We investigated the photosensitizing properties of secondary organic aerosol (SOA) formed during the hydroxyl radical (OH) initiated oxidation of naphthalene. This SOA was injected into an aerosol flow tube and exposed to UV radiation and gaseous volatile organic compounds or sulfur dioxide (SO2). The aerosol particles were observed to grow in size by photosensitized uptake of d‐limonene and β‐pinene. In the presence of SO2, a photosensitized production (0.2–0.3 µg m−3 h−1) of sulfate was observed at all relative humidity (RH) levels. Some sulfate also formed on particles in the dark, probably due to the presence of organic peroxides. The dark and photochemical pathways exhibited different trends with RH, unraveling different contributions from bulk and surface chemistry. As naphthalene and other polycyclic aromatics are important SOA precursors in the urban and suburban areas, these dark and photosensitized reactions are likely to play an important role in sulfate and SOA formation.
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Previous studies have suggested that the photochemistry of nitroaromatics in organic solvents can vary significantly from the photochemistry in aqueous solutions. This work compares the photodegradation of 2-nitrophenol (2NP), 4-nitrophenol (4NP), 2,4-dinitrophenol (24DNP), and 2,4,6-trinitrophenol (246TNP) in 2-propanol and water to better understand the photochemical loss of nitrophenols in atmospheric organic particles and aqueous droplets. Polychromatic quantum yields were determined by monitoring the loss of absorbance of each nitrophenol with UV/vis spectroscopy in the presence of an acid (undissociated nitrophenol) or base (nitrophenolate). There was no orderly variation between loss rates in the organic and aqueous phases: 2NP and 4NP had similar yields in the two solvents. 246TNP was an outlier in these results as it dissociated in both acidified 2-propanol and water due to its exceptionally strong acidity. A notable result is that only for 24DNP was a dramatically increased reactivity found in 2-propanol compared to that in water. Time-dependent density functional theory calculations were carried out to characterize the excited state energies and absorption spectra with a conductor-like polarizable continuum model or explicit solvation by a few solvent molecules. Explicit solvent calculations suggest the enhanced reactivity of 24DNP in 2-propanol is due to the strong interaction between a 2-propanol molecule and an –NO 2 group in the excited state. For the other nitrophenols, the solvent effects on electronic structure were minimal. Overall, the observations in this work suggest that solvent effects on the electronic structure and condensed-phase photochemistry of nitrophenols are minimal, with the exception of 24DNP.more » « less
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Biomass burning organic aerosol (BBOA) is one of the largest sources of organics in the atmosphere. Mineral dust and biomass burning smoke frequently co-exist in the same atmospheric environment. Common biomass burning compounds, such as dihydroxybenzenes and their derivatives, are known to produce light-absorbing, water-insoluble polymeric particles upon reaction with soluble Fe( iii ) under conditions characteristic of aerosol liquid water. However, such reactions have not been tested in realistic mixtures of BBOA compounds. In this study, model organic aerosol (OA), meant to replicate BBOA from smoldering fires, was generated through the pyrolysis of Canary Island pine needles in a tube furnace at 300, 400, 500, 600, 700, and 800 °C in nitrogen gas, and the water-soluble fractions were reacted with iron chloride under dark, acidic conditions. We utilized spectrophotometry to monitor the reaction progress. For OA samples produced at lower temperatures (300 and 400 °C), particles (P300 and P400) formed in solution, were syringe filtered, and extracted in organic solvents. Analysis was conducted with ultrahigh pressure liquid chromatography coupled to a photodiode array spectrophotometer and a high-resolution mass spectrometer (UHPLC-PDA-HRMS). For OA samples formed at higher pyrolysis temperatures (500–800 °C), water-insoluble, black particles (P500–800) formed in solution. In contrast to P300 and P400, P500–800 were not soluble in common solvents. Scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS) and transmission electron microscopy (TEM) were used to image P600 and determine bulk elemental composition. Electron microscopy revealed that P600 had fractal morphology, reminiscent of soot particles, and contained no detectable iron. These results suggest that light-absorbing aerosol particles can be produced from Fe( iii )-catalyzed reactions in aging BBOA plumes produced from smoldering combustion in the absence of any photochemistry. This result has important implications for understanding the direct and indirect effects of aged BBOA on climate.more » « less
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Secondary organic aerosol (SOA) plays a critical, yet uncertain, role in air quality and climate. Once formed, SOA is transported throughout the atmosphere and is exposed to solar UV light. Information on the viscosity of SOA, and how it may change with solar UV exposure, is needed to accurately predict air quality and climate. However, the effect of solar UV radiation on the viscosity of SOA and the associated implications for air quality and climate predictions is largely unknown. Here, we report the viscosity of SOA after exposure to UV radiation, equivalent to a UV exposure of 6 to 14 d at midlatitudes in summer. Surprisingly, UV-aging led to as much as five orders of magnitude increase in viscosity compared to unirradiated SOA. This increase in viscosity can be rationalized in part by an increase in molecular mass and oxidation of organic molecules constituting the SOA material, as determined by high-resolution mass spectrometry. We demonstrate that UV-aging can lead to an increased abundance of aerosols in the atmosphere in a glassy solid state. Therefore, UV-aging could represent an unrecognized source of nuclei for ice clouds in the atmosphere, with important implications for Earth’s energy budget. We also show that UV-aging increases the mixing times within SOA particles by up to five orders of magnitude throughout the troposphere with important implications for predicting the growth, evaporation, and size distribution of SOA, and hence, air pollution and climate.more » « less
