Secondary Organic Aerosol Yield Research Articles

Enhanced organic aerosol formation induced by inorganic aerosol formed in laboratory photochemical experiments

Atmospheric inorganic gases such as NOx, SO2, and NH3 have diverse effects on the formation of secondary organic aerosol (SOA). A comprehensive investigation is necessary to fully understand the atmospheric processing of SOA. In this study, we examined the photooxidation of xylene isomers in the presence of inorganic gases using a combined facility comprising a smog chamber (SC) and an oxidation flow reactor (OFR). SC experiments at higher xylene concentrations and humid conditions revealed SOA yields of 37%, 39%, and 39% with NH3, compared to 15%, 11%, and 13% without NH3, for o-, m-, and p-xylene, respectively. This increase was primarily attributed to the enhanced formation of secondary inorganic aerosol (SIA) in the presence of NH3, consequently increasing aerosol surface area and aerosol water content (AWC). Vapor wall losses (VWL), estimated using a kinetic method, were substantial even with the elevated aerosol surface area provided by SIA. Additional photochemical reactions in the OFR showed a gradual increase in SOA mass and yield over an atmospheric equivalent aging time of 0.5–4.0 days. In the OFR, the SOA yield increased significantly when negligible xylene remained after SC reactions. Fresh SOA formation in the OFR might have decreased the oxygen-to-carbon ratio and oxidation state of carbon, which gradually increased with increasing OFR aging. High OH radical exposure in the OFR likely caused the photodegradation of SC-formed ON, as evidenced by an abrupt decrease in the NO+/NO2+ ratio measured. This study indicates that SOA formation potential of the aromatic hydrocarbon is highly underestimated without considering the combined effects of inorganic gases along with aging.

Interaction between marine and terrestrial biogenic volatile organic compounds: Non-linear effect on secondary organic aerosol formation

Biogenic volatile organic compounds (BVOCs) are the largest source of secondary organic aerosols (SOA) globally. However, the complex interactions between marine and terrestrial BVOCs remain unclear, inhibiting our in-depth understanding of the SOA formation in the coastal areas and its environmental impacts. Here, we performed smog chamber experiments with mixed α-pinene (a typical monoterpene) and dimethyl sulfide (DMS, a typical marine emission BVOC) to investigate their possible interactions and subsequent SOA formation. It is found that DMS has a non-linear effect on SOA generation: The mass concentration and yield of SOA show increasing and then decreasing trends with the increase of the initial concentration of DMS. The increasing trend can be attributed to OH regeneration from isomerization of the CH3SCH2OO radical together with acid-catalyzed heterogeneous reactions by the oxidation of DMS, while the decreasing trend is explained by the less contribution of isomerization reaction and the high OH reactivity that inhibits the formation of low volatility products. The results from infrared spectra and mass spectra together reveal the contribution of sulfur-containing molecules in the mixed system. Moreover, the mass spectra results indicate that acidic products generated by DMS photooxidation enhance the O:C ratio, while organosulfates are produced to contribute to the formation of mixed SOA. In addition, the trends in relative abundance of highly oxygenated organic molecules (HOMs) with C8 - C10 multiple functional groups in different mixed systems agree well with the turning point of the SOA yield. The findings of this study have significant implications for understanding binary or more complex systems in the atmosphere in the coastal areas.

Secondary Organic Aerosol Formation during the Oxidation of Large Aromatic and Other Cyclic Anthropogenic Volatile Organic Compounds.

The secondary organic aerosol (SOA) production from the reactions of anthropogenic large volatile (VOCs) and intermediate volatility organic compounds (IVOCs) with hydroxyl radicals under high NO x conditions was investigated. The organic compounds studied include cyclic alkanes of increasing size (amylcyclohexane, hexylcyclohexane, nonylcyclohexane, and decylcyclohexane) and aromatic compounds (1,3,5-trimethylbenzene, 1,3,5-triethylbenzene and 1,3,5-tritert-butylbenzene). A considerable amount of SOA was formed from all examined compounds. For the studied cyclohexanes (C11-C16) there appears that the SOA yield depends nonlinearly on the length of their substitute chain. The large cyclohexanes had higher yields than the aromatic compounds, but the aromatic precursors produced a more oxidized SOA. This was due to the production of lower volatility and O:C first generation products by the cyclohexanes. Most oxidation products (with C* < 104 μg m-3) in the case of cyclohexanes are SVOCs (∼50%), while of aromatics are IVOCs (∼60%). Structure, molecular size, and length of the substitute chain of the parent hydrocarbon were found to play key roles in SOA formation, oxidation state, and volatility. The SOA volatility distribution, effective vaporization enthalpy, and effective accommodation coefficient were also quantified by combining SOA yields, thermodenuder (TD) and isothermal dilution measurements. Parameterizations for the Volatility Basis Set (VBS) are proposed for future use in chemical transport models.

