Secondary Organic Aerosol Yield Research Articles

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.

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.

Contrasting impacts of humidity on the ozonolysis of monoterpenes: insights into the multi-generation chemical mechanism

Abstract. Secondary organic aerosol (SOA) formed from the ozonolysis of biogenic monoterpenes is a major source of atmospheric organic aerosol. It has been previously found that relative humidity (RH) can influence the SOA formation from some monoterpenes, yet most studies only observed the increase or decrease in SOA yield without further explanations of molecular-level mechanisms. In this study, we chose two structurally different monoterpenes (limonene with an endocyclic double bond and an exocyclic double bond, Δ3-carene with only an endocyclic double bond) to investigate the effect of RH in a set of oxidation flow reactor experiments. We find contrasting impacts of RH on the SOA formation: limonene SOA yield increases by ∼100 % as RH increases, while there is a slight decrease in Δ3-carene SOA yield. Although the complex processes in the particle phase may play a role, we primarily attribute the results to the water-influenced reactions after ozone attack on the exocyclic double bond of limonene, which leads to the increment of lower volatile organic compounds under high-RH conditions. However, as Δ3-carene only has an endocyclic double bond, it cannot undergo such reactions. This hypothesis is further supported by the SOA yield enhancement of β-caryophyllene, a sesquiterpene that also has an exocyclic double bond. These results greatly improve our understanding of how water vapor influences the ozonolysis of biogenic organic compounds and subsequent SOA formation processes.

Effects of driving conditions on aerosol formation from photooxidation of gasoline vehicles exhaust in Hong Kong

The emissions before and after atmospheric oxidation from three gasoline vehicles were characterized under different driving conditions (idling, cruising and New European Driving Cycle (NEDC)). The total quantified volatile organic compounds (VOCs) emission factors for the vehicles ranged from 18.4 to 2728.7 mg/kg depending on driving conditions. The organic aerosol mass concentrations showed substantial increase (∼7.6–10.8 times) after ageing process, implying that vehicular emissions were an important source of secondary organic aerosols (SOAs). The total quantified organic aerosol mass concentrations in aged samples ranged from 77.7 to 480.5 ng m−3 under different test conditions. Aromatic and alkenoic acids were identified as major organic aerosols after ageing. The emission factors of VOCs were higher under idling condition compared to the other driving modes for all vehicles. High VOCs emissions can potentially lead to high secondary organic aerosol (SOA) formation inside the reactor and more robust SOA formation under idling condition in all analysis. The gasoline direct injection (GDI) vehicle with latest year of manufacture in EURO 4 standard can pose lower primary emissions of organic substances, but nevertheless the composition of emitted VOCs demonstrates higher SOA yield and SOA formation. Further analysis proposes engine type is the key factor on primary VOC composition under idling. The findings suggest a need to revise existing regulation of composition of organic substances.

Combined Smog Chamber/Oxidation Flow Reactor Study on Aging of Secondary Organic Aerosol from Photooxidation of Aromatic Hydrocarbons.

Secondary organic aerosol (SOA) is a significant component of atmospheric fine particulate matter (PM2.5), and their physicochemical properties can be significantly changed in the aging process. In this study, we used a combination consisting of a smog chamber (SC) and oxidation flow reactor (OFR) to investigate the continuous aging process of gas-phase organic intermediates and SOA formed from the photooxidation of toluene, a typical aromatic hydrocarbon. Our results showed that as the OH exposure increased from 2.6 × 1011 to 6.3 × 1011 molecules cm-3 s (equivalent aging time of 2.01-4.85 days), the SOA mass concentration (2.9 ± 0.05-28.7 ± 0.6 μg cm-3) and corrected SOA yield (0.073-0.26) were significantly enhanced. As the aging process proceeds, organic acids and multiple oxygen-containing oxidation products are continuously produced from the photochemical aging process of gas-phase organic intermediates (mainly semi-volatile and intermediate volatility species, S/IVOCs). The multigeneration oxidation products then partition to the aerosol phase, while functionalization of SOA rather than fragmentation dominated in the photochemical aging process, resulting in much higher SOA yield after aging compared to that in the SC. Our study indicates that SOA yields as a function of OH exposure should be considered in air quality models to improve SOA simulation, and thus accurately assess the impact on SOA properties and regional air quality.

