Secondary Organic Aerosol Yield Research Articles

Exploring the formation potential and optical properties of secondary organic aerosol from the photooxidation of selected short aliphatic ethers

Secondary organic aerosol (SOA) formation potential for six kinds of short aliphatic ethers has been studied. The size distribution, mass concentration, and yield of SOA formed by ethers photooxidation were determined under different conditions. The results showed that all six ethers can generate SOA via reaction with OH radicals even under no seed and NOx-free condition. The mass concentration for six seedless experiments was less than 10 µg/m3 and the SOA yields were all below 1%. The strong increase in the SOA formation was observed when the system contained ammonium sulfate seed particles, while SOA yield decreased under the high-NOx condition. SOA composition was analyzed using offline methods. Infrared spectra indicated that there are complex components in the particle-phase including carbonyls acid and aldehydes species. Moreover, the aqueous filter extracts were analyzed using ultraviolet-visible spectrometer and fluorescence spectrophotometer. For the fresh methyl n-butyl ether SOA, the largest absorption peak occurs at 280 nm and there exists slightly absorption in the 300–400 nm. Excitation-emission matrices display the distinct peak at excitation/emission = 470 nm/480 nm according to the fluorescence spectrum. These findings are important considerations of formation for ether SOA that can eventually be included in atmospheric models.

Simulation of organic aerosol formation during the CalNex study: updated mobile emissions and secondary organic aerosol parameterization for intermediate-volatility organic compounds.

We describe simulations using an updated version of the Community Multiscale Air Quality model version 5.3 (CMAQ v5.3) to investigate the contribution of intermediate-volatility organic compounds (IVOCs) to secondary organic aerosol (SOA) formation in southern California during the CalNex study. We first derive a model-ready parameterization for SOA formation from IVOC emissions from mobile sources. To account for SOA formation from both diesel and gasoline sources, the parameterization has six lumped precursor species that resolve both volatility and molecular structure (aromatic versus aliphatic). We also implement new mobile-source emission profiles that quantify all IVOCs based on direct measurements. The profiles have been released in SPECIATE 5.0. By incorporating both comprehensive mobile-source emission profiles for semivolatile organic compounds (SVOCs) and IVOCs and experimentally constrained SOA yields, this CMAQ configuration best represents the contribution of mobile sources to urban and regional ambient organic aerosol (OA). In the Los Angeles region, gasoline sources emit 4 times more non-methane organic gases (NMOGs) than diesel sources, but diesel emits roughly 3 times more IVOCs on an absolute basis. The revised model predicts all mobile sources (including on- and off-road gasoline, aircraft, and on- and off-road diesel) contribute ~ 1 μgm-3 to the daily peak SOA concentration in Pasadena. This represents a ~ 70% increase in predicted daily peak SOA formation compared to the base version of CMAQ. Therefore, IVOCs in mobile-source emissions contribute almost as much SOA as traditional precursors such as single-ring aromatics. However, accounting for these emissions in CMAQ does not reproduce measurements of either ambient SOA or IVOCs. To investigate the potential contribution of other IVOC sources, we performed two exploratory simulations with varying amounts of IVOC emissions from nonmobile sources. To close the mass balance of primary hydrocarbon IVOCs, IVOCs would need to account for 12% of NMOG emissions from nonmobile sources (or equivalently 30.7 t d-1 in the Los Angeles-Pasadena region), a value that is well within the reported range of IVOC content from volatile chemical products. To close the SOA mass balance and also explain the mildly oxygenated IVOCs in Pasadena, an additional 14.8% of nonmobile-source NMOG emissions would need to be IVOCs (assuming SOA yields from the mobile IVOCs apply to nonmobile IVOCs). However, an IVOC-to-NMOG ratio of 26.8% (or equivalently 68.5 t d-1 in the Los Angeles-Pasadena region) for nonmobile sources is likely unrealistically high. Our results highlight the important contribution of IVOCs to SOA production in the Los Angeles region but underscore that other uncertainties must be addressed (multigenerational aging, aqueous chemistry and vapor wall losses) to close the SOA mass balance. This research also highlights the effectiveness of regulations to reduce mobile-source emissions, which have in turn increased the relative importance of other sources, such as volatile chemical products.

