Secondary Organic Aerosol Yield Research Articles

Minimizing Errors in Measured Yields of Particle-Phase Products Formed in Environmental Chamber Reactions: Revisiting the Yields of β-Hydroxynitrates Formed from 1-Alkene + OH/NOx Reactions

Environmental chamber studies are widely used for measuring the yields of reaction products and secondary organic aerosol formed from the oxidation of volatile organic compounds, information that c...

Anthropogenic Effects on Biogenic Secondary Organic Aerosol Formation

Anthropogenic emissions alter biogenic secondary organic aerosol (SOA) formation from naturally emitted volatile organic compounds (BVOCs). We review the major laboratory and field findings with regard to effects of anthropogenic pollutants (NOx, anthropogenic aerosols, SO2, NH3) on biogenic SOA formation. NOx participate in BVOC oxidation through changing the radical chemistry and oxidation capacity, leading to a complex SOA composition and yield sensitivity towards NOx level for different or even specific hydrocarbon precursors. Anthropogenic aerosols act as an important intermedium for gas—particle partitioning and particle-phase reactions, processes of which are influenced by the particle phase state, acidity, water content and thus associated with biogenic SOA mass accumulation. SO2 modifies biogenic SOA formation mainly through sulfuric acid formation and accompanies new particle formation and acid-catalyzed heterogeneous reactions. Some new SO2-involved mechanisms for organosulfate formation have also been proposed. NH3/amines, as the most prevalent base species in the atmosphere, influence biogenic SOA composition and modify the optical properties of SOA. The response of SOA formation behavior to these anthropogenic pollutants varies among different BVOCs precursors. Investigations on anthropogenic—biogenic interactions in some areas of China that are simultaneously influenced by anthropogenic and biogenic emissions are summarized. Based on this review, some recommendations are made for a more accurate assessment of controllable biogenic SOA formation and its contribution to the total SOA budget. This study also highlights the importance of controlling anthropogenic pollutant emissions with effective pollutant mitigation policies to reduce regional and global biogenic SOA formation.

A zero-dimensional view of atmospheric degradation of levoglucosan (LEVCHEM_v1) using numerical chamber simulations

Abstract. Here, we developed a zero-dimensional (0-D) modeling framework (LEVCHEM_v1) to provide insights into the atmospheric degradation of a key tracer emitted during biomass burning – levoglucosan (LEV), while additionally exploring its effects on the dynamics of secondary organic aerosols (SOA) and other gases. For this, we updated existing chemical mechanisms (homogeneous gas-phase chemistry and heterogeneous chemistry) in the BOXMOXv1.7 model to include the chemical degradation of LEV and its intermediary degradation products in both phases (gas and aerosol). In addition, we added a gas-particle partitioning mechanism to the model to account for the effect of evaporation and condensation on the phase-specific concentrations of LEV and its degradation products. Comparison of simulation results with measurements from various chamber experiments (spanning summer and winter conditions) show that the degradation timescale of LEV varied by phase, with gas-phase degradation occurring over ∼1.5–5 d and aerosol-phase degradation occurring over ∼8–36 h. These relatively short timescales suggest that most of the initial LEV concentration can be lost chemically or deposited locally before being transported regionally. We varied the heterogeneous reaction rate constant in a sensitivity analysis (for summer conditions only) and found that longer degradation timescales of LEV are possible, particularly in the aerosol phase (7 d), implying that some LEV may be transported regionally. The multiphase chemical degradation of LEV has effects on SOA and other gases. Several first- or second-generation products resulted from its degradation; most of the products include one or two carbonyl groups, one product contains a nitrate group, and a few products show the cleavage of C−C bonds. The relative importance of the products varies depending on the phase and the timing of the maximum concentration achieved during the simulation. Our estimated secondary organic aerosol SOA yields (4 %–32 %) reveal that conversion of LEV to secondary products is significant and occurs rapidly in the studied scenarios. LEV degradation affected other gases by increasing the concentrations of radicals and decreasing those of reactive nitrogen species. Decreases of the mixing ratios of nitrogen oxides appear to drive a more rapid increase in ozone compared with changes in volatile organic compounds levels. An important next step to confirm longer degradation timescales will be to extend the evaluation of the modeled LEV degradation beyond 3–6 h by using more extensive data from chambers and, possibly, from fire plumes. The mechanism developed here can be used in chemical transport models applied to fire plumes to trace LEV and its degradation products from source to deposition, to assess their atmospheric implications and to answer questions relevant to fire tracing, carbon and nitrogen cycling, and climate.