Molecular interaction between ammonium sulfate and secondary organic aerosol from styrene

Secondary organic aerosol (SOA) and inorganic aerosol (SIA) are two major constituents of PM2.5, which are well-studied separately. However, the molecular-level investigation of mechanical interactions between them is still limited, which will affect the understanding of toxicity and optical properties of PM2.5. Styrene contains a benzene ring and a highly reactive double bond, mainly contributing to urban SOA formation. Here, chamber experiments were conducted to explore the effects of the (NH4)2SO4 seeds, as an example of SIA, on styrene SOA formation under varying relative humidity (RH) conditions. The particle-phase products were determined based on a high-resolution orbitrap mass spectrometer. The results showed that in the styrene-H2O2-hv systems, (NH4)2SO4 seeds facilitated the gas-particle partitioning of SOA precursors, leading to slightly higher SOA yields than the unseeded systems at 8.5 % RH. While RH exceeded 44.3 %, the presence of (NH4)2SO4 seeds increased the particle liquid water content, thus enhancing the partitioning of hydrophilic H2O2 to particle phase and the further oxidation of SOA, finally decreasing SOA yields. In the styrene-NOx-hv systems, NH4+ and SO42− were involved in the particle-phase reactions, producing prominent nitrogen- and sulfur-containing compounds of C8H7O2N and C8H9O6NS. In the styrene-O3 dark reaction systems, the existence of (NH4)2SO4 seeds significantly changed the oligomer components under humid conditions. The particle-phase formation pathways of oligomers affected by (NH4)2SO4 seeds were also illustrated based on tandem mass spectra data. This study emphasizes the importance of inorganic seed effects on particle-phase reactions and improves our understanding of the SOA formation pathways in the ambient atmosphere.

A comprehensive evaluation of enhanced temperature influence on gas and aerosol chemistry in the lamp-enclosed oxidation flow reactor (OFR) system

Abstract. Oxidation flow reactors (OFRs) have been extensively utilized to examine the formation of secondary organic aerosol (SOA). However, the UV lamps typically employed to initiate the photochemistry in OFRs can result in an elevated reactor temperature when their implications are not thoroughly evaluated. In this study, we conducted a comprehensive investigation into the temperature distribution within an Aerodyne potential aerosol mass OFR (PAM-OFR) and then examined the subsequent effects on flow and chemistry due to lamp heating. A lamp-induced temperature increase was observed, which was a function of lamp-driving voltage, number of lamps, lamp types, OFR residence time, and positions within the PAM-OFR. Under typical PAM-OFR operational conditions (e.g., &lt; 5 d of equivalent atmospheric OH exposure under low-NOx conditions), the temperature increase typically ranged from 1–5 °C. Under extreme (but less frequently encountered) conditions, the heating could reach up to 15 °C. The influences of the increased temperature over ambient conditions on the flow distribution, gas, and condensed-phase chemistry within PAM-OFR were evaluated. Our findings indicate that the increase in temperature altered the flow field, resulting in a diminished tail on the residence time distribution and corresponding oxidant exposure due to faster recirculation. According to simulation results from a radical chemistry box model, the variation in absolute oxidant concentration within PAM-OFR due to temperature increase was minimal (&lt; 5 %). The temperature influences on seed organic aerosol (OA) and newly formed secondary OA were also investigated, suggesting that an increase in temperature can impact the yield, size, and oxidation levels of representative biogenic and anthropogenic SOA types. Recommendations for temperature-dependent SOA yield corrections and PAM-OFR operating protocols that mitigate lamp-induced temperature enhancement and fluctuations are presented. We recommend blowing air around the reactor's exterior with fans during PAM-OFR experiments to minimize the temperature increase within PAM-OFR. Temperature increases are substantially lower for OFRs utilizing less powerful lamps compared to the Aerodyne version.

