Seeded Crystal Growth of Internally Mixed Organic-Inorganic Aerosols: Impact of Organic Phase State.

Atmospheric aerosols are complex with both inorganic and organic components. The soluble inorganics can transition between aqueous and crystalline phases through efflorescence and deliquescence. This study focuses on the efflorescence of (NH4)2SO4/organic particles by seeded crystal growth through contact with a crystal of (NH4)2SO4. Seeded crystal growth is known to effectively shut down supersaturation of aqueous aerosols. Here, we investigate whether organics can inhibit seeded crystal growth. We demonstrate that poly(ethylene glycol) 400 (PEG-400), which phase-separates from the aqueous (NH4)2SO4 and forms a core-shell structure, did not inhibit seeded crystal growth of (NH4)2SO4 at all relative humidity (RH) values below deliquescence RH. The PEG-400 layer was not viscous enough to prevent the diffusion of species through the coating. In contrast, we find that although raffinose, which stays homogeneously mixed with (NH4)2SO4, did not inhibit seeded crystal growth at RH > 45%, it did inhibit heterogeneous efflorescence at lower humidities. Viscosity measurements using an electrodynamic balance show a significant increase in viscosity as humidity was lowered, suggesting that inhibited diffusion of water and ions prevented efflorescence. The observed efflorescence at the higher RH also demonstrates that collisions can induce efflorescence of mixed aerosols that would otherwise not homogeneously effloresce.

Persisting volcanic ash particles impact stratospheric SO2 lifetime and aerosol optical properties.

Volcanic ash is often neglected in climate simulations because ash particles are assumed to have a short atmospheric lifetime, and to not participate in sulfur chemistry. After the Mt. Kelut eruption in 2014, stratospheric ash-rich aerosols were observed for months. Here we show that the persistence of super-micron ash is consistent with a density near 0.5 g cm-3, close to pumice. Ash-rich particles dominate the volcanic cloud optical properties for the first 60 days. We also find that the initial SO2 lifetime is determined by SO2 uptake on ash, rather than by reaction with OH as commonly assumed. About 43% more volcanic sulfur is removed from the stratosphere in 2 months with the SO2 heterogeneous chemistry on ash particles than without. This research suggests the need for re-evaluation of factors controlling SO2 lifetime in climate model simulations, and of the impact of volcanic ash on stratospheric chemistry and radiation.

Brown Carbon Production by Aqueous-Phase Interactions of Glyoxal and SO2.

Oxalic acid and sulfate salts are major components of aerosol particles. Here, we explore the potential for their respective precursor species, glyoxal and SO2, to form atmospheric brown carbon via aqueous-phase reactions in a series of bulk aqueous and flow chamber aerosol experiments. In bulk aqueous solutions, UV- and visible-light-absorbing products are observed at pH 3-4 and 5-6, respectively, with small but detectable yields of hydroxyquinone and polyketone products formed, especially at pH 6. Hydroxymethanesulfonate (HMS), C2, and C3 sulfonates are major products detected by electrospray ionization mass spectrometry (ESI-MS) at pH 5. Past studies have assumed that the reaction of formaldehyde and sulfite was the only atmospheric source of HMS. In flow chamber experiments involving sulfite aerosol and gas-phase glyoxal with only 1 min residence times, significant aerosol growth is observed. Rapid brown carbon formation is seen with aqueous aerosol particles at >80% relative humidity (RH). Brown carbon formation slows at 50-60% RH and when the aerosol particles are acidified with sulfuric acid but stops entirely only under dry conditions. This chemistry may therefore contribute to brown carbon production in cloud-processed pollution plumes as oxidizing volatile organic compounds (VOCs) interact with SO2 and water.

The Impact of Molecular Oxygen on Anion Composition in a Hazy Archean Earth Atmosphere.

