Feasibility of Photosensitized Reactions with Secondary Organic Aerosol Particles in the Presence of Volatile Organic Compounds

The ability of a complex mixture of organic compounds found in secondary organic aerosol (SOA) to act as a photosensitizer in the oxidation of volatile organic compounds (VOCs) was investigated. Different types of SOAs were produced in a smog chamber by oxidation of various biogenic and anthropogenic VOCs. The SOA particles were collected from the chamber onto an inert substrate, and the resulting material was exposed to 365 nm radiation in an air flow containing ∼200 ppbv of limonene vapor. The mixing ratio of limonene and other VOCs in the flow was observed with a proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS). The photosensitized uptake of limonene was observed for several SOA materials, with a lower limit for the reactive uptake coefficient on the scale of ∼10^–5. The lower limit for the uptake coefficient under conditions of Los Angeles, California on the summer solstice at noon was estimated to be on the order of ∼10^–6. Photoproduction of oxygenated VOCs (OVOCs) resulting from photodegradation of the SOA material also occurred in parallel with the photosensitized uptake of limonene. The estimated photosensitized limonene uptake rates by atmospheric SOA particles and vegetation surfaces appear to be too small to compete with the atmospheric oxidation of limonene by the hydroxyl radical or ozone. However, these processes could play a role in the leaf boundary layer where concentrations of oxidants are depleted and concentrations of VOCs are enhanced relative to the free atmosphere

Photodegradation of Secondary Organic Aerosol Particles as a Source of Small, Oxygenated Volatile Organic Compounds

We investigated the photodegradation of secondary organic aerosol (SOA) particles by near-UV radiation and photoproduction of oxygenated volatile organic compounds (OVOCs) from various types of SOA. We used a smog chamber to generate SOA from α-pinene, guaiacol, isoprene, tetradecane, and 1,3,5-trimethylbenzene under high-NO_<i>x</i>, low-NO_<i>x</i>, or ozone oxidation conditions. The SOA particles were collected on a substrate, and the resulting material was exposed to several mW of near-UV radiation (λ ∼ 300 nm) from a light-emitting diode. Various OVOCs, including acetic acid, formic acid, acetaldehyde, and acetone were observed during photodegradation, and their SOA-mass-normalized fluxes were estimated with a Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-ToF-MS). All the SOA, with the exception of guaiacol SOA, emitted OVOCs upon irradiation. Based on the measured OVOC emission rates, we estimate that SOA particles would lose at least ∼1% of their mass over a 24 h period during summertime conditions in Los Angeles, California. This condensed-phase photochemical process may produce a few Tg/year of gaseous formic acid, the amount comparable to its primary sources. The condensed-phase SOA photodegradation processes could therefore measurably affect the budgets of both particulate and gaseous atmospheric organic compounds on a global scale

Highly Acidic Conditions Drastically Alter the Chemical Composition and Absorption Coefficient of α‑Pinene Secondary Organic Aerosol

Secondary organic aerosols (SOA), formed through the gas-phase oxidation of volatile organic compounds (VOCs), can reside in the atmosphere for many days. The formation of SOA takes place rapidly within hours after VOC emissions, but SOA can undergo much slower physical and chemical processes throughout their lifetime in the atmosphere. The acidity of atmospheric aerosols spans a wide range, with the most acidic particles having negative pH values, which can promote acid-catalyzed reactions. The goal of this work is to elucidate poorly understood mechanisms and rates of acid-catalyzed aging of mixtures of representative SOA compounds. SOA were generated by the ozonolysis of α-pinene in a continuous flow reactor and then collected using a foil substrate. SOA samples were extracted and aged by exposure to varying concentrations of aqueous H2SO4 for 1–2 days. Chemical analysis of fresh and aged samples was conducted using ultra-performance liquid chromatography coupled with photodiode array spectrophotomety and high-resolution mass spectrometry. In addition, UV–vis spectrophotometry and fluorescence spectrophotometry were used to examine the changes in optical properties before and after aging. We observed that SOA that aged in moderately acidic conditions (pH from 0 to 4) experienced small changes in composition, while SOA that aged in a highly acidic environment (pH from −1 to 0) experienced more dramatic changes in composition, including the formation of compounds containing sulfur. Additionally, at highly acidic conditions, light-absorbing and fluorescent compounds appeared, but their identities could not be ascertained due to their small relative abundance. This study shows that acidity is a major driver of SOA aging, resulting in a large change in the chemical composition and optical properties of aerosols in regions where high concentrations of H2SO4 persist, such as upper troposphere and lower stratosphere

Photodegradation of Secondary Organic Aerosol Material Quantified with a Quartz Crystal Microbalance