Simulation of Regional Secondary Organic Aerosol Formation From Monocyclic Aromatic Hydrocarbons Using a Near‐Explicit Chemical Mechanism Constrained by Chamber Experiments

AbstractThe formation of secondary organic aerosol (SOA) is inextricably linked to the photo‐oxidation of aromatic hydrocarbons. However, models still exhibit biases in representing SOA mass and chemical composition. We implemented a box model coupled with a near‐explicit photochemical mechanism, the Master Chemical Mechanism (MCMv3.3.1), to simulate a series of chamber studies and assess model biases in simulating SOA from representative monocyclic aromatic hydrocarbons, that is, toluene and three xylene isomers (TX SOA). The box model underpredicted SOA yields of toluene and xylenes by 4.7%–100%, which could be improved by adjusting the saturation vapor pressure (SVP) of their oxidation products. After updating the SVP values, the mass concentration of TX SOA in the Yangtze River Delta region during summer doubled, and there was also an approximate 3% enhancement in the total SOA. Compared to a lumped mechanism used for simulating TX SOA, MCM predicted comparable mass concentrations but exhibited different volatility distributions and oxidation states.

Modeling the influence of carbon branching structure on secondary organic aerosol formation via multiphase reactions of alkanes

Abstract. Branched alkanes represent a significant proportion of hydrocarbons emitted in urban environments. To accurately predict the secondary organic aerosol (SOA) budgets in urban environments, these branched alkanes should be considered as SOA precursors. However, the potential to form SOA from diverse branched alkanes under varying environmental conditions is currently not well understood. In this study, the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model is extended to predict SOA formation via the multiphase reactions of various branched alkanes. Simulations with the UNIPAR model, which processes multiphase partitioning and aerosol-phase reactions to form SOA, require a product distribution predicted from an explicit gas kinetic mechanism, whose oxygenated products are applied to create a volatility- and reactivity-based αi species array. Due to a lack of practically applicable explicit gas mechanisms, the prediction of the product distributions of various branched alkanes was approached with an innovative method that considers carbon lengths and branching structures. The αi array of each branched alkane was primarily constructed using an existing αi array of the linear alkane with the nearest vapor pressure. Generally, the vapor pressures of branched alkanes and their oxidation products are lower than those of linear alkanes with the same carbon number. In addition, increasing the number of alkyl branches can also decrease the ability of alkanes to undergo autoxidation reactions that tend to form low-volatility products and significantly contribute to alkane SOA formation. To account for this, an autoxidation reduction factor, as a function of the degree and position of branching, was applied to the lumped groups that contain autoxidation products. The resulting product distributions were then applied to the UNIPAR model for predicting branched-alkane SOA formation. The simulated SOA mass was compared to SOA data generated under varying experimental conditions (i.e., NOx levels, seed conditions, and humidity) in an outdoor photochemical smog chamber. Branched-alkane SOA yields were significantly impacted by NOx levels but insignificantly impacted by seed conditions or humidity. The SOA formation from branched and linear alkanes in diesel fuel was simulated to understand the relative importance of branched and linear alkanes with a wide range of carbon numbers. Overall, branched alkanes accounted for a higher proportion of SOA mass than linear alkanes due to their higher contribution to diesel fuel.

Formation of secondary organic aerosols from Cl-initiated oxidation of anisole: Rapid release of ultrafine particles and organic chlorides