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Abstract. Secondary organic aerosol (SOA) constitutes a largefraction of atmospheric aerosol. To assess its impacts on climate and airpollution, knowledge of the number of phases in internal mixtures ofdifferent SOA types is required. Atmospheric models often assume thatdifferent SOA types form a single phase when mixed. Here, we present visualobservations of the number of phases formed after mixing differentanthropogenic and biogenic SOA types. Mixing SOA types generated inenvironmental chambers with oxygen-to-carbon (O/C) ratios between 0.34 and 1.05, we found 6 out of 15 mixtures of two SOA types to result in two phase particles. We demonstrate that the number of phases depends on thedifference in the average O/C ratio between the two SOA types (Δ(O/C)). Using a threshold Δ(O/C) of 0.47, we can predict the phasebehavior of over 90 % of our mixtures, with one- and two-phase particlespredicted for Δ(O/C)<0.47 and Δ(O/C)≥0.47,respectively. This threshold ΔO/C value provides a simple parameterto predict whether mixtures of fresh and aged SOA form one- or two-phase particles in the atmosphere. In addition, we show that phase-separated SOAparticles form when mixtures of volatile organic compounds emitted from realtrees are oxidized.more » « less
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Abstract. Secondary organic aerosol (SOA) generated from the photooxidationof aromatic compounds in the presence of oxides of nitrogen (NOx) isknown to efficiently absorb ultraviolet and visible radiation. With exposureto sunlight, the photodegradation of chromophoric compounds in the SOAcauses this type of SOA to slowly photobleach. These photodegradationreactions may occur in cloud droplets, which are characterized by lowconcentrations of solutes, or in aerosol particles, which can have highlyviscous organic phases and aqueous phases with high concentrations ofinorganic salts. To investigate the effects of the surrounding matrix on therates and mechanisms of photodegradation of SOA compounds, SOA was preparedin a smog chamber by photooxidation of toluene in the presence of NOx.The collected SOA was photolyzed for up to 24 h using near-UV radiation(300–400 nm) from a xenon arc lamp under different conditions: directly onthe filter, dissolved in pure water, and dissolved in 1 M ammonium sulfate.The SOA mass absorption coefficient was measured as a function ofirradiation time to determine photobleaching rates. Electrospray ionizationhigh-resolution mass spectrometry coupled to liquid chromatographyseparation was used to observe changes in SOA composition resulting from theirradiation. The rate of decrease in SOA mass absorption coefficient due tophotobleaching was the fastest in water, with the presence of 1 M ammoniumsulfate modestly slowing down the photobleaching. By contrast,photobleaching directly on the filter was slower. The high-resolutionmass spectrometry analysis revealed an efficient photodegradation ofnitrophenol compounds on the filter but not in the aqueous phases, withrelatively little change observed in the composition of the SOA irradiatedin water or 1 M ammonium sulfate despite faster photobleaching than in theon-filter samples. This suggests that photodegradation of nitrophenolscontributes much more significantly to photobleaching in the organic phasethan in the aqueous phase. We conclude that the SOA absorption coefficientlifetime with respect to photobleaching and lifetimes of individualchromophores in SOA with respect to photodegradation will depend strongly onthe sample matrix in which SOA compounds are exposed to sunlight.more » « less
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Abstract. The viscosity of secondary organic aerosol (SOA) is needed to improve predictions of air quality, climate, and atmospheric chemistry. Many techniques have been developed to measure the viscosity of micrometer-sized materials at room temperature; however, few techniques are able to measure viscosity as a function of temperature for these small sample sizes. SOA in the troposphere experience a wide range of temperatures, so measurement of viscosity as a function of temperature is needed. To address this need, a new method was developed based on hot-stage microscopy combined with fluid dynamics simulations. The current method can be used to determine viscosities in the range of roughly 104 to 108 Pa s at temperatures greater than room temperature. Higher viscosities may be measured if experiments are carried out over multiple days. To validate our technique, the viscosities of 1,3,5-tris(1-naphthyl)benzene and phenolphthalein dimethyl ether were measured and compared with values reported in the literature. Good agreement was found between our measurements and literature data. As an application to SOA, the viscosity as a function of temperature for lab-generated farnesene SOA material was measured, giving values ranging from 3.1×106 Pa s at 51 ∘C to 2.6×104 Pa s at 67 ∘C. We fit the temperature-dependent data to the Vogel–Fulcher–Tammann (VFT) equation and obtained a fragility parameter for the material of 7.29±0.03, whichis very similar to the fragility parameter of 7 reported for α-pinene SOA by Petters and Kasparoglu (2020). These results demonstrate that the viscosity as a function of temperature can be measured for lab-generated SOA material using our hot-stage microscopy method.more » « less