M. Lizabeth Alexander

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.

Effect of hydrophobic primary organic aerosols on secondary organic aerosol formation from ozonolysis of α-pinene

[1] Semi-empirical secondary organic aerosol (SOA) models typically assume a well-mixed organic aerosol phase even in the presence of hydrophobic primary organic aerosols (POA). This assumption significantly enhances the modeled SOA yields as additional organic mass is made available to absorb greater amounts of oxidized secondary organic gases than otherwise. We investigate the applicability of this critical assumption by measuring SOA yields from ozonolysis of a-pinene (a major biogenic SOA precursor) in a smog chamber in the absence and in the presence of dioctyl phthalate (DOP) and lubricating oil seed aerosol. These particles serve as surrogates for urban hydrophobic POA. The results show that these POA did not enhance the SOA yields. If these results are found to apply to other biogenic SOA precursors, then the semiempirical models used in many global models would predict significantly less biogenic SOA mass and display reduced sensitivity to anthropogenic POA emissions than previously thought. Citation: Song, C., R. A. Zaveri, M. L. Alexander, J. A. Thornton, S. Madronich, J. V. Ortega, A. Zelenyuk, X.-Y. Yu, A. Laskin, and D. A. Maughan (2007), Effect of hydrophobic primary organic aerosols on secondary organic aerosol formation from ozonolysis of a-pinene, Geophys. Res. Lett., 34, L20803,

Comparison of FTIR and Particle Mass Spectrometry for the Measurement of Particulate Organic Nitrates

While multifunctional organic nitrates are formed during the atmospheric oxidation of volatile organic compounds, relatively little is known about their signatures in particle mass spectrometers. High resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS) and FTIR spectroscopy on particles impacted on ZnSe windows were applied to NH(4)NO(3), NaNO(3), and isosorbide 5-mononitrate (IMN) particles, and to secondary organic aerosol (SOA) from NO(3) radical reactions at 22 degrees C and 1 atm in air with alpha- and beta-pinene, 3-carene, limonene, and isoprene. For comparison, single particle laser ablation mass spectra (SPLAT II) were also obtained for IMN and SOA from the alpha-pinene reaction. The mass spectra of all particles exhibit significant intensity at m/z 30, and for the SOA, weak peaks corresponding to various organic fragments containing nitrogen [C(x)H(y)N(z)O(a)](+) were identified using HR-ToF-AMS. The NO(+)/NO(2)(+) ratios from HR-ToF-AMS were 10-15 for IMN and the SOA from the alpha- and beta-pinene, 3-carene, and limonene reactions, approximately 5 for the isoprene reaction, 2.4 for NH(4)NO(3) and 80 for NaNO(3). The N/H ratios from HR-ToF-AMS for the SOA were smaller by a factor of 2 to 4 than the -ONO(2)/C-H ratios measured using FTIR. FTIR has the advantage that it provides identification and quantification of functional groups. The NO(+)/NO(2)(+) ratio from HR-ToF-AMS can indicate organic nitrates if they are present at more than 15-60% of the inorganic nitrate, depending on whether the latter is NH(4)NO(3) or NaNO(3). However, unique identification of specific organic nitrates is not possible with either method.

Ambient Gas-Particle Partitioning of Tracers for Biogenic Oxidation

Exchange of atmospheric organic compounds between gas and particle phases is important in the production and chemistry of particle-phase mass but is poorly understood due to a lack of simultaneous measurements in both phases of individual compounds. Measurements of particle- and gas-phase organic compounds are reported here for the southeastern United States and central Amazonia. Polyols formed from isoprene oxidation contribute 8% and 15% on average to particle-phase organic mass at these sites but are also observed to have substantial gas-phase concentrations contrary to many models that treat these compounds as nonvolatile. The results of the present study show that the gas-particle partitioning of approximately 100 known and newly observed oxidation products is not well explained by environmental factors (e.g., temperature). Compounds having high vapor pressures have higher particle fractions than expected from absorptive equilibrium partitioning models. These observations support the conclusion that many commonly measured biogenic oxidation products may be bound in low-volatility mass (e.g., accretion products, inorganic-organic adducts) that decomposes to individual compounds on analysis. However, the nature and extent of any such bonding remains uncertain. Similar conclusions are reach for both study locations, and average particle fractions for a given compound are consistent within ∼25% across measurement sites.