Recent studies have highlighted the increased occurrence of reactive chlorine, drawing significant attention to the process of chlorinated chemical oxidation of oxygenated aromatics emitted from biomass burning (BB) in the formation of secondary organic aerosols (SOA). This study selected an oxygenated aromatic, anisole, as a representative of BB, and investigated the products and mechanisms of its reaction with Cl•, as well as exploring the implications of precursor-to-oxidant ratio ([anisole/Cl2]0), NOx levels, and seed particles on SOA generation. The gas-phase composition, SOA composition, and particle information were determined using a single-photon ionization time-of-flight mass spectrometry (SPIMS), a thermal desorption unit gas chromatography mass spectrometry (TDU-GC/MS), and a scanning mobility particle sizer (SMPS), respectively. Experimental results indicate that within minutes of turning on the ultraviolet (UV) lights, a large quantity of ultrafine particles (UFPs) (diameter <100 nm) is immediately formed. The SOA yield is significantly dependent on [anisole/Cl2]0, decreasing from 66.2% to 20.0% as the [anisole/Cl2]0 increases. Upon oxidation by Cl•, anisole promptly released organic chlorides, including 2-chlorophenol and 2,4,6-trichlorophenol. The addition of NOx decreased the SOA yield, enhanced the role of OH• in the reaction process, and led to the formation of organic nitrogen products, such as C6H5NO3 and C7H7NO4. Furthermore, Cl• primarily initiates reactions through H-abstraction and Cl-substitution, resulting in the oxidation products largely retaining the benzene ring. This provides a potential explanation for the high SOA yield induced by Cl• in this study. Overall, our work suggests that the release of UFPs and organic chlorides can be found in the Cl-initiated oxidation of anisole, which contributes to high SOA yields. Against the backdrop of increasing wildfire frequency due to global warming, it is necessary to consider the contributions and sources of UFPs and organic chlorides caused by the reaction of wildfire emissions with Cl atoms.

Impact of HO2∕RO2 ratio on highly oxygenated α-pinene photooxidation products and secondary organic aerosol formation potential

Abstract. Highly oxygenated molecules (HOMs) from the atmospheric oxidation of biogenic volatile organic compounds are important contributors to secondary organic aerosol (SOA). Organic peroxy radicals (RO2) and hydroperoxy radicals (HO2) are key species influencing the HOM product distribution. In laboratory studies, experimental requirements often result in overemphasis on RO2 cross-reactions compared to reactions of RO2 with HO2. We analyzed the photochemical formation of HOMs from α-pinene and their potential to contribute to SOA formation under high (≈1/1) and low (≈1/100) HO2/RO2 conditions. As HO2/RO2 &gt; 1 is prevalent in the daytime atmosphere, sufficiently high HO2/RO2 is crucial to mimic atmospheric conditions and to prevent biases by low HO2/RO2 on the HOM product distribution and thus SOA yield. Experiments were performed under steady-state conditions in the new, continuously stirred tank reactor SAPHIR-STAR at Forschungszentrum Jülich. The HO2/RO2 ratio was increased by adding CO while keeping the OH concentration constant. We determined the HOM's SOA formation potential, considering its fraction remaining in the gas phase after seeding with (NH4)2SO4 aerosol. An increase in HO2/RO2 led to a reduction in SOA formation potential, with the main driver being a ∼ 60 % reduction in HOM-accretion products. We also observed a shift in HOM-monomer functionalization from carbonyl to hydroperoxide groups. We determined a reduction of the HOM's SOA formation potential by ∼ 30 % at HO2/RO2 ≈1/1 compared to HO2/RO2 ≈ 1/100. Particle-phase observations measured a similar decrease in SOA mass and yield. Our study shows that too low HO2/RO2 ratios compared to the atmosphere can lead to an overestimation of SOA yields.

Unpacking the diversity of monoterpene oxidation pathways via nitrooxy–alkyl radical ring-opening reactions and nitrooxy–alkoxyl radical bond scissions

Terrestrial vegetation emits vast quantities of monoterpenes to the atmosphere. These compounds, once oxidized, can contribute to the formation and growth of secondary organic aerosol (SOA) particles. However, studies report widely different SOA yields from atmospheric oxidation of different monoterpenes, despite their structural similarities. The NO3-radical-initiated oxidation of α-pinene for instance, leads to minimal SOA yields, whereas with Δ-carene a high SOA yield is observed. A previous study indicated that their oxidation mechanisms diverge after formation of a nitrooxy–alkoxyl radical intermediate, whose C–C bond scission reactions can either lead to early termination of the oxidative chain, thus limiting the yield of condensable vapors, or further propagate it, leading to low-volatility products. In this study, we employ computational methods to investigate these reactions in the NO3-radical oxidation of five other monoterpenes: limonene, sabinene, β-pinene, α-thujene and camphene. Additionally, we explore the possibility of rearrangement via ring-opening of the nitrooxy-alkyl radical adducts produced immediately after NO3 radical attack. Our calculations predict that alkyl radical rearrangement is dominant over O2-addition for sabinene, minor but competitive for α-thujene and β-pinene, and negligible for camphene. These rearrangements can induce further propagation of the oxidative chain, and thus higher SOA yields. Concerning alkoxyl radical C–C bond scissions, our results indicate that endocyclic nitrate species (derived from limonene and α-thujene) react preferentially via the channel leading to oxidative chain termination, whereas exocyclic nitrate species (sabinene, β-pinene, and camphene) react preferentially via channels leading to further propagation.