Atmospheric organic hazes are common in planetary bodies in our solar system and likely exoplanet atmospheres as well. In addition, geochemical data support the existence of an organic haze in the early Earth's atmosphere. Much of what is known about organic haze formation derives from studies of Saturn's moon Titan. It is believed that on Titan ions play an important role in haze formation. It is possible, by using Titan as an analog for the Archean Earth, to consider that an Archean haze could have formed by similar processes. Here, we examine the anion chemistry that occurs during laboratory simulations of early Earth haze formation and measure the composition of gaseous anions as a function of O2 mixing ratio. Gaseous anion composition and relative abundances are measured by an atmospheric pressure interface time-of-flight mass spectrometer and are compared to previous photochemical haze mass loading measurements. Numerous anions are observed spanning from mass-to-charge ratio 26 to 246, with a majority of the identified anions containing carbon, hydrogen, nitrogen, and/or oxygen. A shift in the anion composition occurs with increasing the precursor O2 mixing ratio. With 0-20 ppmv O2 in CH4/CO2/N2 mixtures, ions contain mostly organic nitrogen, with CNO- being the most intense ion peak. As the precursor O2 is increased to 200 and 2000 ppmv, inorganic nitrogen ions become the dominant chemical group, with NO3- having the most intense ion signal. The clear shift in the ionic composition could be indicative of a modification to the gas-phase chemistry that occurs in the transition from an anoxic atmosphere to an oxygen-containing atmosphere, with potential astrobiological significance.

Immersion and Contact Efflorescence Induced by Mineral Dust Particles.

The phase state of inorganic salt aerosols impacts their properties, including the ability to undergo hygroscopic growth, catalyze heterogeneous reactions, and act as cloud condensation nuclei. Here, we report the first observation of contact efflorescence by mineral dust aerosol. The efflorescence of aqueous ammonium sulfate ((NH4)2SO4) and sodium chloride (NaCl) droplets by contact with three types of mineral dust particles (illite, montmorillonite, and NX illite), were examined using an optical levitation chamber. Immersion mode efflorescence was also studied for comparison. We find that in the presence of mineral dust particles, crystallization occurred at a higher relative humidity (RH) when compared to the homogeneous phase transition. Additionally, crystallization by contact mode efflorescence occurred at a higher RH than the corresponding immersion mode. Crystallization efficiencies in the contact mode exhibited an ion-specific trend consistent with the Hoffmeister series. Estimates for lifetimes of a salt droplet to collide with dust particles suggests that collisions between the two aerosol types are likely to occur before the salt aerosol is removed by other atmospheric processes. Such collisions could then lead to the crystallization of salt droplets that would otherwise have remained liquid, changing the overall impact that salt aerosols have on atmospheric chemistry and climate.

Laboratory Investigations on the Survival of Bacillus subtilis Spores in Deliquescent Salt Mars Analog Environments.

Observed features such as recurring slope lineae suggest that liquid water may exist on the surface and near-subsurface of Mars today. The presence of this liquid water, likely in the form of a brine, has important implications for the present-day water cycle, habitability, and planetary protection policies. It is possible that this water is formed, at least partially, by deliquescence of salts, a process during which hygroscopic salts absorb water vapor from the atmosphere and form a saturated liquid brine. We performed laboratory experiments to examine the ability of Bacillus subtilis (B-168) spores, alone or mixed with calcium perchlorate salt (Ca(ClO4)2), to form liquid water via deliquescence under Mars-relevant conditions. Spore survival after exposure to these conditions was examined. An environmental chamber was used to expose the samples to temperature and relative humidity (RH) values similar to those found on Mars, and Raman microscopy was used to identify the phases of water and salt that were present and to confirm the presence of spores. We found that B-168 spores did not condense any detectable water vapor on their own during the diurnal cycle, even at 100% RH. However, when spores were mixed with perchlorate salt, the entire sample deliquesced at low RH values, immersing the spores in a brine solution during the majority of the simulated martian temperature and humidity cycle. After exposure to the simulated diurnal cycles and, in some cases, perchlorate brine, the impact of each environmental scenario on spore survival was estimated by standard plate assay. We found that, if there are deliquescent salts in contact with spores, there is a mechanism for the spores to acquire liquid water starting with only atmospheric water vapor as the H2O source. Also, neither crystalline nor liquid Ca(ClO4)2 is sporicidal despite the low water activity. Key Words: Raman microscopy-Mars-Planetary protection-Salts-Water activity. Astrobiology 17, 997-1008.

Crystal nucleation initiated by transient ion-surface interactions at aerosol interfaces.