Smog chamber study of the effects of NOx and NH3 on the formation of secondary organic aerosols and optical properties from photo-oxidation of toluene

Secondary organic aerosols (SOAs) have been receiving significant attention because of their significant impacts on air quality and human health. In this study, the influences of nitrogen oxides (NOx) and ammonia (NH3) on SOA formation from photooxidation of toluene was investigated in the Shanghai university smog chamber. The chemical and physical characteristics of gas-phase products and SOAs from toluene photo-oxidation were characterized using laboratory-developed single photon ionization time-of-flight mass spectrometry, single particle aerosol mass spectrometry, and cavity ring-down aerosol extinction albedo spectroscopy instruments. It was observed that increasing the initial nitrogen oxides ([NOx]0) under low-[NOx]0 conditions enhanced the SOA yield, while increasing [NOx]0 under high-[NOx]0 conditions suppressed the SOA yield. After adding NH3, the number concentration, average SOA diameter, and extinction and scattering coefficients showed an immediate and rapid increase due to the formation of significant amounts of condensable ammonium nitrate and nitrogen-containing (NOC) compounds. Moreover, a simplified reaction mechanism for the photooxidation of toluene initiated by the hydroxyl radical (OH) was believed to follow two reaction channels: minor H abstraction, and major OH addition, which continuously induced the subsequent reactions. The results of this study presented rapid analytical method for the joint use of a smog chamber with on-line analytical instruments to immediately characterize the effects of SOA formation, which will help in understanding the new particle formation and particle growth, and thus provides a new insight for in-depth understanding of the haze pollution in China.

NOx enhances secondary organic aerosol formation from nighttime γ-terpinene ozonolysis

As an important component of anthropogenic emissions, nitrogen oxides (NOx) are well known to interfere with daytime oxidation of biogenic volatile organic compounds (BVOCs) and secondary organic aerosol (SOA) formation. Nighttime chemistry is highly related to O3 and NOx level but, NOx effects on SOA formation from the ozonolysis of BVOCs, especially polyolefinic monoterpenes, have not been well understood. In the present study, SOA formation from pure and NOx-involved γ-terpinene ozonolysis was studied in a smog chamber under dark conditions. At atmospherically relevant particle mass loading of 10 μg m−3, the SOA yield from pure ozonolysis is estimated by a two-product model to be 8.6%. When NOx were incorporated into γ-terpinene ozonolysis, both the particle size and SOA yields increased simultaneously with elevated NOx mixing ratios. SOA yields doubled (from 0.38 to 0.77) when the system moved from NOx-free to [γ-terpinene]0/[NOx]0 = 3.5 (ppbC/ppb). The characteristic absorption of organic nitrates was detected by Fourier transform infrared (FTIR) spectroscopy and the fraction of organic nitrates increased with increasing NOx mixing ratios. Identification of the new constituents in SOA from NOx-involved γ-terpinene ozonolysis and their formation channels suggest that the formation of organic nitrates follows NO3 chemistry. NOx affects γ-terpinene ozonolysis via the enhanced generation of NO3 at high NOx and its subsequent more favored consumption of γ-terpinene than O3. The first-generation products from NO3 oxidation of γ-terpinene could be further oxidized by ozone, forming more oxidized products that contribute to SOA formation. Our investigation suggests that at night with high NOx levels, γ-terpinene may be a significant source of SOA and organic nitrates through anthropogenic-biogenic interactions.

Aqueous-Phase Production of Secondary Organic Aerosols from Oxidation of Dibenzothiophene (DBT)

Intermediate-volatility organic compounds (IVOCs) have been recognized as an important contributor to the secondary organic aerosol (SOA) formation via gas-phase reactions. However, it is unclear whether or not IVOCs-SOA can be produced in the aqueous phase. This work investigated aqueous oxidation of one model compound of IVOCs, dibenzothiophene (DBT). Results show that DBT can be degraded by both hydroxyl radical and the triplet excited states of organic light chromophores (3C*). Aqueous dark oxidation of DBT was also possible. SOA yields of 32% and 15% were found for hydroxyl radical (OH)-mediated photo-oxidation and dark oxidation, respectively. A continuous and significant increase of oxidation degree of SOA was observed during OH photo-oxidation, but not during the dark oxidation. Factor analyses revealed that there was a persistent production of highly oxygenated compounds from the less oxygenated species. OH-initiated photochemical reactions can also produce species with a relatively large light-absorbing ability, while such photo-enhancement due to direct light irradiation and 3C*-initiated oxidation could occur, but is much less important. In the future, studies on the second-order rate constants, molecular characterization of the oxidation products from this and other IVOCs precursors are needed to better understand the role of this reaction pathway in SOA budget, air quality and climate change.