The production and hydrolysis of organic nitrates from OH radical oxidation of <i>β</i>-ocimene

Abstract. Biogenic volatile organic compounds (BVOCs) emitted by plants represent the largest source of non-methane hydrocarbon emissions on Earth. Photochemical oxidation of BVOCs represents a significant pathway in the production of secondary organic aerosol (SOA), affecting Earth's radiative balance. Organic nitrates (RONO2), formed from the oxidation of BVOCs in the presence of NOx, represent important aerosol precursors and affect the oxidative capacity of the atmosphere, in part by sequestering NOx. In the aerosol phase, RONO2 hydrolyze to form nitric acid and numerous water-soluble products, thus contributing to an increase in aerosol mass. However, only a small number of studies have investigated the production of RONO2 from OH oxidation of terpenes, and among those, few have studied their hydrolysis. Here, we report a laboratory study of OH-initiated oxidation of β-ocimene, an acyclic, tri-olefinic monoterpene released during the daytime from vegetation, including forests, agricultural landscapes, and grasslands. We conducted studies of the OH oxidation of β-ocimene in the presence of NOx using a 5.5 m3 all-Teflon photochemical reaction chamber, during which we quantified the total (gas- and particle-phase) RONO2 yield and the SOA yields. We sampled the organic nitrates produced and measured their hydrolysis rate constants across a range of atmospherically relevant pH. The total organic nitrate yield was determined to be 38(±9) %, consistent with the available literature regarding the dependence of organic nitrate production (from RO2 + NO) on carbon number. We found the hydrolysis rate constants to be highly pH dependent, with a hydrolysis lifetime of 51(±13) min at pH = 4 and 24(±3) min at pH = 2.5, a typical pH for deliquesced aerosols. We also employed high-resolution mass spectrometry for preliminary product identification. The results indicate that the ocimene SOA yield (< 1 %) under relevant aerosol mass loadings in the atmosphere is significantly lower than reported yields from cyclic terpenes, such as α-pinene, likely due to alkoxy radical decomposition and formation of smaller, higher-volatility products. This is also consistent with the observed lower particle-phase organic nitrate yields of β-ocimene – i.e., 1.5(±0.5) % – under dry conditions. We observed the expected hydroxy nitrates by chemical ionization mass spectrometry (CIMS) and some secondary production of the dihydroxy dinitrates, likely produced by oxidation of the first-generation hydroxy nitrates. Lower RONO2 yields were observed under high relative humidity (RH) conditions, indicating the importance of aerosol-phase RONO2 hydrolysis under ambient RH. This study provides insight into the formation and fate of organic nitrates, β-ocimene SOA yields, and NOx cycling in forested environments from daytime monoterpenes not currently included in atmospheric models.

Nitrate radical, ozone and hydroxyl radical initiated aging of limonene secondary organic aerosol

