Total Secondary Organic Aerosol Research Articles

Species-specific effect of particle viscosity and particle-phase reactions on the formation of secondary organic aerosol

Secondary organic aerosol (SOA) is a major component of atmospheric fine particulate matter. Both particle viscosity and particle-phase chemistry play a crucial role in the formation and evolution of SOA; however, our understanding on how these two factors together with gas-phase chemistry collectively determine the formation of SOA is still limited. Here we developed a kinetic aerosol multilayer model coupled with gas-phase and particle-phase chemistry to simulate SOA formation. We take the atmospherically important α-pinene + OH oxidation system as an example application of the model. The simulations show that although the particle viscosity has negligible to small influences on the total SOA mass concentration, it strongly changes the concentration and distribution of individual compounds within the particle. This complicated effect of particle viscosity on SOA formation is a combined result of inhibited condensation or evaporation of specific organics due to slowed particle-phase diffusion. Furthermore, the particle-phase reactions alter the volatility and abundance of specific compounds and exacerbate their non-uniform distribution in highly viscous particles. Our results highlight an important species-specific effect of particle viscosity and particle-phase chemistry on SOA formation and demonstrate the capability of our model for quantifying such complicated effects on SOA formation and evolution.

Anthropogenic-driven changes in concentrations and sources of winter volatile organic compounds in an urban environment in the Yangtze River Delta of China between 2013 and 2021

Volatile organic compounds (VOCs) serve as crucial precursors to surface ozone and secondary organic aerosols (SOA). In response to severe air pollution challenges, China has implemented key air quality control policies from 2013 to 2021. Despite these efforts, a comprehensive understanding of the chemical composition and sources of urban atmospheric VOCs and their responses to emission reduction measures remains limited. Our study focuses on analyzing VOCs composition and concentrations during the winters of 2013 and 2021 through online field observations in urban Nanjing, a typical city in the Yangtze River Delta region of China. Using a machine learning approach, we found a notable reduction in total VOCs concentration from 52.4 ± 30.4 ppb to 33.9 ± 21.6 ppb between the two years, with dominant contributions (approximately 94.3 %) associated with anthropogenic emission control. Furthermore, alkanes emerged as the major contributors (48.6 %) to such anthropogenic-driven decline. The total SOA formation potential decreased by approximately 27.4 %, with aromatics identified as the major contributing species. Positive matrix factorization analysis identified six sources. In 2013, prominent contributors were solid fuel combustion (43.6 %), vehicle emission (16.7 %), and paint and solvent use (12.8 %). By 2021, major sources shifted to solid fuel combustion (31.9 %), liquefied petroleum gas and natural gas (26.8 %), and vehicle emission (25.5 %). Solid fuel combustion emerged as the primary driver for total VOCs reduction. The lifetime carcinogenic risk in 2021 decreased by 72.6 % relative to 2013, emphasizing the need to address liquefied petroleum gas and natural gas source, and vehicle emissions for improved human health. Our findings contribute critical insights for policymakers working on effective air quality management.

Obscured Contribution of Oxygenated Intermediate-Volatility Organic Compounds to Secondary Organic Aerosol Formation from Gasoline Vehicle Emissions.

Secondary organic aerosol (SOA) formation from gasoline vehicles spanning a wide range of emission types was investigated using an oxidation flow reactor (OFR) by conducting chassis dynamometer tests. Aided by advanced mass spectrometric techniques, SOA precursors, including volatile organic compounds (VOCs) and intermediate/semivolatile organic compounds (I/SVOCs), were comprehensively characterized. The reconstructed SOA produced from the speciated VOCs and I/SVOCs can explain 69% of the SOA measured downstream of an OFR upon 0.5-3 days' OH exposure. While VOCs can only explain 10% of total SOA production, the contribution from I/SVOCs is 59%, with oxygenated I/SVOCs (O-I/SVOCs) taking up 20% of that contribution. O-I/SVOCs (e.g., benzylic or aliphatic aldehydes and ketones), as an obscured source, account for 16% of total nonmethane organic gas (NMOG) emission. More importantly, with the improvement in emission standards, the NMOG is effectively mitigated by 35% from China 4 to China 6, which is predominantly attributed to the decrease of VOCs. Real-time measurements of different NMOG components as well as SOA production further reveal that the current emission control measures, such as advances in engine and three-way catalytic converter (TWC) techniques, are effective in reducing the "light" SOA precursors (i.e., single-ring aromatics) but not for the I/SVOC emissions. Our results also highlight greater effects of O-I/SVOCs to SOA formation than previously observed and the urgent need for further investigation into their origins, i.e., incomplete combustion, lubricating oil, etc., which requires improvements in real-time molecular-level characterization of I/SVOC molecules and in turn will benefit the future design of control measures.