Particle collisions are a common occurrence in the atmosphere, but no empirical observations exist to fully predict the potential effects of these collisions on air quality and climate projections. The current consensus of heterogeneous crystal nucleation pathways relevant to the atmosphere dictates that collisions with amorphous particles have no effect on the crystallization relative humidity (RH) of aqueous inorganic aerosols because there is no stabilizing ion-surface interaction to facilitate the formation of crystal nuclei. In contrast to this view of heterogeneous nucleation, we report laboratory observations demonstrating that collisions with hydrophobic amorphous organic aerosols induced crystallization of aqueous inorganic microdroplets at high RH, the effect of which was correlated with destabilizing water-mediated ion-specific surface interactions. These same organic aerosols did not induce crystallization once internally mixed in the droplet, pointing toward a previously unconsidered transient ion-specific crystal nucleation pathway that can promote aerosol crystallization via particle collisions.

Follow the Carbon: Isotopic Labeling Studies of Early Earth Aerosol.

Despite the faint young Sun, early Earth might have been kept warm by an atmosphere containing the greenhouse gases CH4 and CO2 in mixing ratios higher than those found on Earth today. Laboratory and modeling studies suggest that an atmosphere containing these trace gases could lead to the formation of organic aerosol haze due to UV photochemistry. Chemical mechanisms proposed to explain haze formation rely on CH4 as the source of carbon and treat CO2 as a source of oxygen only, but this has not previously been verified experimentally. In the present work, we use isotopically labeled precursor gases and unit-mass resolution (UMR) and high-resolution (HR) aerosol mass spectrometry to examine the sources of carbon and oxygen to photochemical aerosol formed in a CH4/CO2/N2 atmosphere. UMR results suggest that CH4 contributes 70-100% of carbon in the aerosol, while HR results constrain the value from 94% to 100%. We also confirm that CO2 contributes approximately 10% of the total mass to the aerosol as oxygen. These results have implications for the geochemical interpretations of inclusions found in Archean rocks on Earth and for the astrobiological potential of other planetary atmospheres. Key Words: Atmosphere-Early Earth-Planetary atmospheres-Carbon dioxide-Methane. Astrobiology 16, 822-830.

Contact efflorescence as a pathway for crystallization of atmospherically relevant particles.

Inadequate knowledge of the phase state of atmospheric particles represents a source of uncertainty in global climate and air quality models. Hygroscopic aqueous inorganic particles are often assumed to remain liquid throughout their atmospheric lifetime or only (re)crystallize at low relative humidity (RH) due to the kinetic limitations of efflorescence (salt crystal nucleation and growth from an aqueous solution). Here we present experimental observations of a previously unexplored heterogeneous nucleation pathway that we have termed "contact efflorescence," which describes efflorescence initiated by an externally located solid particle coming into contact with the surface of a metastable aqueous microdroplet. This study demonstrates that upon a single collision, contact efflorescence is a pathway for crystallization of atmospherically relevant aqueous particles at high ambient RH (≤80%). Soluble inorganic crystalline particles were used as contact nuclei to induce efflorescence of aqueous ammonium sulfate [(NH4)2SO4], sodium chloride (NaCl), and ammonium nitrate (NH4NO3), with efflorescence being observed in several cases close to their deliquescence RH values (80%, 75%, and 62%, respectively). To our knowledge, these observations represent the highest reported efflorescence RH values for microdroplets of these salts. These results are particularly important for considering the phase state of NH4NO3, where the contact efflorescence RH (∼20-60%) is in stark contrast to the observation that NH4NO3 microdroplets do not homogeneously effloresce, even when exposed to extremely arid conditions (<1% RH). Considering the occurrence of particle collisions in the atmosphere (i.e., coagulation), these observations of contact efflorescence challenge many assumptions made about the phase state of inorganic aerosol.

Long Working-Distance Optical Trap for in Situ Analysis of Contact-Induced Phase Transformations.

A novel optical trapping technique is described that combines an upward propagating Gaussian beam and a downward propagating Bessel beam. Using this optical arrangement and an on-demand droplet generator makes it possible to rapidly and reliably trap particles with a wide range of particle diameters (∼1.5-25 µm), in addition to crystalline particles, without the need to adjust the optical configuration. Additionally, a new image analysis technique is described to detect particle phase transitions using a template-based autocorrelation of imaged far-field elastically scattered laser light. The image analysis allows subtle changes in particle characteristics to be quantified. The instrumental capabilities are validated with observations of deliquescence and homogeneous efflorescence of well-studied inorganic salts. Then, a novel collision-based approach to seeded crystal growth is described in which seed crystals are delivered to levitated aqueous droplets via a nitrogen gas flow. To our knowledge, this is the first account of contact-induced phase changes being studied in an optical trap. This instrument offers a novel and simple analytical technique for in situ measurements and observations of phase changes and crystal growth processes relevant to atmospheric science, industrial crystallization, pharmaceuticals, and many other fields.