The gas-particle mixture produced in a smog chamber from the ozonolysis of limonene was further oxidised with NO 3 radicals, O 3 and OH radicals to study the NO 3 , O 3 and OH initiated aging of biogenic secondary organic aerosol (SOA). The results of aerosol mass spectrometry analysis showed that similar yields of SOA were produced by all three oxidants used in the experiments after 1-h of aging, suggesting that NO 3 and O 3 initiated aging have similar SOA formation potentials to OH initiated aging. The results of proton transfer reaction-quadrupole interface time-of-flight mass spectrometry analysis showed that the signals of m/z 139, m/z 151, m/z 153 and m/z 167 decreased upon subsequent oxidation by all three oxidants, suggesting the degradation of gaseous unsaturated first-generation products formed from limonene ozonolysis such as limonaketone, limononaldehyde, limonalic acid and limononic acid. The results of liquid chromatography-mass spectrometry analysis showed that chromatographic peaks of m/z 185 and m/z 199 degraded upon subsequent oxidation, indicating that particle phase unsaturated products, including limonic acid and 5- or 7-hydroxylimononic acid, reacted in the gas or the particle phase with all three oxidants injected. The results of chemical kinetic and gas-particle partitioning calculations suggest that unsaturated particle phase products decrease due to reactions with NO 3 radicals, O 3 and OH radicals in the gas phase, whereas reactions in the particle phase are not excluded. New organic nitrate products were produced by NO 3 initiated aging whereas saturated organic compounds, including ketolimonic acid, 5- or 7-hydroxyketolimononic acid, and a portion of highly functionalised limonene ozonolysis products of m/z 215 and m/z 217 increased by O 3 and OH initiated aging. • Secondary aerosol formed by limonene ozonolysis was exposed to NO 3 , O 3 and OH. • Increases in aerosol yield during exposure were similar among all three oxidants. • Unsaturated products in gas and particle phases were reactive with three oxidants. • Highly functionalised compounds were produced after exposure to oxidants.

A comparative and experimental study of the reactivity with nitrate radical of two terpenes: <i>α</i>-terpinene and <i>γ</i>-terpinene

Abstract. Biogenic volatile organic compounds (BVOCs) are intensely emitted by forests and crops into the atmosphere. During the night, they react very rapidly with the nitrate radical (NO3), leading to the formation of a variety of functionalized products including organic nitrates and to large amounts of secondary organic aerosols (SOAs). Organic nitrates (ONs) have been shown not only to play a key role in the transport of reactive nitrogen and consequently in the ozone budget but also to be important components of the total organic-aerosol mass, while SOAs are known to play a direct and indirect role in the climate. However, the reactivity of BVOCs with NO3 remains poorly studied. The aim of this work is to provide new kinetic and mechanistic data for two monoterpenes (C10H16), α- and γ-terpinene, through experiments in simulation chambers. These two compounds, which have very similar chemical structures, have been chosen in order not only to overcome the lack of experimental data but also to highlight the influence of the chemical structure on the reactivity. Rate constants have been measured using both relative and absolute methods. They were found to be (1.2±0.5)×10-10 and (2.9±1.1)×10-11 cm3 molecule−1 s−1 for α- and γ-terpinene respectively. Mechanistic studies have also been conducted in order to identify and quantify the main reaction products. Total organic nitrate and SOA yields have been determined. While organic nitrate formation yields appear to be similar, SOA yields exhibit large differences with γ-terpinene being a much more efficient precursor of aerosols. In order to provide explanations for this difference, chemical analysis of the gas-phase products was performed at the molecular scale. Detected products allowed for proposing chemical mechanisms and providing explanations through peroxy and alkoxy reaction pathways.

Autoxidation mechanism for atmospheric oxidation of tertiary amines: Implications for secondary organic aerosol formation

Tertiary amines are one kind of identified amines in the atmosphere. Here, the atmospheric oxidation mechanism and kinetics of tertiary amines were investigated by using computational methods. As proxies of these amines, trimethylamine (TMA) and triethylamine (TEA) have been selected. Results indicate that N-containing peroxy radicals (NRO2⋅), which are key intermediates in ⋅OH initiated oxidation of TMA and TEA, can follow a so-called autoxidation mechanism (a chain reaction of H-shift followed by O2 addition) even on the condition of high NO/HO2⋅ concentration. Such unique mechanism can be ascribed to the ability of N-atom in facilitating the unimolecular H-shift of NRO2⋅ and the absence of H-atoms on N-atom. However, different from TMA reaction system, the pathway dissociating into fragmental products can compete with the autoxidation pathway for TEA system. More importantly, TEA reaction system cannot lead to the formation of products with high O/C ratio due to the autoxidation pathway terminated by the release of fragmental molecules. Such difference can be corroborated by previously observing lower secondary organic aerosol yield of TEA oxidation than that of TMA oxidation. The unveiled mechanism enhances current understanding on atmospheric fate of amines and autoxidation mechanism.