Secondary organic aerosols from aromatic hydrocarbons and their contribution to fine particulate matter in Atlanta, Georgia

Tracers of secondary organic aerosols (SOA) from thirteen aromatic hydrocarbons were quantified in laboratory smog chamber experiments. Class-specific SOA tracers emerged, including 2,3-dihydroxy-4-oxo-pentatonic acid (DHOPA) from monoaromatic volatile organic compounds (VOCs), phthalic acid from naphthalene and 1-methylnaphthalene, and methyl-nitrocatechol isomers from o,m,p-cresol oxidation. Organic carbon mass fractions (fSOC) for these and other tracers were determined and extend the SOA tracer method widely used to apportion biogenic secondary organic carbon (SOC). The extended SOA tracer model was applied to evaluate the sources of SOC in Atlanta, GA during summer 2015 and winter 2016 after modifying the chamber-derived fSOC values to reflect SOA yields and local VOC levels (fSOC’). Monoaromatic, diaromatic, and cresol SOC contributed an average of 24%, 8%, and 0.12% of organic carbon (OC) mass during summer and 17%, 5%, and 0.27% during winter, respectively. Cresol SOC peaked during winter and was highly correlated with levoglucosan (r = 0.83, p < 0.001), consistent with its' precursors originating from biomass burning. Together, aromatic, biogenic, and biomass burning derived SOC accounted for an average of 77% and 28% of OC in summer and winter, respectively. The new understanding of SOA composition from aromatic VOCs advances the tracer-based method by including important precursors of SOC and enables a better understanding of the sources of atmospheric aerosol.

Secondary organic aerosol formation from OH-initiated oxidation of &amp;lt;i&amp;gt;m&amp;lt;/i&amp;gt;-xylene: effects of relative humidity on yield and chemical composition

Abstract. The effect of relative humidity (RH) on secondary organic aerosol (SOA) formation from the photooxidation of m-xylene initiated by OH radicals in the absence of seed particles was investigated in a Teflon reactor. The SOA yields were determined based on the particle mass concentrations measured with a scanning mobility particle sizer (SMPS) and reacted m-xylene concentrations measured with a gas chromatograph–mass spectrometer (GC-MS). The SOA components were analyzed using a Fourier transform infrared (FTIR) spectrometer and an ultrahigh-performance liquid chromatograph–electrospray ionization–high-resolution mass spectrometer (UPLC-ESI-HRMS). A significant decrease was observed in SOA mass concentration and yield variation with the increasing RH conditions. The SOA yields are 14.0 %–16.5 % and 0.8 %–3.2 % at low RH (14 %) and high RH (74 %–79 %), respectively, with the difference being nearly 1 order of magnitude. Some of the reduction in the apparent yield may be due to the faster wall loss of semi-volatile products of oxidation at higher RH. The chemical mechanism for explaining the RH effects on SOA formation from m-xylene–OH system is proposed based on the analysis of both FTIR and HRMS measurements, and the Master Chemical Mechanism (MCM) prediction is used as the assistant. The FTIR analysis shows that the proportion of oligomers with C-O-C groups from carbonyl compounds in SOA at high RH is higher than that at low RH, but further information cannot be provided by the FTIR results to well explain the negative RH effect on SOA formation. In the HRMS spectra, it is found that C2H2O is one of the most frequent mass differences at low and high RHs, that the compounds with a lower carbon number in the formula at low RH account for a larger proportion than those at high RH and that the compounds at high RH have higher O : C ratios than those at low RH. The HRMS results suggest that the RH may suppress oligomerization where water is involved as a by-product and may influence the further particle-phase reaction of highly oxygenated organic molecules (HOMs) formed in the gas phase. In addition, the negative RH effect on SOA formation is enlarged based on the gas-to-particle partitioning rule.