Insight into the crucial reason causing the difference in secondary organic aerosol yields of monocyclic aromatic hydrocarbons with different methyl substituent numbers

The secondary organic aerosol (SOA) yield of toluene photooxidation was reported to substantially higher than that of trimethylbenzene due to the effect of the number of methyl substituents. However, the intrinsic mechanism for this disparity is not clear enough. In this study, a highly-sensitive thermal-desorption photoinduced associative ionization mass spectrometer (TD-PAI-MS) was used to real-time characterize the molecular composition and its evolution of the SOA generated from the photooxidation of toluene and 1,2,3-trimethylbenzene (1,2,3-TMB) in a smog chamber. In the new particle formation (NPF) stage, toluene generated more variety of nucleation precursors, such as benzaldehyde (MW 106) and benzoic acid (MW 122), resulting in a much higher nucleation rate and SOA number concentration. In the SOA growth/aging stage, the key SOA components of toluene were mainly dialdehydes, e.g., 2-oxopropanedial (MW 86) and 4-oxopent-2-enedial (MW 112), which played an important role in the formation of highly oxidized species (HOS) through oligomerization or cyclization reactions. In contrast, due to the presence of more methyl groups, 1,2,3-TMB was inclined to produce ketones, e.g., 2,3-butanedione (MW 86) and 3-methyl-4-oxopent-2-enal (MW 112), which would be cleaved into high-volatility low molecular compounds, e.g., acetic acid, through fragmentation. Taken together, relative to 1,2,3-TMB, the higher nucleation rate during NPF and the significant oligomerization/functionalization process during SOA growth are thought to be the major reasons resulting in the higher SOA yield of toluene. This work provides a reference for the insight into the different SOA yields of monocyclic aromatic hydrocarbons (MAHs) through further revealing the SOA formation mechanism during toluene and 1,2,3-TMB photooxidation.

Modeling of secondary organic aerosols (SOA) based on two commonly used air quality models in China: Consistent S/IVOCs contribution but large differences in SOA aging

Secondary organic aerosol (SOA) is an important component of atmospheric fine particulate matter (PM2.5), with contributions from anthropogenic and biogenic volatile organic compounds (AVOC and BVOC) and semi- (SVOC) and intermediate volatility organic compounds (IVOC). Policymakers need to know which SOA precursors are important but accurate simulation of SOA magnitude and contributions remain uncertain. Findings from existing SOA modeling studies have many inconsistencies due to differing emission inventory methodologies/assumptions, air quality model (AQM) algorithms, and other aspects of study methodologies. To address some of the inconsistencies, we investigated the role of different AQM SOA algorithms by applying two commonly used models, CAMx and CMAQ, with consistent emission inventories to simulate SOA concentrations and contributions for July and November 2018 in China. Both models have a volatility basis set (VBS) SOA algorithm but with different parameters and treatments of SOA photochemical aging. SOA generated from BVOC (i.e., BSOA) is found to be more important in southern China. In contrast, SOA generated from anthropogenic precursors is more prevalent in the North China Plain (NCP), Yangtze River Delta (YRD), Sichuan Basin and Central China. Both models indicate negligible SOA formation from SVOC emissions compared to other precursors. In July, when BVOC emissions are abundant, SOA is predominantly contributed by BSOA (except for NCP), followed by IVOC-SOA (i.e., SOA produced from IVOC) and ASOA (i.e., SOA produced from anthropogenic VOC). In contrast, in November, IVOC became the leading SOA contributor for all selected regions except PRD, illustrating the important contribution of IVOC emissions to SOA formation.While both models generally agree in terms of the spatial distributions and seasonal variations of different SOA components, CMAQ tends to predict higher BSOA, while CAMx generates higher ASOA concentrations. As a result, CMAQ results suggest that BSOA concentration is always higher than ASOA in November, while CAMx emphasizes the importance of ASOA. Utilizing a conceptual model, we found that different treatment of SOA aging between the two models is a major cause of differences in simulated ASOA concentrations. The step-wise SOA aging scheme implemented in the CAMx VBS (based on gas-phase reactions with OH radical and similar to other models) exhibits a strong enhancement effect on simulated ASOA concentrations, and this effect increases with the ambient organic aerosol (OA) concentrations. The CMAQ aerosol module implements a different SOA aging scheme that represents particle-phase oligomerization and has smaller impacts on total OA. Different structures and/or parameters of the SOA aging schemes are being used in current models, which could greatly affect model simulations of OA in ways that are difficult to anticipate. Our results indicate that future control policies should aim at reducing IVOC emissions as well as traditional VOC emissions. In addition, aging schemes are the major driver in CMAQ vs. CAMx treatments of ASOA and their resulting predicted mass. More sophisticated measurement data (e.g., with resolved OA components) and/or chamber experiments (e.g., investigating how aging influences SOA yields) are needed to better characterize SOA aging and constrain model parameterizations.