Role of Relative Humidity in the Secondary Organic Aerosol Formation from High-NOx Photooxidation of Long-Chain Alkanes: n-Dodecane Case Study

The role of relative humidity (RH) in secondary organic aerosol (SOA) formation from high-NOx photooxidation of long-chain alkanes was investigated by performing simulation chamber experiments on n-dodecane (C12H26). This molecule was chosen as a model compound for the class of long-chain alkanes. The experiments span a wide range of RH conditions from <1 to 70%. The humidity was found to reduce the SOA production yield by a factor of 2, from extremely dry (<1%) to humid (RH ≥ 5%) conditions. Measurements of major oxidation products in the gaseous and aerosol phases revealed the effect of water on a series of multiphasic reaction mechanisms and SOA production. Under very low RH, an acid-catalyzed “dehydration” reaction of polyfunctional molecules leads to lower volatility products. This pathway was found to be inhibited from dry to ambient RH conditions, explaining the SOA yield reduction. In addition to the previously established carbonyls and hydroxycarbonyls, novel tracers, that is, lactone and carboxylic acid, were identified using authentic standards, providing evidence for water-sensitive multiphasic pathways. Among the species formed via the dehydration channel, we find not only volatile species but also very reactive intermediates (e.g., dihydrofurans) which partition back to the gas phase. Owing to its double bond, it can be further oxidized to lower volatility secondary products, which forms a complex multiphasic scheme involving many condensation reaction–evaporation steps.

Measurements of higher alkanes using NO&amp;lt;sup&amp;gt;+&amp;lt;/sup&amp;gt; chemical ionization in PTR-ToF-MS: important contributions of higher alkanes to secondary organic aerosols in China

Abstract. Higher alkanes are a major class of intermediate-volatility organic compounds (IVOCs), which have been proposed to be important precursors of secondary organic aerosols (SOA) in the atmosphere. Accurate estimation of SOA from higher alkanes and their oxidation processes in the atmosphere is limited, partially due to the difficulty of their measurement. High-time-resolution (10 s) measurements of higher alkanes were performed using NO+ chemical ionization in proton transfer reaction time-of-flight mass spectrometry (NO+ PTR-ToF-MS) at an urban site in Guangzhou in the Pearl River Delta (PRD) and at a rural site in the North China Plain (NCP). High concentrations were observed in both environments, with significant diurnal variations. At both sites, SOA production from higher alkanes is estimated from their photochemical losses and SOA yields. Higher alkanes account for significant fractions of SOA formation at the two sites, with average contributions of 7.0 % ± 8.0 % in Guangzhou and 9.4 % ± 9.1 % in NCP, which are comparable to or even higher than both single-ring aromatics and naphthalenes. The significant contributions of higher alkanes to SOA formation suggests that they should be explicitly included in current models for SOA formation. Our work also highlights the importance of NO+ PTR-ToF-MS in measuring higher alkanes and quantifying their contributions to SOA formation.

