their evaporation rates. To gain insight into SOA/POA interactions we present a detailed experimental investigation of the morphologies of SOA particles formed during ozonolysis of α-pinene in the presence of dioctyl phthalate (DOP) particles, serving as a simplified model of hydrophobic POA, using a single-particle mass spectrometer. Ultraviolet laser depth-profiling experiments were used to characterize two different types of mixed SOA/DOP particles: those formed by condensation of the oxidized α-pinene products on size-selected DOP particles and by condensation of DOP on size-selected α-pinene SOA particles. The results show that the hydrophilic SOA and hydrophobic DOP do not mix but instead form layered phases. In addition, an examination of homogeneously nucleated SOA particles formed in the presence of DOP vapor shows them to have an adsorbed DOP coating layer that is ∼4 nm thick and carries 12% of the particles mass. These results may have implications for SOA formation and behavior in the atmosphere, where numerous organic compounds with various volatilities and different polarities are present.

Characterization of the Nashville urban plume on July 3 and July 18, 1995

This paper reports results from the Southern Oxidants Study field campaign designed to characterize the formation and distribution of ozone and related species in the Nashville urban region. Data from several airborne platforms as well as surface observations on July 3 and 18 are examined to gain insight into the factors that control O{sub 3} formation rates and concentrations in the regional plumes. On both days, well-defined urban and power plant plumes were sampled. Utilizing both aircraft and surface data, a detailed kinetic analysis of the chemical evolution of the urban plume is performed to derive NO{sub x} lifetime, ozone production efficiency, OH concentration, HNO{sub 3} dry deposition rate, and the relative importance of natural and anthropogenic hydrocarbons to O{sub 3} production. Analysis of the urban plume data revealed a very active photochemical system (average [OH]{approximately}1.2{times}10{sup 7}hmoleculeshcm{sup {minus}3}) which consumed 50{percent} of the NO{sub x} within approximately 2 hours, at an ozone production efficiency of 2.5 to 4 molecules for each molecule of NO{sub x}. Anthropogenic hydrocarbons provided approximately 44{percent} of the fuel for ozone production by the urban plume. The dry deposition rate for HNO{sub 3} in the urban plume was estimated to be of the order of 5morexa0» to 7 cmhs{sup {minus}1}. {copyright} 1998 American Geophysical Union«xa0less