We used a quartz crystal microbalance (QCM) to quantify the mass loss resulting from exposure of secondary organic aerosol (SOA) particles deposited on the QCM crystal to 254, 305, and 365 nm radiation. We coupled the QCM setup to a proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS) to chemically resolve the photoproduced volatile organic compounds (VOCs) responsible for the mass loss. The photoproduced VOCs detected by the PTR-ToF-MS accounted for ∼50% of the mass loss rates measured with the QCM. Weakly absorbing SOA produced by ozonolysis of α-pinene or d-limonene exhibited a much larger mass loss rate in both the QCM and the PTR-ToF-MS data compared to that of strongly absorbing SOA produced by photooxidation of guaiacol. We predict that the fractional mass loss rate of α-pinene ozonolysis SOA should be as high as ∼1%/h on the summer solstice in Los Angeles in the lower troposphere and ∼4%/h in the stratosphere. The mass loss rates for SOA particles crossing a typical 254 nm oxidation flow reactor, which is routinely used for rapid aging of organic aerosol particles, are expected to be negligible because of the short residence time inside the reactor

High-Resolution Mass Spectrometry and Molecular Characterization of Aqueous Photochemistry Products of Common Types of Secondary Organic Aerosols

This work presents a systematic investigation of the molecular level composition and the extent of aqueous photochemical processing in different types of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors including α-pinene, β-pinene, β-myrcene, d-limonene, α-humulene, 1,3,5-trimethylbenzene, and guaiacol, oxidized by ozone (to simulate a remote atmosphere) or by OH in the presence of NO_<i>x</i> (to simulate an urban atmosphere). Chamber- and flow-tube-generated SOA samples were collected, extracted in a methanol/water solution, and photolyzed for 1 h under identical irradiation conditions. In these experiments, the irradiation was equivalent to about 3–8 h of exposure to the sun in its zenith. The molecular level composition of the dissolved SOA was probed before and after photolysis with direct-infusion electrospray ionization high-resolution mass spectrometry (ESI-HR-MS). The mass spectra of unphotolyzed SOA generated by ozone oxidation of monoterpenes showed qualitatively similar features and contained largely overlapping subsets of identified compounds. The mass spectra of OH/NO_<i>x</i>-generated SOA had more unique visual appearance and indicated a lower extent of product overlap. Furthermore, the fraction of nitrogen-containing species (organonitrates and nitroaromatics) was highly sensitive to the SOA precursor. These observations suggest that attribution of high-resolution mass spectra in field SOA samples to specific SOA precursors should be more straightforward under OH/NO_<i>x</i> oxidation conditions compared to the ozone-driven oxidation. Comparison of the SOA constituents before and after photolysis showed the tendency to reduce the average number of atoms in the SOA compounds without a significant effect on the overall O/C and H/C ratios. SOA prepared by OH/NO_<i>x</i> photooxidation of 1,3,5-trimethylbenzene and guaiacol were more resilient to photolysis despite being the most light-absorbing. The composition of SOA prepared by ozonolysis of monoterpenes changed more significantly as a result of the photolysis. The results indicate that aqueous photolysis of dissolved SOA compounds in cloud/fog water can occur in various types of SOA, and on atmospherically relevant time scales. However, the extent of the photolysis-driven change in molecular composition depends on the specific type of SOA

Formation of Chromophores from <i>cis</i>-Pinonaldehyde Aged in Highly Acidic Conditions

Sulfuric acid in the atmosphere can participate in acid-catalyzed and acid-driven reactions, including those within secondary organic aerosols (SOA). Previous studies have observed enhanced absorption at visible wavelengths and significant changes in the chemical composition when SOA was exposed to sulfuric acid. However, the specific chromophores responsible for these changes could not be identified. The goals of this study are to identify the chromophores and determine the mechanism of browning in highly acidified α-pinene SOA by following the behavior of specific common α-pinene oxidation products, namely, cis-pinonic acid and cis-pinonaldehyde, when they are exposed to highly acidic conditions. The products of these reactions were analyzed with ultra-performance liquid chromatography coupled with photodiode array spectrophotometry and high-resolution mass spectrometry, UV–vis spectrophotometry, and nuclear magnetic resonance spectroscopy. cis-Pinonic acid (2) was found to form homoterpenyl methyl ketone (4), which does not absorb visible radiation, while cis-pinonaldehyde (3) formed weakly absorbing 1-(4-(propan-2-ylidene)cyclopent-1-en-1-yl)ethan-1-one (5) and 1-(4-isopropylcyclopenta-1,3-dien-1-yl)ethan-1-one (6) via an acid-catalyzed aldol condensation. This chemistry could be relevant for environments characterized by high sulfuric acid concentrations, for example, during the transport of organic compounds from the lower to the upper atmosphere by fast updrafts

Excitation–Emission Spectra and Fluorescence Quantum Yields for Fresh and Aged Biogenic Secondary Organic Aerosols