Secondary organic aerosol formation from the ozonolysis and oh-photooxidation of 2,5-dimethylfuran

In this study, the O3 and OH radical oxidation of 2,5-dimethylfuran (2,5-DMF) were investigated in two different chambers at (296±1) K and atmospheric pressure to examine secondary organic aerosol (SOA) formation. Results for OH-photooxidation indicate that SOA yieldsdecrease (from 6.2 to 0.4) with the rise of 2,5-DMF concentration (from10 to 1000 ppb). In the absence of NOx and under high relative humidity (RH) conditions (60%), higher aerosol yields are favoured. SOA formation is dependent on the initial seed surface for two kinds of inorganic seed particles ((NH4)2SO4 and CaCl2), being the effect slightly greater for CaCl2. The ozonolysis only generates particles in the presence of SO2 and the increase of relative humidity from 0 to 15% lowers the particle number and particle mass concentrations. The water-to-SO2 rate constant ratio of the Criegee intermediate was derived from the SOA yield in experiments with different relative humidity values, with kH2O/kSO2 = (1.6±0.4)x10−5.

Study of Secondary Organic Aerosol Formation from Chlorine Radical-Initiated Oxidation of Volatile Organic Compounds in a Polluted Atmosphere Using a 3D Chemical Transport Model.

The impact of chlorine (Cl) chemistry on the formation of secondary organic aerosol (SOA) during a severe wintertime air pollution episode is investigated in this study. The Community Multiscale Air Quality (CMAQ) model v5.0.1 with a modified SAPRC-11 gas-phase mechanism and heterogeneous reactions for reactive chlorine species is updated to include the formation of chlorine radical (Cl•)-initiated SOA (Cl-SOA) from aromatic compounds, terpenes, and isoprene. Reported SOA yield data on Cl-SOA formation from environmental chamber studies are used to derive the mass yield and volatility data for the two-product equilibrium-partitioning model. The heterogeneous reaction of particulate chloride (pCl-) leads to a significant increase in the Cl• and hydroxyl radical (OH) concentrations throughout the domain. Monthly Cl-SOA concentrations range from 0.7 to 3.0 μg m-3, with increasing anthropogenic Cl emissions leading to higher Cl-SOA concentrations. Indirectly, this also leads to an increase of monthly SOA by up to 2.5-3.0 g μm-3 from the traditional OH oxidation pathways as well as the surface uptake of glyoxal and methylglyoxal. Increased OH concentrations, however, do not always lead to higher overall SOA concentrations in the entire domain. High OH reduces the lifetime of glyoxal/methylglyoxal (GLY/MGLY), making them less available to form SOA. In the Sichuan Basin (SCB) and part of Southwest China where high O3 concentrations meet high pCl emissions, a higher Cl•/OH ratio leads to net O3 loss from the Cl• + O3 reaction, thus reducing SOA formation from the O3 oxidation of volatile organic compounds (VOCs). Also, the competition between Cl• and OH for VOCs could lead to lower overall SOA because the molar yields of the semivolatile products in Cl-VOC reactions are lower than their OH + VOC reaction counterparts. When Cl• concentrations are further increased with higher emissions of Cl, precursor gases can be depleted and become the limiting factor in SOA formation. This study reveals the direct and indirect impacts of chlorine chemistry on SOA in polluted winter conditions, which are greatly affected by the Cl emissions, the ambient O3 level, and the availability of SOA precursors.

Relative contributions of selected multigeneration products to chamber SOA formed from photooxidation of a range (C10–C17) of n-alkanes under high NOx conditions

A series of chamber experiments was conducted to investigate the composition of secondary organic aerosol (SOA) following oxidation of a range of parent n-alkanes (C10–C17) in the presence of NOx. The relative contribution of selected species representing first, second, and higher generation products to SOA mass was measured using a high-resolution aerosol mass spectrometer. Gas chromatography was also used for a limited set of amenable species. Relative contributions varied substantially across the range of investigated alkanes reflecting slight changes in SOA composition. The contribution of first-generation cyclic hemiacetal is minimal toward the small end of the investigated range and gradually increases with n-alkane size. The relative contributions of second generation and higher nitrate-containing species, in contrast, decrease with an increased alkane size. A similar trend is observed for relative contribution of organonitrates to SOA. Finally, SOA yield and composition are sensitive to water vapor concentrations. This sensitivity is limited to a narrow range (dry to ~15% RH) with little, if any, impact above 15% suggesting that this impact may be negligible under ambient conditions. The impact of water vapor also appears to decrease with increasing alkane carbon number.