Elemental analysis of complex organic aerosol using isotopic labeling and unit-resolution mass spectrometry.

Elemental analysis of unit-mass resolution (UMR) mass spectra is limited by the amount of information available to definitively elucidate the molecular formula of a molecule ionized by electron impact. The problem is compounded when a mixture of organic molecules (such as those found in organic aerosols) is analyzed without the benefit of prior separation. For this reason, quadrupole mass spectrometry is not usually suited to the elemental analysis of organic mixtures. Here, we present a mathematical method for the elemental analysis of UMR mass spectra of a complex organic aerosol through the use of isotopic labeling. Quadrupole aerosol mass spectrometry was used to obtain UMR data of (13)C-labeled and unlabeled aerosol generated by far ultraviolet (FUV) photochemistry of gas mixtures containing 0.1% of either CH4 or (13)CH4 in N2. In this method, the differences in the positions of ion groups in the resulting spectra are used to estimate the mass fraction of carbon in the aerosol, and estimation of the remaining elements follows. Analysis of the UMR data yields an elemental composition of 63 ± 7% C, 8 ± 1% H, and 29 ± 7% N by mass. Unlabeled aerosols formed under the same conditions are found by high-resolution time-of-flight aerosol mass spectrometry to have an elemental composition of 63 ± 3% C, 8 ± 1% H, 20 ± 4% N, and 9 ± 3% O by mass, in good agreement with the UMR method. This favorable comparison verifies the method, which expands the UMR mass spectrometry toolkit.

Chemical and physical transformations of aluminosilicate clay minerals due to acid treatment and consequences for heterogeneous ice nucleation.

Mineral dust aerosol is one of the largest contributors to global ice nuclei, but physical and chemical processing of dust during atmospheric transport can alter its ice nucleation activity. In particular, several recent studies have noted that sulfuric and nitric acids inhibit heterogeneous ice nucleation in the regime below liquid water saturation in aluminosilicate clay minerals. We have exposed kaolinite, KGa-1b and KGa-2, and montmorillonite, STx-1b and SWy-2, to aqueous sulfuric and nitric acid to determine the physical and chemical changes that are responsible for the observed deactivation. To characterize the changes to the samples upon acid treatment, we use X-ray diffraction, transmission electron microscopy, and inductively coupled plasma-atomic emission spectroscopy. We find that the reaction of kaolinite and montmorillonite with aqueous sulfuric acid results in the formation of hydrated aluminum sulfate. In addition, sulfuric and nitric acids induce large structural changes in montmorillonite. We additionally report the supersaturation with respect to ice required for the onset of ice nucleation for these acid-treated species. On the basis of lattice spacing arguments, we explain how the chemical and physical changes observed upon acid treatment could lead to the observed reduction in ice nucleation activity.

Heterogeneous ice nucleation on simulated secondary organic aerosol.

In this study, we have explored the phase behavior and the ice nucleation properties of secondary organic aerosol made from aqueous processing (aqSOA). AqSOA was made from the dark reactions of methylglyoxal with methylamine in simulated evaporated cloud droplets. The resulting particles were probed from 215 to 250 K using Raman spectroscopy coupled to an environmental cell. We find these particles are in a semisolid or glassy state based upon their behavior when exposed to mechanical pressure as well as their flow behavior. Further, we find that these aqSOA particles are poor depositional ice nuclei, in contrast to previous studies on simple mixtures of glassy organics. Additionally, we have studied the effect of ammonium sulfate on the phase, morphology, and ice nucleation behavior of the aqSOA. We find that the plasticizing effect of ammonium sulfate lowers the viscosity of the aqSOA, allowing the ammonium sulfate to effloresce within the aqSOA matrix. Upon humidification, the aqSOA matrix liquefies before it can depositionally nucleate ice, and the effloresced ammonium sulfate can act as an immersion mode ice nucleus. This change in the mode of nucleation is accompanied by an increase in the overall ice nucleation efficiency of the aqSOA particles.

Formation of semisolid, oligomerized aqueous SOA: lab simulations of cloud processing.