Nighttime reactions of a series of unsaturated alcohols with NO3•: Kinetics, products and mechanisms study

Unsaturated alcohols are a class of Biogenic volatile organic compounds (BVOCs) emitted in large quantities by plants when damaged or under adverse environmental conditions, and studies on their atmospheric degradation at night are still lacking. We used chamber experiments to study the gas-phase reactions of three unsaturated alcohols, E-2-penten-1-ol, Z-2-hexen-1-ol and Z-3-hepten-1-ol, with NO3 radicals (NO3•) during the night. The rate constants of these reactions were (11.7 ± 1.76) × 10−13, (8.55 ± 1.33) × 10−13 and (6.08 ± 0.47) × 10−13 cm3/(molecule·s) at 298K and 760 Torr, respectively. In contrast, the reaction rate of similar substances with ozone was about 10−18 cm3/(molecule·s), which indicates that the reaction with NO3• is the main oxidation pathway for unsaturated alcohols at night. Small molecule aldehydes and ketones were the main gas-phase organic products of the reaction of three aldehydes and ketones with NO3•, and the total small molecule aldehydes and ketones yields can reach between 45%-60%. They mainly originate from the breakage of alkoxy radicals, and different breakage sites determine different product distributions. In addition, the SOA yields of the three unsaturated alcohols with NO3• were 7.1% ± 1.0%, 12.5% ± 1.9% and 30.0% ± 4.5%, respectively, which were much higher than those of similarly structured substances with O3 or OH radicals (•OH). The results of high-resolution mass spectrometry shows that the main components of Secondary organic aerosol (SOA) of the three unsaturated alcohols are dimeric compounds containing several nitrate groups, which are formed through the polymerization of oxyalkyl radicals.

Multi-generation oxidation mechanism of M-xylene: Unexpected implications for secondary organic aerosol formation

Secondary organic aerosol (SOA) affects air quality, human health and climate. The multi-generation reactions of volatile organic compounds (VOCs) have become key process for explaining the SOA formation. M-xylene, as one of the most important VOCs in urban atmosphere, has got extensive study. However, the reaction mechanism of the first-generation products hydroperoxides (M-ROOH) and organonitrates (M-RONO2) remain unknown. In this work, the hydroxyl radicals (·OH) initiated reactions of M-ROOH and M-RONO2 were investigated by employing quantum chemical methods and kinetics modeling. The results show that new ring-retaining epoxides, a range of dialdehydes and less volatile hydroperoxides and organonitrates are formed, contributing to SOA formation. By adopting the unveiled new mechanism into the SOSAA box modeling, we found that the yield of SOA from m-xylene oxidation is up to 38%, which is comparable to the experimental value (36%). This work advances current understanding of multi-generation chemistry and elucidates the role of aromatic hydrocarbons oxidation in the formation of SOA.

Production of oxygenated volatile organic compounds from the ozonolysis of coastal seawater

Abstract. Dry deposition of ozone (O3) to the ocean surface and the ozonolysis of organics in the sea surface microlayer (SSML) are potential sources of volatile organic compounds (VOCs) to the marine atmosphere. We use a gas chromatography system coupled to a Vocus proton-transfer-reaction time-of-flight mass spectrometer to determine the chemical composition and product yield of select VOCs formed from ozonolysis of coastal seawater collected from Scripps Pier in La Jolla, California. Laboratory-derived results are interpreted in the context of direct VOC vertical flux measurements made at Scripps Pier. The dominant products of laboratory ozonolysis experiments and the largest non-sulfur emission fluxes measured in the field correspond to Vocus CxHy+ and CxHyOz+ ions. Gas chromatography (GC) analysis suggests that C5–C11 oxygenated VOCs, primarily aldehydes, are the largest contributors to these ion signals. In the laboratory, using a flow reactor experiment, we determine a VOC yield of 0.43–0.62. In the field at Scripps Pier, we determine a maximum VOC yield of 0.04–0.06. Scaling the field and lab VOC yields for an average O3 deposition flux and an average VOC structure results in an emission source of 10.7 to 167 Tg C yr−1, competitive with the DMS source of approximately 20.3 Tg C yr−1. This study reveals that O3 reactivity to dissolved organic carbon can be a significant carbon source to the marine atmosphere and warrants further investigation into the speciated VOC composition from different seawater samples and the reactivities and secondary organic aerosol (SOA) yields of these molecules in marine-relevant, low NOx conditions.