A large-scale outdoor atmospheric simulation smog chamber for studying atmospheric photochemical processes: Characterization and preliminary application

Understanding the formation mechanisms of secondary air pollution is very important for the formulation of air pollution control countermeasures in China. Thus, a large-scale outdoor atmospheric simulation smog chamber was constructed at Chinese Research Academy of Environmental Sciences (the CRAES Chamber), which was designed for simulating the atmospheric photochemical processes under the conditions close to the real atmospheric environment. The chamber consisted of a 56-m3 fluorinated ethylene propylene (FEP) Teflon film reactor, an electrically-driven stainless steel alloy shield, an auxiliary system, and multiple detection instrumentations. By performing a series of characterization experiments, we obtained basic parameters of the CRAES chamber, such as the mixing ability, the background reactivity, and the wall loss rates of gaseous compounds (propene, NO, NO2, ozone) and aerosols (ammonium sulfate). Oxidation experiments were also performed to study the formation of ozone and secondary organic aerosol (SOA), including α-pinene ozonolysis, propene and 1,3,5-trimethylbenzene photooxidation. Temperature and seed effects on the vapor wall loss and SOA yields were obtained in this work: higher temperature and the presence of seed could reduce the vapor wall loss; SOA yield was found to depend inversely on temperature, and the presence of seed could increase SOA yield. The seed was suggested to be used in the chamber to reduce the interaction between the gas phase and chamber walls. The results above showed that the CRAES chamber was reliable and could meet the demands for investigating tropospheric chemistry.

Always Lost but Never Forgotten: Gas-Phase Wall Losses Are Important in All Teflon Environmental Chambers.

Yields of secondary organic aerosol (SOA) formation from oxidation of volatile organic compounds are measured in laboratory chambers and then applied in regional and global models. Gas-phase losses to large Teflon-walled environmental chambers have been recently shown to reduce SOA yields. Historically, most chambers have operated in batch mode. Increasingly, however, continuous flow (CF) mode is being used, in which reactants and products are continuously introduced and exhausted from the chamber. Recent literature reports indicate a belief that SOA yields measured in CF chambers are not affected by gas-phase wall losses (GWL). Here, we use an experimentally-constrained box model to show that gas-phase wall losses impact both types of chambers when run under similar conditions. We find CF experiments do mitigate some effects of gas-phase wall losses after long (>2 days) experiment run times, but they have significant losses for typical literature experiment times of 1 day. However, this mitigation phenomenon is an experiment- and mechanism-dependent, and GWL still affects the absolute SOA yield. Finally, we show that at condensation sink values higher than the wall loss rate a lack of change in yield vs seed surface area does not necessarily indicate whether GWL affects the experiment and does not suggest the magnitude.

Measuring Biosphere-Atmosphere Exchange of Short-Lived Climate Forcers and Their Precursors.