A New Aerosol Flow System for Photochemical and Thermal Studies of Tropospheric Aerosols

For studying the formation and photochemical/thermal reactions of aerosols relevant to the troposphere, a unique, high-volume, slow-flow, stainless steel aerosol flow system equipped with UV lamps has been constructed and characterized experimentally. The total flow system length is 8.5 m and includes a 1.2 m section used for mixing, a 6.1 m reaction section and a 1.2 m transition cone at the end. The 45.7 cm diameter results in a smaller surface to volume ratio than is found in many other flow systems and thus reduces the potential contribution from wall reactions. The latter are also reduced by frequent cleaning of the flow tube walls which is made feasible by the ease of disassembly. The flow tube is equipped with ultraviolet lamps for photolysis. This flow system allows continuous sampling under stable conditions, thus increasing the amount of sample available for analysis and permitting a wide variety of analytical techniques to be applied simultaneously. The residence time is of the order of an hour, and sampling ports located along the length of the flow tube allow for time-resolved measurements of aerosol and gas-phase products. The system was characterized using both an “inert” gas (CO 2 ) and particles (atomized NaNO 3 ). Instruments interfaced directly to this flow system include a NO x analyzer, an ozone analyzer, relative humidity and temperature probes, a scanning mobility particle sizer spectrometer, an aerodynamic particle sizer spectrometer, a gas chromatograph-mass spectrometer, an integrating nephelometer, and a Fourier transform infrared spectrophotometer equipped with a long path (64 m) cell. Particles collected with impactors and filters at the various sampling ports can be analyzed subsequently by a variety of techniques. Formation of secondary organic aerosol from α-pinene reactions (NO x photooxidation and ozonolysis) are used to demonstrate the capabilities of this new system.

Nitrate ion photochemistry at interfaces : a new mechanism for oxidation of α-pinene

The photooxidation of 0.6-0.9 ppm alpha-pinene in the presence of a deliquesced thin film of NaNO(3), and for comparison increasing concentrations of NO(2), was studied in a 100 L Teflon(R) chamber at relative humidities from 72-88% and temperatures from 296-304 K. The loss of alpha-pinene and the formation of gaseous products were followed with time using proton transfer mass spectrometry. The yields of gas phase products were smaller in the NaNO(3) experiments than in NO(2) experiments. In addition, pinonic acid, pinic acid, trans-sobrerol and other unidentified products were detected in the extracts of the wall washings only for the NaNO(3) photolysis. These data indicate enhanced loss of alpha-pinene at the NaNO(3) thin film during photolysis. Supporting the experimental results are molecular dynamics simulations which predict that alpha-pinene has an affinity for the surface of the deliquesced nitrate thin film, enhancing the opportunity for oxidation of the impinging organic gas during the nitrate photolysis. This new mechanism of oxidation of organics may be partially responsible for the correlation between nitrate and the organic component of particles observed in many field studies, and may also contribute to the missing source of SOA needed to reconcile model predictions and field measurements. In addition, photolysis of nitrate on surfaces in the boundary layer may lead to oxidation of co-adsorbed organics.

Laser ablation isotope ratio mass spectrometry for enhanced sensitivity and spatial resolution in stable isotope analysis

Stable isotope analysis permits the tracking of physical, chemical, and biological reactions and source materials at a wide variety of spatial scales. We present a laser ablation isotope ratio mass spectrometry (LA-IRMS) method that enables δ(13)C measurement of solid samples at 50 µm spatial resolution. The method does not require sample pre-treatment to physically separate spatial zones. We use laser ablation of solid samples followed by quantitative combustion of the ablated particulates to convert sample carbon into CO(2). Cryofocusing of the resulting CO(2) coupled with modulation in the carrier flow rate permits coherent peak introduction into an isotope ratio mass spectrometer, with only 65 ng carbon required per measurement. We conclusively demonstrate that the measured CO(2) is produced by combustion of laser-ablated aerosols from the sample surface. We measured δ(13)C for a series of solid compounds using laser ablation and traditional solid sample analysis techniques. Both techniques produced consistent isotopic results but the laser ablation method required over two orders of magnitude less sample. We demonstrated that LA-IRMS sensitivity coupled with its 50 µm spatial resolution could be used to measure δ(13) C values along a length of hair, making multiple sample measurements over distances corresponding to a single days growth. This method will be highly valuable in cases where the δ(13)C analysis of small samples over prescribed spatial distances is required. Suitable applications include forensic analysis of hair samples, investigations of tightly woven microbial systems, and cases of surface analysis where there is a sharp delineation between different components of a sample.