Differences in Secondary Organic Aerosol Formation from α-Pinene Photooxidation in a Chamber with Purified Air and Ambient Air as Matrices: Preliminary Results

α-Pinene is a biogenic volatile organic compound (BVOC) that significantly contributes to secondary organic aerosols (SOA) in the atmosphere due to its high emission rate, reactivity, and SOA yield. However, the SOA yield measured in chamber studies from α-pinene photooxidation is limited in a purified air matrix. Assessing SOA formation from α-pinene photooxidation in real urban ambient air based on studies conducted in purified air matrices may be subject to uncertainties. In this study, α-pinene photooxidation and SOA yield were investigated in a smog chamber in the presence of NO and SO2 under purified air and ambient air matrices. With the accumulation of ozone (O3) during the photooxidation, an increasing part of α-pinene was consumed by O3 and finally nearly half of the α-pinene was oxidized by O3, facilitating the production of highly oxidized organic molecules and thereby SOA formation. Although the ambient air we introduced as matrix air was largely clean, with initial organic aerosol mass concentrations of ~1.5 μg m−3, the α-pinene SOA yield in the ambient air matrix was 42.3 ± 5.3%, still higher than that of 32.4 ± 0.4% in the purified air matrix. The chemical characterization of SOA by the high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) revealed that CxHy accounted for 53.7 ± 1.1% of the total signal in the ambient air matrix experiments, higher than 48.1 ± 0.3% in the purified air, while CxHyO and CxHyO&gt;1 together constituted 45.0 ± 0.9% in the ambient air matrix, lower than 50.1 ± 1.0% in the purified air. The O:C ratio in the ambient air matrix experiments was 0.41 ± 0.01, lower than 0.46 ± 0.01 in the purified air. The higher SOA yield of α-pinene in the ambient air matrix compared to that in the purified air matrix was partly due to the presence of initial aerosols in the ambient air, which facilitated the low volatile organic compounds produced from photochemical oxidation to enter the aerosol phase through gas-particle partitioning. The in-situ aerosol acidity calculated by the ISORROPIA-II model in the ambient air matrix experiments was approximately six times higher than that in purified air, and the higher SOA yield in the ambient air matrix experiments might also be attributed to acid-catalyzed SOA formation.

Review of Smog Chamber Experiments for Secondary Organic Aerosol Formation

In this study, we reviewed smog chamber systems and methodologies used in secondary organic aerosol (SOA) formation studies. Many important chambers across the world have been reviewed, including 18 American, 24 European, and 8 Asian chambers. The characteristics of the chambers (location, reactor size, wall materials, and light sources), measurement systems (popular equipment and working principles), and methodologies (SOA yield calculation and wall-loss correction) are summarized. This review discussed key experimental parameters such as surface-to-volume ratio (S/V), temperature, relative humidity, light intensity, and wall effect that influence the results of the experiment, and how the methodologies have evolved for more accurate simulation of atmospheric processes. In addition, this review identifies the sources of uncertainties in finding SOA yields that are originated from experimental systems and methodologies used in previous studies. The intensity of the installed artificial lights (photolysis rate of NO2 varied from 0.1/min to 0.40/min), SOA density assumption (varied from 1 g/cm3 to 1.45 g/cm3), wall-loss management, and background contaminants were identified as important sources of uncertainty. The methodologies developed in previous studies to minimize those uncertainties are also discussed.