Exchange of reactive trace gases over the biosphere is a key source of reactive organic carbon to the atmosphere and thus influences the formation of both ozone (O3) and secondary organic aerosol (SOA). Both O3 and aerosol particles are short-lived climate forcers and impact the radiative balance of the planet, and their sources and sinks are chemically complex. However, the biosphere also acts as a deposition sink for organic and inorganic compounds, including O3, aerosols, and their precursors. Wet and dry deposition provides a key lever on the lifetime of trace gases and particles in the atmosphere and thus on their potential to influence the radiative balance of the planet. The fluxes of reactive trace gases and particles are part of an atmospheric biogeochemical cycle that includes feedbacks through drought and other climate components.Recent advances in measurement techniques have enabled new field observations of trace gas and particle fluxes. Our method development has focused on the leaf, branch, and forest level, although satellite measurements coupled to modeling also provide promising new approaches to constraining trace gas fluxes. Leaf chamber measurements of volatile organic compound (VOC) emissions highlight leaf-to-leaf and plant-to-plant variability in both photosynthesis and emissions of individual VOCs, in addition to differences in emissions across different isomers of monoterpenes. Isomers obviously have different chemical properties (e.g., reaction rates with OH radicals, SOA yield) and thus hold different potentials as precursors for short-lived climate forcers.The biosphere acts as both sources and sinks of the oxidation products of monoterpenes and other biogenic VOCs. Developments in chemical ionization mass spectrometry have recently enabled measurements of volatile organic acids, which demonstrate a strong temperature-dependent ecosystem source, as well as a source from in-canopy chemistry. In-canopy chemistry also influences particle fluxes, although deposition should dominate their net exchange. Our field observations of chemically resolved particle fluxes demonstrate the simultaneous, competing processes driving forest exchange. To separate out these competing processes, we use black carbon as an inert tracer for particle deposition. Our recent measurements demonstrate the importance of wet deposition in controlling particle lifetime in the atmosphere. Overall, new measurement techniques have enabled both field and laboratory observations to improve our understanding of biosphere-atmosphere interactions and their influence on climate processes.

Gas-Phase Reaction of trans-2-Methyl-2-butenal with Cl: Kinetics, Gaseous Products, and SOA Formation

The gas-phase reaction between trans-2-methyl-2-butenal and chlorine (Cl) atoms has been studied in a simulation chamber at 298 ± 2 K and 760 ± 5 Torr of air under free-NOx conditions. The rate coefficient of this reaction was determined as k = (2.45 ± 0.32) × 10-10 cm3 molecule−1 s−1 by using a relative method and Fourier transform infrared spectroscopy. In addition to this technique, gas chromatography coupled to mass spectrometry and proton transfer time-of-flight mass spectrometry were used to detect and monitor the time evolution of the gas-phase reaction products. The major primary reaction product from the addition of Cl to the C-3 of trans-2-methyl-2-butenal was 3-chloro-2-butanone, with a molar yield (YProd) of (52.5 ± 7.3)%. Acetaldehyde (Y = (40.8 ± 0.6)%) and HCl were also identified, indicating that the H-abstraction by Cl from the aldehyde group is a reaction pathway as well. Secondary organic aerosol (SOA) formation was investigated by using a fast mobility particle sizer spectrometer. The SOA yield in the Cl + trans-2-methyl-2-butenal reaction is reported to be lower than 2.4%, thus its impact can be considered negligible. The atmospheric importance of the titled reaction is similar to the corresponding OH reaction in areas with high Cl concentration.

A Near-Explicit Mechanistic Evaluation of Isoprene Photochemical Secondary Organic Aerosol Formation and Evolution: Simulations of Multiple Chamber Experiments with and without Added NOx

Experimentally determined yields of secondary organic aerosol (SOA) from the photochemical oxidation of isoprene in the absence of aqueous acidic aerosol vary substantially, both within a given exp...

Effect of the nitrate group on yields and composition of secondary organic aerosol formed from reactions of alkyl nitrates with OH radicals in the presence of NOx

A systematic study was conducted on the effect of a nitrate functional group on secondary organic aerosol (SOA) products and yields from reactions of C10 alkyl nitrate isomers with OH radicals in the presence of NOx. The 1- through 5-decyl nitrate isomers were synthesized from their corresponding alcohols, reacted in an environmental chamber, and the precursors and SOA were analyzed using online and offline techniques. SOA products were analogous to those formed from similar reactions of the C10 n-alkane (decane), but with an additional nitrate group. The SOA yield was highest when the nitrate group was on the terminal carbon and decreased monotonically from 0.51 to 0.50, 0.44, 0.28, and 0.15 as it moved toward the center of the molecule, at which point it was similar to that from decane. The explanation for this trend, which is supported by results of calculations performed using a kinetics model, involves a combination of the effects of the nitrate group on product vapor pressures and reaction branching ratios. In general, although the nitrate group lowers the vapor pressures of products relative to the corresponding products of the decane reaction, thus enhancing gas-to-particle partitioning and SOA formation, as it moves toward the center of the molecule it also alters the branching ratios for reaction pathways so as to enhance the formation of more volatile products. The results are compared with those from similar studies on ketone and alcohol isomers to gain a more comprehensive understanding of the effects of functional groups on SOA composition and yields.Copyright © 2020 American Association for Aerosol Research