Aerosol Optical Tweezers Constrain the Morphology Evolution of Liquid-Liquid Phase-Separated Atmospheric Particles

Summary Chemical models of atmospheric particles are vital in understanding the role of aerosol particles in atmospheric chemistry, air pollution, human health, and climate change. Advancing these models requires new frameworks that can realistically predict how critical particle properties evolve. We present such a framework for predicting particle phase separation and which morphology will prevail; this controls how each particle interacts with and affects the atmosphere. We studied the mixing behavior of α-pinene secondary organic aerosol (SOA) with different organic phases, as relative humidity was varied to determine the interplay between polarity, miscibility, interfacial tension, and the resulting morphology. Using measurements from aerosol optical tweezers experiments and literature data, a general trend in morphology with increasing atmospheric oxidation was observed, from biphasic partially engulfed (where both phases are immediately accessible to the gas phase) to biphasic core shell (where the organic shell conceals the core) and finally to a single-phase, homogeneous morphology.

Exposure to Dimethyl Selenide (DMSe)-Derived Secondary Organic Aerosol Alters Transcriptomic Profiles in Human Airway Epithelial Cells.

Dimethyl selenide (DMSe) is one of the major volatile organoselenium compounds released from aquatic and terrestrial environments through microbial transformation and plant metabolism. The detailed processes of DMSe leading to secondary organic aerosol (SOA) formation and the pulmonary health effects induced by inhalation of DMSe-derived SOA remain largely unknown. In this study, we characterized the chemical composition and formation yields of SOA produced from the oxidation of DMSe with OH radicals and O3 in controlled chamber experiments. Further, we profiled the transcriptome-wide gene expression changes in human airway epithelial cells (BEAS-2B) after exposure to DMSe-derived SOA. Our analyses indicated a significantly higher SOA yield resulting from the OH-initiated oxidation of DMSe. The oxidative potential of DMSe-derived SOA, as measured by the dithiothreitol (DTT) assay, suggested the presence of oxidizing moieties in DMSe-derived SOA at levels higher than typical ambient aerosols. Utilizing RNA sequencing (RNA-Seq) techniques, gene expression profiling followed by pathway enrichment analysis revealed several major biological pathways perturbed by DMSe-derived SOA, including elevated genotoxicity, DNA damage, and p53-mediated stress responses, as well as downregulated cholesterol biosynthesis, glycolysis, and interleukin IL-4/IL-13 signaling. This study highlights the significance of DMSe-derived SOA as a stressor in human airway epithelial cells.

Aerosol mass yields of selected biogenic volatile organic compounds – a theoretical study with nearly explicit gas-phase chemistry

Abstract. In this study we modeled secondary organic aerosol (SOA) mass loadings from the oxidation (by O3, OH and NO3) of five representative biogenic volatile organic compounds (BVOCs): isoprene, endocyclic bond-containing monoterpenes (α-pinene and limonene), exocyclic double-bond compound (β-pinene) and a sesquiterpene (β-caryophyllene). The simulations were designed to replicate an idealized smog chamber and oxidative flow reactors (OFRs). The Master Chemical Mechanism (MCM) together with the peroxy radical autoxidation mechanism (PRAM) were used to simulate the gas-phase chemistry. The aim of this study was to compare the potency of MCM and MCM + PRAM in predicting SOA formation. SOA yields were in good agreement with experimental values for chamber simulations when MCM + PRAM was applied, while a stand-alone MCM underpredicted the SOA yields. Compared to experimental yields, the OFR simulations using MCM + PRAM yields were in good agreement for BVOCs oxidized by both O3 and OH. On the other hand, a stand-alone MCM underpredicted the SOA mass yields. SOA yields increased with decreasing temperatures and NO concentrations and vice versa. This highlights the limitations posed when using fixed SOA yields in a majority of global and regional models. Few compounds that play a crucial role (&gt;95 % of mass load) in contributing to SOA mass increase (using MCM + PRAM) are identified. The results further emphasized that incorporating PRAM in conjunction with MCM does improve SOA mass yield estimation.