Impact of temperature on the role of Criegee intermediates and peroxy radicals in dimer formation from β-pinene ozonolysis

Abstract. Stabilized Criegee intermediates (SCIs) and organic peroxy radicals (RO2) are critical in atmospheric oxidation processes and secondary organic aerosol (SOA) formation. However, the influence of temperature on their corresponding reaction mechanisms in SOA formation is unclear. Through utilizing formic acid as a SCI scavenger and regulating the ratio of hydroperoxyl radials (HO2) to RO2 ([HO2]/[RO2]) from ∼ 0.3 to ∼ 1.9 using different concentrations of CO, the roles of RO2 and SCIs in SOA formation were investigated from 248 to 298 K, particularly for dimer formation in β-pinene ozonolysis. The SOA yield increased by 21 % from 298 to 273 K, while it decreased by 40 % from 273 to 248 K. Both changing [HO2]/[RO2] and scavenging SCIs significantly affect SOA yield and composition. SCI reactions accounted for more than 40 % of dimer and SOA mass formation for all temperatures. Increasing [HO2]/[RO2] inhibited dimer and SOA formation, and this inhibition became larger with decreasing temperature. Compared to low [HO2]/[RO2] (0.30–0.34), the dimer abundance at high [HO2]/[RO2] (1.53–1.88) decreased by about 31 % at 298 K and 70 % at 248 K. [HO2]/[RO2] has a specific impact on SCI-controlled dimers at lower temperatures by especially influencing the C9–SCI reactions with RO2. The dimers formed from C9–SCI reactions with RO2 were estimated to decrease by 61 % at high [HO2]/[RO2] compared to low [HO2]/[RO2] at 248 K. The high reactivity and substantial contribution to SOA of β-pinene-derived SCIs at lower temperatures observed in this study suggest that monoterpene-derived SCI reactions should be accounted for in describing colder regions of the atmosphere.

Organic aerosol formation from 222 nm germicidal light: ozone-initiated vs. non-ozone pathways.

Germicidal ultraviolet lamps outputting 222 nm light (GUV222) have the potential to reduce the airborne spread of disease through effective inactivation of pathogens, while remaining safe for direct human exposure. However, recent studies have identified these lamps as a source of ozone and other secondary pollutants such as secondary organic aerosol (SOA), and the health effects of these pollutants must be balanced against the benefits of pathogen inactivation. While ozone reactions are likely to account for much of this secondary indoor air pollution, 222 nm light may initiate additional non-ozone chemical processes, including the formation of other oxidants and direct photolytic reactions, which are not as well understood. This work examines the impacts of GUV222 on SOA formation and composition by comparing limonene oxidation under GUV222 and O3-only control conditions in a laboratory chamber. Differences between these experiments enable us to distinguish patterns in aerosol formation driven by ozone chemistry from those driven by other photolytic processes. These experiments also examine the influence of the addition of NO2 and nitrous acid (HONO), and investigate SOA formation in sampled outdoor air. SOA composition and yield vary only slightly with respect to GUV222vs. ozone-only conditions; NO2 and HONO photolysis do not appreciably affect the observed chemistry. In contrast, we observe consistent new particle formation under high-fluence 222 nm light (45 μW cm-2) that differs substantially from ozone-only experiments. This observed new particle formation represents an additional reason to keep GUV222 fluence rates to the lowest effective levels.

Insights into secondary organic aerosol formation from the day- and nighttime oxidation of polycyclic aromatic hydrocarbons and furans in an oxidation flow reactor

Abstract. Secondary organic aerosols (SOAs) formed by oxidation of typical precursors largely emitted by biomass burning, such as polycyclic aromatic hydrocarbons (PAHs) and furans, are still poorly characterized. We evaluated and compared the formation yields, effective density (ρeff), absorption Ångström exponent (α), and mass absorption coefficient (MAC) of laboratory-generated SOAs from three furan compounds and four PAHs. SOAs were generated in an oxidation flow reactor under day- (OH radicals) or nighttime (NO3 radicals) conditions. The ρeff, formation yields, α, and MAC of the generated SOAs varied depending on the precursor and oxidant considered. The ρeff of SOAs formed with OH and NO3 tended to increase with particle size before reaching a “plateau”, highlighting potential differences in SOA chemical composition and/or morphology, according to the particle size. Three times lower SOA formation yields were obtained with NO3 compared with OH. The yields of PAH SOAs (18 %–76 %) were five to six times higher than those obtained for furans (3 %–12 %). While furan SOAs showed low or negligible light absorption properties, PAH SOAs had a significant impact in the UV–visible region, implying a significant contribution to atmospheric brown carbon. No increase in the MAC values was observed from OH to NO3 oxidation processes, probably due to a low formation of nitrogen-containing chromophores with NO3 only (without NOx). The results obtained demonstrated that PAHs are significant SOA precursors emitted by biomass burning, through both, day- and nighttime processes, and have a substantial impact on the aerosol light absorption properties.