Glyoxal, methylglyoxal, glycolaldehyde, and hydroxyacetone form N-containing and oligomeric compounds during simulated cloud processing with small amines. Using a novel hygroscopicity tandem differential mobility analysis (HTDMA) system that allows varied humidification times, the hygroscopic growth (HG) of each of the resulting products of simulated cloud processing was measured. Continuous water uptake (gradual deliquescence) was observed beginning at ∼ 40% RH for all aldehyde-methylamine products. Particles containing ionic reaction products of either glyoxal or glycine were most hygroscopic, with HG between 1.16 and 1.20 at 80% RH. Longer humidification times (up to 20 min) produced an increase in growth factors for glyoxal-methylamine (19% by vol) and methylglyoxal-methylamine (8% by vol) aerosol, indicating that unusually long equilibration times can be required for HTDMA measurements of such particles. Glyoxal- and methylglyoxal-methylamine aerosol particles shattered in Raman microscopy impact-flow experiments, revealing that the particles were semisolid. Similar experiments on glycolaldehyde- and hydroxyacetone-methylamine aerosol found that the aerosol particles were liquid when dried for <1 h, but semisolid when dried for 20 h under ambient conditions. The RH required for flow (liquification) during humidification experiments followed the order methylglyoxal > glyoxal > glycolaldehyde = hydroxyacetone, likely caused by the speed of oligomer formation in each system.

Impact of organic coating on optical growth of ammonium sulfate particles.

Light extinction by particles in Earth's atmosphere is strongly dependent on particle size, chemical composition, hygroscopic growth properties, and particle mixing state. Here, the influence of an organic coating on particle optical growth was studied. The particle optical growth factor, fRHext, was measured using cavity ring-down aerosol extinction spectroscopy at 532 nm. The particles were composed of ammonium sulfate (AS), 1,2,6-hexanetriol, and mixed particles containing a wet or dry ammonium sulfate core and a 1,2,6-hexanetriol coating. Dry, coated particles were generated by atomization followed by drying. Wet, coated particles were formed via liquid-liquid phase separation (LLPS). LLPS was achieved by deliquescing and then drying the particles to a relative humidity (RH) between the phase separation RH and the efflorescence RH. For the LLPS particles, the fRHext at each RH was between the fRHext of ammonium sulfate and that of 1,2,6-hexanetriol. In contrast, for the mixed dry, coated particles, the fRHext was the same as 1,2,6-hexanetriol particles. At room temperature, the water uptake properties of AS coated with 1,2,6-hexanetriol are largely dictated by the phase of the AS. Thus, the total water uptake depends on the RH history of the particle and the resulting phase of AS.

Depositional ice nucleation on monocarboxylic acids: effect of the O:C ratio.

The heterogeneous ice nucleation efficiency of a series of thin C3-C6 monocarboxylic acid films between 180 and 200 K has been investigated using a Knudsen cell flow reactor. At each temperature, the critical ice saturation ratio for depositional nucleation as well as the effective contact angle was found to be strongly dependent on the chemical nature of the film. For the organic acids used in this study, increasing the O:C ratio lowered the supersaturation required for the onset of heterogeneous ice nucleation and decreased the effective angle of contact. This could be the result of an increase in surface hydrophilicity, which allows the film to better adsorb a metastable, icelike layer of water that serves as a template for the new phase of ice. These ice nucleation results are in excellent agreement with ice nucleation on laboratory generated α-pinene secondary organic aerosol as well as on predominantly organic particles collected in Mexico City.

Nitrogen incorporation in CH(4)-N(2) photochemical aerosol produced by far ultraviolet irradiation.

Nitrile incorporation into Titan aerosol accompanying hydrocarbon chemistry is thought to be driven by extreme UV wavelengths (λ<120 nm) or magnetospheric electrons in the outer reaches of the atmosphere. Far UV radiation (120-200 nm), which is transmitted down to the stratosphere of Titan, is expected to affect hydrocarbon chemistry only and not initiate the formation of nitrogenated species. We examined the chemical properties of photochemical aerosol produced at far UV wavelengths, using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), which allows for elemental analysis of particle-phase products. Our results show that aerosol formed from CH(4)/N(2) photochemistry contains a surprising amount of nitrogen, up to 16% by mass, a result of photolysis in the far UV. The proportion of nitrogenated organics to hydrocarbon species is shown to be correlated with that of N(2) in the irradiated gas. The aerosol mass greatly decreases when N(2) is removed, which indicates that N(2) plays a major role in aerosol production. Because direct dissociation of N(2) is highly improbable given the immeasurably low cross section at the wavelengths studied, the chemical activation of N(2) must occur via another pathway. Any chemical activation of N(2) at wavelengths >120 nm is presently unaccounted for in atmospheric photochemical models. We suggest that reaction with CH radicals produced from CH(4) photolysis may provide a mechanism for incorporating N into the molecular structure of the aerosol. Further work is needed to understand the chemistry involved, as these processes may have significant implications for how we view prebiotic chemistry on early Earth and similar planets.