Secondary organic aerosol formation from photooxidation of furan: effects of NO&amp;lt;sub&amp;gt;&amp;lt;i&amp;gt;x&amp;lt;/i&amp;gt;&amp;lt;/sub&amp;gt; and humidity

Abstract. Atmospheric furan is a primary and secondary pollutant in the atmosphere, and its emission contributes to the formation of ultrafine particles. We investigate the effects of NOx level and humidity on the formation of secondary organic aerosol (SOA) generated from the photooxidation of furan in the presence of NaCl seed particles. SOA mass concentration and yield were determined under different NOx and humidity levels. A significant difference is observed both in the variation of SOA mass concentration and SOA yield with the initial experimental conditions. Varying VOC (volatile organic compound) ∕ NOx ratios over the range 48.1 to 8.2 contributes to the effective formation of SOA in the presence of NaCl seed particles, with the SOA mass concentration and SOA yield ranging from 0.96 to 23.46 µg m−3 and from 0.04 % to 1.01 %, respectively. We found that there was a favourable relationship between the SOA yields and NOx concentration. In particular, the increase in SOA yield with increasing NOx concentration was continuously observed at high NOx levels owing to a corresponding increase in the amount of low-volatility hydroxyl nitrates and dihydroxyl dinitrates that can partition into the particle phase. In addition, varying relative humidity (RH) from 5 % to 88 % increased the SOA yield from 1.01 % to 5.03 %. The enhanced SOA formation from humid conditions may result from the high OH concentration, rapid furan decay rate, enhanced carbonyl-rich products condensation, and the aqueous-phase reactions. Using hybrid quadrupole-orbitrap mass spectrometer equipped with electrospray ionization (HESI-Q Exactive-Orbitrap MS), three carbonyl-rich products and three kinds of organonitrates were identified in the collected SOA. Based on the HESI-Q Exactive-Orbitrap MS analysis and Fourier transform infrared spectroscopy (FTIR), the reaction mechanism of furan photooxidation was proposed. This study demonstrates the effects of NOx and humidity on SOA formation during the furan–NOx–NaCl photooxidation and provides new insights into the oxidation regime and SOA composition in furan photooxidation. The results also illustrate the importance of studying SOA formation over a comprehensive range of environmental conditions. Only such evaluations can induce meaningful SOA mechanisms to be implemented in air quality models.

Photochemical Aging Alters Secondary Organic Aerosol Partitioning Behavior

Organic aerosol is the largest fraction of the atmospheric nonrefractory aerosol mass and has a significant impact on climate, visibility, and human health. A significant portion of organic aerosol is secondary organic aerosol (SOA), which forms when volatile organic compounds (VOCs) are oxidized and the reaction products partition to the particle phase. SOA formation and aging have been described using semivolatile partitioning theory, and a typical assumption invoked is that gas-particle partitioning rapidly reaches equilibrium. However, several studies have called into question whether traditional equilibrium assumptions are valid, either due to particle-phase diffusion limitations, particle-phase reactions, or liquid/liquid phase separation and immiscibility of organic phases. Here, we investigate the ability of equilibrium partitioning to describe laboratory SOA formation experiments using SOA mass and yield as the evaluation metric. We conduct two types of experiments: (1) co-condensation experiment...

Tropospheric fate of allyl cyanide (CH2[dbnd]CHCH2CN): Kinetics, reaction products and secondary organic aerosol formation

Allyl cyanide, CH2CHCH2CN, is a volatile organic compound that is emitted by biogenic and anthropogenic sources. Daytime atmospheric degradation of CH2CHCH2CN may be initiated by reaction with OH radicals, Cl atoms and O3. In this work, we report the gas-phase rate coefficients for the reaction of these atmospheric oxidants with CH2CHCH2CN (k1, k2 and k3, respectively) determined in an atmospheric simulation chamber at 298 ± 2 K and 760 ± 5 Torr of air, in a NOx-free environment. A relative kinetic method was employed for OH and Cl kinetic studies, obtaining k1 = (1.58 ± 0.39) × 10−11 cm3 molecule−1 s−1 and k2 = (2.26 ± 0.30) × 10−10 cm3 molecule−1 s−1. For the O3+CH2CHCH2CN reaction, k3 = (6.01 ± 0.24) × 10−19 cm3 molecule−1 s−1 was obtained using an absolute kinetic method under pseudo-first order conditions (excess of allyl cyanide). In both cases, Fourier Transform Infrared (FTIR) spectroscopy was used for monitoring the loss of CH2CHCH2CN relative to the loss of a reference compound and the loss of ozone, respectively. The estimated tropospheric lifetime considering all the homogeneous processes evaluated in this work is 16 h, with the major degradation route being the reaction with OH radicals. Gas-phase products detected in the IR spectrum have been identified by comparison with IR experimental spectra and/or theoretical spectra computed using density functional theory (DFT) calculations. In the Cl and O3 reactions, among others, HC(O)CN, HC(O)CH2CN, HC(O)H, and CO were identified as products, indicating that these reactions proceed mainly by addition of the oxidant to the double bond of CH2CHCH2CN. Even though allyl cyanide absorbs in the atmospheric IR window, due to its short lifetime it has a negligible contribution to the radiative forcing of climate. The formation of secondary organic aerosols (SOAs) has been investigated in the Cl reaction by a Fast Particle Mobility Sizer spectrometer. The determined SOA yield is lower than 6%, which could indicate a negligible impact on human health that could also be extrapolated to the OH reaction.

