Atmospheric nucleation is the dominant source of aerosol particles in the global atmosphere and an important player in aerosol climatic effects. The key steps of this process occur in the sub-2-nanometer (nm) size range, in which direct size-segregated observations have not been possible until very recently. Here, we present detailed observations of atmospheric nanoparticles and clusters down to 1-nm mobility diameter. We identified three separate size regimes below 2-nm diameter that build up a physically, chemically, and dynamically consistent framework on atmospheric nucleation--more specifically, aerosol formation via neutral pathways. Our findings emphasize the important role of organic compounds in atmospheric aerosol formation, subsequent aerosol growth, radiative forcing and associated feedbacks between biogenic emissions, clouds, and climate.

The formation of oligomeric molecules, an important step in secondary organic aerosol production, is reported. Aerosols were produced by the reaction of alpha-pinene and ozone in the presence of acid seed aerosol and characterized by exact mass measurements and tandem mass spectrometry. Oligomeric products between 200 and 900 u were detected with both electrospray ionization and matrix-assisted laser desorption ionization. The exact masses and dissociation products of these ions were consistent with various combinations of the known primary products of this reaction ("monomers") with and/or without the expected acid-catalyzed decomposition products of the monomers. Oligomers as large as tetramers were detected. Both aldol condensations and gem-diol reactions are suggested as possible pathways for oligomer formation. Exact mass measurements also revealed reaction products that cannot be explained by simple oligomerization of monomers and monomer decomposition products, suggesting the existence of complex reaction channels. Chemical reactions leading to oligomer formation provide a reasonable answer to a difficult problem associated with secondary organic aerosol production in the atmosphere. It is unlikely that monomers alone play an important role in the formation and growth of nuclei in the atmosphere as their Kelvin vapor pressures are too high for them to significantly partition into the particle phase. Polymerization provides a mechanism by which partitioning to the particle phase becomes favored.

The formation of secondary organic aerosol (SOA) by reaction of ozone with monoterpenes (beta-pinene, delta3-carene, limonene, and sabinene) was studied on a short time scale of 3-22 s with a flow tube reactor. Online chemical analysis was performed with the Photoionization Aerosol Mass Spectrometer (PIAMS) to obtain molecular composition and the Nanoaerosol Mass Spectrometer (NAMS) to obtain elemental composition. Molecular composition data showed that dimers and higher order oligomers are formed within seconds after the onset of reaction, indicating that there is no intrinsic kinetic barrier to oligomer formation. Because oligomer formation is fast, it is unlikely that a large number of steps are involved in their formation. Therefore, ion distributions in the PIAMS spectra were interpreted through reactions of intermediates postulated in previous studies with monomer end products or other intermediates. Based on ion signal intensities in the mass spectra, organic peroxides appear to comprise a greater fraction of the aerosol than secondary ozonides. This conclusion is supported by elemental composition data from NAMS that gave C:O ratios in the 2.2-2.7 range.

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The molecular composition of secondary organic aerosol (SOA) from the ozonolysis of monoterpenes (α-pinene and β-pinene) was studied by liquid chromatography mass spectrometry and high-resolution Fourier transform ion cyclotron resonance mass spectrometry techniques, both employing electrospray ionization (ESI). SOA particles were generated in a flow tube reactor with a reaction time of 23 s. A microsampling assembly in combination with ESI-FTICR analysis permitted SOA with a mass loading as low as 3.5 μg/m(3) to be characterized with high accuracy and precision mass analysis. Hundreds of product molecular formulas were identified that were common to all mass loadings; however the relative intensities changed significantly. In particular, a species with the (neutral molecule) formula C(17)H(26)O(8) increased substantially in intensity relative to other products as the mass loading decreased. Tandem mass spectrometry (MS(n)) of this species showed it to be a dimer of C(9)H(14)O(4) and C(8)H(12)O(4), most likely pinic acid and terpenylic acid, respectively. LCMS analysis showed different elution times for the dimer and monomer species, confirming that the dimer was not an artifact of ESI analysis. The particle number concentration increased linearly with ozone concentration (the limiting reactant in the experiment), arguing against gas phase dimerization as the rate limiting step in particle formation.

The composition and structure of freshly formed oligomers in alpha- and beta- pinene SOA are studied with high performance mass spectrometry to provide insight into the SOA formation mechanism. Van Krevelen plots (H:C ratio vs O:C ratio) are interpreted in the context of distinct structural domains that correspond to separate oligomer formation routes. The domain containing most of the signal intensity encompasses elemental formulas that correspond to oligomerization reactions of intermediates and/or stable molecule monomers produced by ozonolysis of the precursor. While oligomers involving reactive intermediates from the hydroperoxide channel dominate the product distribution, products are also observed that uniquely map to the stable Criegee intermediate and/ or combinations of stable molecule monomers. A second domain encompasses molecules having lower H:C ratios but similar O:C ratios to the first domain. Many of the products observed in this domain have double bond equivalents greater than the maximum number possible when forming dimers by standard reaction mechanisms and are interpreted in the context of repeated self-reactions of alkoxy/peroxy radicals. A third domain encompasses molecules having very high H:C and O:C ratios consistent with polymerization of formaldehyde and/or acetaldehyde. These domains remain distinguishable from experiment to experiment and among different extraction solvents (50/50 methanol-water, 50/50 acetonitrile-water,100% water).

Aerosol mass spectrometers allow particles to be counted on the basis of size and chemical composition. In most instruments, individual particles are ablated with a pulsed laser to obtain a mass spectrum. Using this method to characterize ambient aerosols requires an understanding of biases induced by the measurement process. For particles less than 200 nm diameter, the efficiency of detection is shown to be dependent on both size and composition. These dependencies arise from the transmission characteristics of the particle inlet and the intrinsic ability of a particle to be vaporized and ionized. The relative contributions of each are determined for a series of atmospherically relevant test aerosols. Small particles are generally more difficult to detect and analyze than large particles because they are more difficult to focus through the inlet into a tight beam and because they are more difficult to ablate. Particles composed of polycyclic aromatic hydrocarbons, ammonium nitrate, and alkali metal ions are efficiently ablated by laser ablation. Aliphatic organics are less efficiently ablated, and ammonium sulfate is very difficult to detect in a positive ion spectrum. The mass spectra of ultrafine particles show extensive fragmentation, making it difficult to distinguish aliphatic and aromatic components. However, organic particles may be classified on the basis of inorganic impurities. Initial field measurements of ambient ultrafine particles are consistent with these conclusions.

A new method, photoionization aerosol mass spectrometry (PIAMS), is described for real-time analysis of organic components in airborne particles below approximately 300 nm in diameter. Particles are focused through an aerodynamic lens assembly into the mass spectrometer where they are collected on a probe in the source region. After a sufficient amount of sample has been collected, the probe is irradiated with a pulsed infrared laser beam to vaporize organic components, which are then softly ionized with coherent vacuum ultraviolet radiation at 118 nm (10.5 eV). Since the photon energy is close to the ionization energies of most organic compounds, fragmentation is minimized. Both aliphatic and aromatic compounds of atmospheric relevance are detected and quantified in the low- to midpicogram range. The photoionization signal intensity increases linearly with the amount of material sampled and is independent of particle size. The fragmentation induced by laser desorption is greater than that observed with thermal vaporization, suggesting that the internal energy imparted by the former is greater. Although some molecular fragmentation is observed, mass spectra from common sources of ambient organic aerosol are distinguishable and consistent with previous off-line measurements by gas chromatography/mass spectrometry. These results illustrate the potential of PIAMS for molecular characterization of organic aerosols in ambient and smog chamber measurements.