Synergistic generation mechanisms of SOA and ozone from the photochemical oxidation of 1,3,5-trimethylbenzene: Influence of precursors ratio, temperature and radiation intensity

Aromatic hydrocarbons (AHs) are important anthropogenic precursors for both secondary organic aerosol (SOA) and ozone (O3) in urban areas. Knowledge about the synergistic processes and influence mechanisms of SOA and O3 during the photochemical oxidation of AHs is still relatively limited. In this study, the synergistic formation processes of SOA and O3 through the photochemical reactions of a representative AHs (1,3,5-trimethylbenzene, 135TMB) under different initial volatile organic compound/nitrogen oxides ([VOC]/[NOX]) ratios, temperatures and radiation intensities were investigated. The results showed that temperature and radiation significantly affected the reaction products and yields: the O3 production rates under high temperatures and radiation were greater than those under low temperatures and radiation, whereas the mass concentrations and yields of SOA under low temperatures and radiation were much higher than those under high temperatures and radiation. It was also found that the SOA yield increased with increasing NOX concentration within a specific initial [135TMB]/[NOX] ratio, but it decreased with increasing NOX concentration beyond a specific initial [135TMB]/[NOX] ratio. In addition, the concentrations of SOA and O3 in all the experiments increased simultaneously regardless of low temperatures or high temperatures. From these phenomena, it can be inferred that appropriate strategies for O3 precursor abatement can simultaneously reduce the concentration of SOA, which means that the coordinated control of fine particles and O3 could be achieved by taking coordinated emission reduction measures for VOCs and NOX precursors. The analysis of the organic components revealed that intramolecular hydrogen transfer occurred in some reactions in 135TMB photooxidation, and low-volatility and high-oxidative state organics were formed. The master chemical mechanism (MCM) results showed that the existing MCM mechanism does not yet fully meet the need to simulate the atmospheric photochemical reaction processes of 135TMB in the real atmosphere in China, and a localized MCM mechanism needs to be developed in the future.

Estimation of secondary organic aerosol formation parameters for the volatility basis set combining thermodenuder, isothermal dilution, and yield measurements

Abstract. Secondary organic aerosol (SOA) is a major fraction of the total organic aerosol (OA) in the atmosphere. SOA is formed by the partitioning onto pre-existent particles of low-vapor-pressure products of the oxidation of volatile, intermediate-volatility, and semivolatile organic compounds. Oxidation of the precursor molecules results in a myriad of organic products, making the detailed analysis of smog chamber experiments difficult and the incorporation of the corresponding results into chemical transport models (CTMs) challenging. The volatility basis set (VBS) is a framework that has been designed to help bridge the gap between laboratory measurements and CTMs. The parametrization of SOA formation for the VBS has been traditionally based on fitting yield measurements of smog chamber experiments. To reduce the uncertainty in this approach, we developed an algorithm to estimate the SOA product volatility distribution, effective vaporization enthalpy, and effective accommodation coefficient combining SOA yield measurements with thermograms (from thermodenuders) and areograms (from isothermal dilution chambers) from different experiments and laboratories. The algorithm is evaluated with “pseudo-data” produced from the simulation of the corresponding processes, assuming SOA with known properties and introducing experimental error. One of the novel features of our approach is that the proposed algorithm estimates the uncertainty in the predicted yields for different atmospheric conditions (temperature, SOA concentration levels, etc.). The uncertainty in these predicted yields is significantly smaller than that of the estimated volatility distributions for all conditions tested.