Influence of High Relative Humidity on Secondary Organic Carbon: Observations at a Background Site in East China

To investigate the impacts of relative humidity (RH) on secondary organic aerosol (SOA) concentrations and chemical reactions, the carbonaceous aerosol components [i.e., organic carbon (OC) and element carbon (EC)] were quantified in daily PM2.5 samples collected at a background site in East China during summer 2015. Based on the method of EC-tracer, the concentration of secondary organic carbon (SOC) demonstrated an obvious negative relationship with RH higher than 60%. Moreover, the ratio of SOC/EC also exhibited obvious decreasing trends with increasing RH, indicating negative effects for chemical production of SOA under high RH conditions. Due to high RH, photochemistry was weakened, gaseous oxidant concentrations was lowered (e.g., significantly decreased O3 levels), and the production rates of SOA were relatively low. On the other hand, because of more water uptake under higher RH conditions, the aerosol droplet acidity was reduced and enhancement of SOA formation by acidity was accordingly absent. In addition, high RH also plays an important role in changing viscosity of pre-existing aerosol coatings, which can affect reactive uptake yield of SOA. Overall, the results from this study imply that SOA production may be more associated with photochemical processes, while aqueous-phase chemistry is not very important for some SOA formation in a moist ambient environment. In the ambient atmosphere, oxidant concentrations, reaction rates, airborne species, etc., are highly variable. How do these factors affect SOA yields under given ambient environment warrants further detailed investigations.

Primary particulate matter emissions and estimates of secondary organic aerosol formation potential from the exhaust of a China V diesel engine

Vehicle emissions contribute to ambient particulate matter (PM) pollution directly via emissions of PM and indirectly by secondary aerosol formation, as a result of trace gas emissions. In this paper, we determined the emission factors of primary pollutants and estimated the secondary organic aerosol (SOA) formation potential of a China V heavy-duty diesel engine tested under ETC (European Transient Cycle) and ESC (European Stationary Cycle) with different types of fuels using an engine dynamometer. Volatile organic compounds (VOCs) emission factors were 55.7–121 mg/kwh, while primary PM emission factors were 15.0–26.8 mg/kwh. These values were substantially lower than those of older diesel vehicles that met pre-China V standards. Based on the SOA yields of the measured VOCs, the SOA formation potential of diesel engines were estimated to be 2.8–15.9 mg/kg fuel. The ratios of potential SOA/primary PM ranged from 0.07 to 0.16. We further showed that VOCs emission factors, SOA formation potential and the ratios of SOA/primary PM were highly dependent on the test cycle, whereas the primary PM emission factors on both test cycles and fuel quality.

Quantification of the impact of cooking processes on indoor concentrations of volatile organic species and primary and secondary organic aerosols.

Cooking is recognized as an important source of particulate pollution in indoor and outdoor environments. We conducted more than 100 individual experiments to characterize the particulate and non‐methane organic gas emissions from various cooking processes, their reaction rates, and their secondary organic aerosol yields. We used this emission data to develop a box model, for simulating the cooking emission concentrations in a typical European home and the indoor gas‐phase reactions leading to secondary organic aerosol production. Our results suggest that about half of the indoor primary organic aerosol emission rates can be explained by cooking. Emission rates of larger and unsaturated aldehydes likely are dominated by cooking while the emission rates of terpenes are negligible. We found that cooking dominates the particulate and gas‐phase air pollution in non‐smoking European households exceeding 1000 μg m−3. While frying processes are the main driver of aldehyde emissions, terpenes are mostly emitted due to the use of condiments. The secondary aerosol production is negligible with around 2 μg m−3. Our results further show that ambient cooking organic aerosol concentrations can only be explained by super‐polluters like restaurants. The model offers a comprehensive framework for identifying the main parameters controlling indoor gas‐ and particle‐phase concentrations.