Certain biogenic secondary organic aerosols (SOA) become absorbent and fluorescent when exposed to reduced nitrogen compounds such as ammonia, amines, and their salts. Fluorescent SOA may potentially be mistaken for biological particles by detection methods relying on fluorescence. This work quantifies the spectral distribution and effective quantum yields of fluorescence of water-soluble SOA generated from two monoterpenes, limonene and α-pinene, and two different oxidants, ozone (O₃) and hydroxyl radical (OH). The SOA was generated in a smog chamber, collected on substrates, and aged by exposure to ∼100 ppb ammonia in air saturated with water vapor. Absorption and excitation–emission matrix (EEM) spectra of aqueous extracts of aged and control SOA samples were measured, and the effective absorption coefficients and fluorescence quantum yields (∼0.005 for 349 nm excitation) were determined from the data. The strongest fluorescence for the limonene-derived SOA was observed for λ_excitation = 420 ± 50 nm and λ_emission = 475 ± 38 nm. The window of the strongest fluorescence shifted to λ_excitation = 320 ± 25 nm and λ_emission = 425 ± 38 nm for the α-pinene-derived SOA. Both regions overlap with the EEM spectra of some of the fluorophores found in primary biological aerosols. Despite the low quantum yield, the aged SOA particles may have sufficient fluorescence intensities to interfere with the fluorescence detection of common bioaerosols

A Real-Time Fast-Flow Tube Study of VOC and Particulate Emissions from Electronic, Potentially Reduced-Harm, Conventional, and Reference Cigarettes

<div><p>Tobacco-free electronic cigarettes (e-cigarettes), which are currently not regulated by the FDA, have become widespread as a “safe” form of smoking. One approach to evaluate the potential toxicity of e-cigarettes and other types of potentially “reduced-harm” cigarettes is to compare their emissions of volatile organic compounds (VOCs), including reactive organic electrophilic compounds such as acrolein, and particulate matter to those of conventional and reference cigarettes. Our newly designed fast-flow tube system enabled us to analyze VOC composition and particle number concentration in real-time by promptly diluting puffs of mainstream smoke obtained from different brands of combustion cigarettes and e-cigarettes. A proton transfer reaction time-of-flight mass spectrometer (PTRMS) was used to analyze real-time cigarette VOC emissions with a 1-s time resolution. Particles were detected with a condensation particle counter (CPC). This technique offers real-time analysis of VOCs and particles in each puff without sample aging and does not require any sample pretreatment or extra handling. Several important determining factors in VOC and particle concentration were investigated: (1) puff frequency; (2) puff number; (3) tar content; (4) filter type. Results indicate that electronic cigarettes are not free from acrolein and acetaldehyde emissions and produce comparable particle number concentrations to those of combustion cigarettes, more specifically to the 1R5F reference cigarette. Unlike conventional cigarettes, which emit different amounts of particles and VOCs each puff, there was no significant puff dependence in the e-cigarette emissions. Charcoal filter cigarettes did not fully prevent the emission of acrolein and other VOCs.</p><p>Copyright 2015 American Association for Aerosol Research</p></div

Applications of High-Resolution Electrospray Ionization Mass Spectrometry to Measurements of Average Oxygen to Carbon Ratios in Secondary Organic Aerosols

The applicability of high-resolution electrospray ionization mass spectrometry (HR ESI-MS) to measurements of the average oxygen to carbon ratio (O/C) in secondary organic aerosols (SOAs) was investigated. Solutions with known average O/C containing up to 10 standard compounds representative of low-molecular-weight SOA constituents were analyzed and the corresponding electrospray ionization efficiencies were quantified. The assumption of equal ionization efficiency commonly used in estimating O/C ratios of SOAs was found to be reasonably accurate. We found that the accuracy of the measured O/C ratios increases by averaging the values obtained from both the posive and negative modes. A correlation was found between the ratio of the ionization efficiencies in the positive (+) and negative (−) ESI modes and the octanol–water partition constant and, more importantly, the compound’s O/C. To demonstrate the utility of this correlation for estimating average O/C values of unknown mixtures, we analyzed the ESI (+) and ESI (−) data for SOAs produced by oxidation of limonene and isoprene and compared them online to O/C measurements using an aerosol mass spectrometer (AMS). This work demonstrates that the accuracy of the HR ESI-MS method is comparable to that of the AMS with the added benefit of molecular identification of the aerosol constituents

Effect of Alkyl Chain Length on Hygroscopicity of Nanoparticles and Thin Films of Imidazolium-Based Ionic Liquids

This work focuses on the interaction of water vapor with ionic liquids (ILs) consisting of [C_<i>n</i>MIM]⁺ (<i>n</i> = 2, 4, or 6) cations paired with Cl^– or BF₄^– anions to examine the effect of alkyl chain length on IL hygroscopicity. Tandem nanodifferential mobility analysis (TDMA) and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy were used to study IL nanoparticles and thin films. Studying IL nanoparticles overcomes kinetic limitations potentially present in bulk experiments as true IL–water vapor equilibrium is quickly established. Growth curves recorded in TDMA experiments showed steady uptake of water vapor with increasing RH. ILs containing Cl^– absorbed more water than those containing BF₄^– over the entire RH range, and IL hygroscopicity decreased with increasing alkyl chain length. The intensities of water stretching vibrations in IL thin films exposed to water vapor measured with ATR-FTIR were in qualitative agreement with the TDMA measurements. Water molar fractions for IL nanoparticles were calculated, and the performance of several water activity coefficient models were evaluated by fits to the experimental data. These combined experimental and modeling techniques help provide a more complete picture for these two families of ILs in the presence of water