Oligomer formation from cross-reaction of Criegee intermediates in the styrene-isoprene-O3 mixed system

Alkene ozonolysis can produce stabilized Criegee intermediates (SCIs), which play a key role in oligomers' formation. Though styrene and isoprene coexist in the ambient atmosphere as important anthropogenic and biogenic secondary organic aerosol (SOA) precursors, respectively, their cross-reactions have not received attention. This study investigated the interactions of SCIs from styrene and isoprene ozonolysis for the first time. The high-resolution Orbitrap mass spectrometer was used to determine the unique ion mass spectra of the isoprene-styrene-O3 mixture. The results show that the signal intensities of new ions account for >8.4% of total ions in the mass spectra of the styrene-isoprene-O3 mixed system. Styrene and isoprene ozonolysis can produce characteristic C7–SCI and C4–SCI, respectively. C7–SCI and C4–SCI can be involved in the cross-reactions, and the results of tandem mass spectra directly confirmed both C7–SCI and C4–SCI as chain units. The O/C and H/C ratios of cross-products are in the range of 0.38–1.07 and 1.00–1.50, respectively, which are consistent with cross-reaction products. Adding a C7–SCI unit reduces the oligomer's volatility by 1.3–1.4 orders of magnitude lower than adding a C4–SCI unit. Thus, C4–SCI can compete with C7–SCI to react with styrene-derived RO2/RC(O)OH to produce more volatile cross-products, while the less volatile cross-products can be formed when isoprene-derived RO2/RC(O)OH reacted with C7–SCI instead of C4–SCI. The SOA yield of the mixed system is lower than that of the single styrene-O3 system but higher than that of the single isoprene-O3 system. Ambient particles were also collected, and 5 possible SCI-related cross-products were identified. This study illustrates the effects of SCI-related cross-reactions on SOA components and physicochemical properties, providing a basis for future research on SCI-related cross-reactions that frequently occur in the ambient atmosphere.

Predicted and observed changes in summertime biogenic and total organic aerosol in the southeast United States from 2001 to 2010

Biogenic secondary organic aerosol (bSOA) is a major component of atmospheric particulate matter (PM2.5) in the southeast United States especially during the summer, when emissions of biogenic volatile organic compound (VOCs) are high and emissions from anthropogenic sources enhance the formation of secondary particulate matter. In this work we test the hypothesis whether a chemical transport model (PMCAMx) that includes a detailed description of gas-phase chemistry, secondary organic aerosol (SOA) formation based on the volatility basis set (VBS), and interactions among compounds based on partitioning theory can predict organic aerosol (OA) concentrations that are consistent with the observed changes in OA in response to significant changes in anthropogenic emissions during the summers of 2001 and 2010. The model had good performance for OA for both periods and its predictions were consistent with the observed changes in both the urban and rural areas. The fractional error of OA predictions remained practically the same (0.41 and 0.44 at Chemical Speciation Network (CSN) sites and 0.40 to 0.41 at Interagency Monitoring of Protected Visual Environments (IMPROVE) sites in the summers of 2001 and 2010 respectively) in the two examined periods. The fractional bias of OA predictions increased from 0.10 to 0.22 at CSN sites and decreased from 0 to −0.09 at IMPROVE sites between the two periods. Average predicted bSOA concentrations in the southeast US did not change appreciably from the summer of 2001 to the summer of 2010, while the anthropogenic SOA decreased by 45%. As a result, the biogenic fraction of predicted total OA increased from 0.46 in 2001 to 0.63 in 2010. Partitioning effects due to reduced anthropogenic OA from 2001 resulted in 0.4 μg m−3 less biogenic OA on average in the southeast US in the summer of 2010. This was offset by biogenic SOA increases due to higher biogenic vapor emissions in the warmer 2010 summer. Removing the NOx-dependence of SOA formation yields resulted in higher fractional error and fractional bias at both CSN and IMPROVE sites in both summer periods, demonstrating the efficacy of the current formulation of SOA yields. The results of the analysis support the conclusion that a CTM that simulates NOx-dependent SOA chemistry and semivolatile partitioning of SOA material can consistently predict the observed changes in a region rich in biogenic VOCs and SOA.