Chamber-based insights into the factors controlling epoxydiol (IEPOX) secondary organic aerosol (SOA) yield, composition, and volatility

Abstract. We present measurements utilizing the Filter Inlet for Gases and Aerosols (FIGAERO) applied to chamber measurements of isoprene-derived epoxydiol (IEPOX) reactive uptake to aqueous acidic particles and associated secondary organic aerosol (SOA) formation. Similar to recent field observations with the same instrument, we detect two molecular components desorbing from the IEPOX SOA in high abundance: C5H12O4 and C5H10O3. The thermal desorption signal of the former, presumably 2-methyltetrols, exhibits two distinct maxima, suggesting it arises from at least two different SOA components with significantly different effective volatilities. Isothermal evaporation experiments illustrate that the most abundant component giving rise to C5H12O4 is semi-volatile, undergoing nearly complete evaporation within 1 h while the second, less volatile component remains unperturbed and even increases in abundance. We thus confirm, using controlled laboratory studies, recent analyses of ambient SOA measurements showing that IEPOX SOA is of very low volatility and commonly measured IEPOX SOA tracers such as C5H12O4 and C5H10O3, presumably 2-methyltetrols and C5-alkene triols or 3-MeTHF-3,4-diols, result predominantly from thermal decomposition in the FIGAERO-CIMS. We infer that other measurement techniques using thermal desorption or prolonged heating for analysis of SOA components may also lead to reported 2-methyltetrols and C5-alkene triols or 3-MeTHF-3,4-diol structures. We further show that IEPOX SOA volatility continues to evolve via acidity-enhanced accretion chemistry on the timescale of hours, potentially involving both 2-methyltetrols and organosulfates.

A new model mechanism for atmospheric oxidation of isoprene: global effects on oxidants, nitrogen oxides, organic products, and secondary organic aerosol

Abstract. Atmospheric oxidation of isoprene, the most abundantly emitted non-methane hydrocarbon, affects the abundances of ozone (O3), the hydroxyl radical (OH), nitrogen oxide radicals (NOx), carbon monoxide (CO), oxygenated and nitrated organic compounds, and secondary organic aerosol (SOA). We analyze these effects in box models and in the global GEOS-Chem chemical transport model using the new reduced Caltech isoprene mechanism (RCIM) condensed from a recently developed explicit isoprene oxidation mechanism. We find many similarities with previous global models of isoprene chemistry along with a number of important differences. Proper accounting of the isomer distribution of peroxy radicals following the addition of OH and O2 to isoprene influences the subsequent distribution of products, decreasing in particular the yield of methacrolein and increasing the capacity of intramolecular hydrogen shifts to promptly regenerate OH. Hydrogen shift reactions throughout the mechanism lead to increased OH recycling, resulting in less depletion of OH under low-NO conditions than in previous mechanisms. Higher organonitrate yields and faster tertiary nitrate hydrolysis lead to more efficient NOx removal by isoprene and conversion to inorganic nitrate. Only 20 % of isoprene-derived organonitrates (excluding peroxyacyl nitrates) are chemically recycled to NOx. The global yield of formaldehyde from isoprene is 22 % per carbon and less sensitive to NO than in previous mechanisms. The global molar yield of glyoxal is 2 %, much lower than in previous mechanisms because of deposition and aerosol uptake of glyoxal precursors. Global production of isoprene SOA is about one-third from each of the following: isoprene epoxydiols (IEPOX), organonitrates, and tetrafunctional compounds. We find a SOA yield from isoprene of 13 % per carbon, much higher than commonly assumed in models and likely offset by SOA chemical loss. We use the results of our simulations to further condense RCIM into a mini Caltech isoprene mechanism (Mini-CIM) for less expensive implementation in atmospheric models, with a total size (108 species, 345 reactions) comparable to currently used mechanisms.