Composition and volatility of secondary organic aerosol (SOA) formed from oxidation of real tree emissions compared to simplified volatile organic compound (VOC) systems

Abstract. Secondary organic aerosol (SOA) is an important constituent of the atmosphere where SOA particles are formed chiefly by the condensation or reactive uptake of oxidation products of volatile organic compounds (VOCs). The mass yield in SOA particle formation, as well as the chemical composition and volatility of the particles, is determined by the identity of the VOC precursor(s) and the oxidation conditions they experience. In this study, we used an oxidation flow reactor to generate biogenic SOA from the oxidation of Scots pine emissions. Mass yields, chemical composition and volatility of the SOA particles were characterized and compared with SOA particles formed from oxidation of α-pinene and from a mixture of acyclic–monocyclic sesquiterpenes (farnesenes and bisabolenes), which are significant components of the Scots pine emissions. SOA mass yields for Scots pine emissions dominated by farnesenes were lower than for α-pinene but higher than for the artificial mixture of farnesenes and bisabolenes. The reduction in the SOA yield in the farnesene- and bisabolene-dominated mixtures is due to exocyclic C=C bond scission in these acyclic–monocyclic sesquiterpenes during ozonolysis leading to smaller and generally more volatile products. SOA particles from the oxidation of Scots pine emissions had similar or lower volatility than SOA particles formed from either a single precursor or a simple mixture of VOCs. Applying physical stress to the Scots pine plants increased their monoterpene, especially monocyclic β-phellandrene, emissions, which further decreased SOA particle volatility and increased SOA mass yield. Our results highlight the need to account for the chemical complexity and structure of real-world biogenic VOC emissions and stress-induced changes to plant emissions when modelling SOA production and properties in the atmosphere. These results emphasize that a simple increase or decrease in relative monoterpene and sesquiterpene emissions should not be used as an indicator of SOA particle volatility.

Effects of NOx and SO2 on the secondary organic aerosol formation from the photooxidation of 1,3,5-trimethylbenzene: A new source of organosulfates

1,3,5-Trimethylbeneze (TMB) is an important constituent of anthropogenic volatile organic compounds that contributes to the formation of secondary organic aerosol (SOA). A series of chamber experiments were performed to probe the effects of NOx and SO2 on SOA formation from TMB photooxidation. The molecular composition of TMB SOA was investigated by ultra-high performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS). We found that the SOA yield increases notably with elevated NOx concentrations under low-NOx condition ([TMB]0/[NOx]0 > 10 ppbC ppb−1), while an opposite trend is observed in high-NOx experiments ([TMB]0/[NOx]0 < 10 ppbC ppb−1). The increase in SOA yield in low-NOx regime is attributed to the increase of NOx-induced OH concentrations. The formation of low-volatility species might be suppressed, thereby leading to a lower SOA yield in high-NOx conditions. Moreover, SOA formation was promoted in experiment with SO2 addition. Multifunctional products containing carbonyl, acid, alcohol, and nitrate functional groups were characterized in TMB/NOx photooxidation, whereas several organosulfates (OSs) and nitrooxy organosulfates were identified in TMB/NOx/SO2 photooxidation based on HR-Q-TOFMS analysis. The formation mechanism relevant to the detected compounds in SOA were proposed. Based on our measurements, the photooxidation of TMB in the presence of SO2 may be a new source of OSs in the atmosphere. The results presented here also deepen the understanding of SOA formation under relatively complex polluted environments.