Optical properties of the products of α-dicarbonyl and amine reactions in simulated cloud droplets.

Secondary organic aerosol makes up a significant fraction of the total aerosol mass, and a growing body of evidence indicates that reactions in the atmospheric aqueous phase are important contributors to aerosol formation and can help explain observations that cannot be accounted for using traditional gas-phase chemistry. In particular, aqueous phase reactions between small organic molecules have been proposed as a source of light absorbing compounds that have been observed in numerous locations. Past work has established that reactions between α-dicarbonyls and amines in evaporating water droplets produces particle-phase products that are brown in color. In the present study, the complex refractive indices of model secondary organic aerosol formed by aqueous phase reactions between the α-dicarbonyls glyoxal and methylglyoxal and the primary amines glycine and methylamine have been determined. The reaction products exhibit significant absorption in the visible, and refractive indices are similar to those for light absorbing species isolated from urban aerosol. However, the optical properties are different from the values used in models for secondary organic aerosol, which typically assume little to no absorption of visible light. As a result, the climatic cooling effect of such aerosols in models may be overestimated.

Potential climatic impact of organic haze on early Earth.

We have explored the direct and indirect radiative effects on climate of organic particles likely to have been present on early Earth by measuring their hygroscopicity and cloud nucleating ability. The early Earth analog aerosol particles were generated via ultraviolet photolysis of an early Earth analog gas mixture, which was designed to mimic possible atmospheric conditions before the rise of oxygen. An analog aerosol for the present-day atmosphere of Saturn's moon Titan was tested for comparison. We exposed the early Earth aerosol to a range of relative humidities (RHs). Water uptake onto the aerosol was observed to occur over the entire RH range tested (RH=80-87%). To translate our measurements of hygroscopicity over a specific range of RHs into their water uptake ability at any RH < 100% and into their ability to act as cloud condensation nuclei (CCN) at RH > 100%, we relied on the hygroscopicity parameter κ, developed by Petters and Kreidenweis. We retrieved κ=0.22 ±0.12 for the early Earth aerosol, which indicates that the humidified aerosol (RH < 100 %) could have contributed to a larger antigreenhouse effect on the early Earth atmosphere than previously modeled with dry aerosol. Such effects would have been of significance in regions where the humidity was larger than 50%, because such high humidities are needed for significant amounts of water to be on the aerosol. Additionally, Earth organic aerosol particles could have activated into CCN at reasonable-and even low-water-vapor supersaturations (RH > 100%). In regions where the haze was dominant, it is expected that low particle concentrations, once activated into cloud droplets, would have created short-lived, optically thin clouds. Such clouds, if predominant on early Earth, would have had a lower albedo than clouds today, thereby warming the planet relative to current-day clouds.

Formation of nitrogen-containing oligomers by methylglyoxal and amines in simulated evaporating cloud droplets.

Reactions of methylglyoxal with amino acids, methylamine, and ammonium sulfate can take place in aqueous aerosol and evaporating cloud droplets. These processes are simulated by drying droplets and bulk solutions of these compounds (at low millimolar and 1 M concentrations, respectively) and analyzing the residuals by scanning mobility particle sizing, nuclear magnetic resonance, aerosol mass spectrometry (AMS), and electrospray ionization MS. The results are consistent with imine (but not diimine) formation on a time scale of seconds, followed by the formation of nitrogen-containing oligomers, methylimidazole, and dimethylimidazole products on a time scale of minutes to hours. Measured elemental ratios are consistent with imidazoles and oligomers being major reaction products, while effective aerosol densities suggest extensive reactions take place within minutes. These reactions may be a source of the light-absorbing, nitrogen-containing oligomers observed in urban and biomass-burning aerosol particles.