The roles of volatile organic compound deposition and oxidation mechanisms in determining secondary organic aerosol production: a global perspective using the UKCA chemistry–climate model (vn8.4)

Abstract. The representation of volatile organic compound (VOC) deposition and oxidation mechanisms in the context of secondary organic aerosol (SOA) formation are developed in the United Kingdom Chemistry and Aerosol (UKCA) chemistry–climate model. Impacts of these developments on both the global SOA budget and model agreement with observations are quantified. Firstly, global model simulations were performed with varying VOC dry deposition and wet deposition fluxes. Including VOC dry deposition reduces the global annual-total SOA production rate by 2 %–32 %, with the range reflecting uncertainties in surface resistances. Including VOC wet deposition reduces the global annual-total SOA production rate by 15 % and is relatively insensitive to changes in effective Henry's law coefficients. Without precursor deposition, simulated SOA concentrations are lower than observed with a normalised mean bias (NMB) of −51 %. Hence, including SOA precursor deposition worsens model agreement with observations even further (NMB =-66 %). Secondly, for the anthropogenic and biomass burning VOC precursors of SOA (VOCANT∕BB), model simulations were performed by (a) varying the parent hydrocarbon reactivity, (b) varying the number of reaction intermediates, and (c) accounting for differences in volatility between oxidation products from various pathways. These changes were compared to a scheme where VOCANT∕BB adopts the reactivity of a monoterpene (α-pinene), and is oxidised in a single-step mechanism with a fixed SOA yield. By using the chemical reactivity of either benzene, toluene, or naphthalene for VOCANT∕BB, the global annual-total VOCANT∕BB oxidation rate changes by −3 %, −31 %, or −66 %, respectively, compared to when using α-pinene. Increasing the number of reaction intermediates, by introducing a peroxy radical (RO2), slightly slows the rate of SOA formation, but has no impact on the global annual-total SOA production rate. However, RO2 undergoes competitive oxidation reactions, forming products with substantially different volatilities. Accounting for the differences in product volatility between RO2 oxidation pathways increases the global SOA production rate by 153 % compared to using a single SOA yield. Overall, for relatively reactive compounds such as toluene and naphthalene, the reduction in reactivity for VOCANT∕BB oxidation is outweighed by accounting for the difference in volatility of RO2 products, leading to a net increase in the global annual-total SOA production rate of 85 % and 145 %, respectively, and improvements in model agreement (NMB of −46 % and 56 %, respectively). However, for benzene, the reduction in VOCANT∕BB oxidation is not outweighed by accounting for the difference in SOA yield pathways, leading to a small change in the global annual-total SOA production rate of −3 %, and a slight worsening of model agreement with observations (NMB =-77 %). These results highlight that variations in both VOC deposition and oxidation mechanisms contribute to substantial uncertainties in the global SOA budget and model agreement with observations.

A comprehensive investigation of aqueous-phase photochemical oxidation of 4-ethylphenol

Secondary organic aerosol (SOA) species formed in atmospheric aqueous phases is recently recognized as an important contributor to fine aerosols, which is known to be a prominent human health risk factor internationally. This work, for the first time, systematically investigated aqueous-phase photochemical oxidation of 4-ethylphenol (4-EP) - a model compound from biomass burning and a surrogate of intermediate volatility organic compounds, under both ultraviolet (UV) (Hg lamp) and simulated sunlight (Xe lamp). We found that 4-EP could degrade upon hydroxal radical (OH) oxidation under UV light nearly 15 times faster than that under simulated sunlight, but large aqueous SOA (aqSOA) yields (108%–122%) were observed under both situations. AqSOA masses and oxidation states continuously increased under simulated sunlight, yet they increased first then decreased quickly under UV light. We proposed a reaction scheme based on identified products, showing that oligomerization, functionalization and fragmentation all can occur during 4-EP oxidation. Our results demonstrate that OH radical may suppress oligomerization and functionalization, but is favorable for fragmentation. Under UV light with H2O2 (high OH), fragmentation was dominant, producing more volatile and smaller molecules, and less aqSOA in later oxidation; Under simulated sunlight with H2O2 (moderate OH), functionalization that can form hydroxylated monomer was more important. Moreover, 4-EP oxidation by the organic triplet excited state (3C*) could form species with stronger visible light absorptivity than those from OH-mediated oxidation, and the absorptivity showed positive link with contents of humic-like substances.