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

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

Observation-constrained kinetic modeling of isoprene SOA formation in the atmosphere

Abstract. Isoprene has the largest global non-methane hydrocarbon emission, and the oxidation of isoprene plays a crucial role in the formation of secondary organic aerosol (SOA). Two primary processes are known to contribute to SOA formation from isoprene oxidation: (1) the reactive uptake of isoprene-derived epoxides on acidic or aqueous particle surfaces and (2) the absorptive gas–particle partitioning of low-volatility oxidation products. In this study, we developed a new multiphase condensed isoprene oxidation mechanism that includes these processes with key molecular intermediates and products. The new mechanism was applied to simulate isoprene gas-phase oxidation products and SOA formation from previously published chamber experiments under a variety of conditions and atmospheric observations during the Southern Oxidant and Aerosol Studies (SOAS) field campaign. Our results show that SOA formation from most of the chamber experiments is reasonably reproduced using our mechanism, except when the concentration ratios of initial nitric oxide to isoprene exceed ∼ 2, the formed SOA is significantly underpredicted. The SOAS simulations also reasonably agree with the measurements regarding the diurnal pattern and concentrations of different product categories, while the total isoprene SOA remains underestimated. The molecular compositions of the modeled SOA indicate that multifunctional low-volatility products contribute to isoprene SOA more significantly than previously thought, with a median mass contribution of ∼ 57 % to the total modeled isoprene SOA. However, this contribution is intricately intertwined with IEPOX-derived SOA (IEPOX: isoprene-derived epoxydiols), posing challenges for their differentiation using bulk aerosol composition analysis (e.g., the aerosol mass spectrometer with positive matrix factorization). Furthermore, the SOA from these pathways may vary greatly, mainly dependent on the volatility estimation and treatment of particle-phase processes (i.e., photolysis and hydrolysis). Our findings emphasize that the various pathways to produce these low-volatility species should be considered in models to more accurately predict isoprene SOA formation. The new condensed isoprene chemical mechanism can be further incorporated into regional-scale air quality models, such as the Community Multiscale Air Quality Modelling System (CMAQ), to assess isoprene SOA formation on a larger scale.

Modeling the molecular composition of secondary organic aerosol under highly polluted conditions: A case study in the Yangtze River Delta Region in China

A near-explicit mechanism, the master chemical mechanism (MCMv3.3.1), coupled with the Community Multiscale Air Quality (CMAQ) model (CMAQ-MCM-SOA), was applied to investigate the characteristics of secondary organic aerosol (SOA) during a pollution event in the Yangtze River Delta (YRD) region in summer 2018. Model performances in predicting explicit volatile organic compounds (VOCs), organic aerosol (OA), secondary organic carbon (SOC), and other related pollutants in Taizhou, as well as ozone (O3) and fine particulate matter (PM2.5) in multiple cities in this region, were evaluated against observations and model predictions by the CMAQ model coupled with a lumped photochemical mechanism (SAPRC07tic, S07). MCM and S07 exhibited similar performances in predicting gaseous species, while MCM better captured the observed PM2.5 and inorganic aerosols. Both models underpredicted OA concentrations. When excluding data during biomass burning events, SOC concentrations were underpredicted by the CMAQ-MCM-SOA model (−28.4 %) and overpredicted by the CMAQ-S07 model (134.4 %), with better agreement with observations in the trend captured by the CMAQ-MCM-SOA model. Dicarbonyl SOA accounted for a significant fraction of total SOA in the YRD, while organic nitrates originating from aromatics were the most abundant species contributing to the SOA formation from gas-particle partitioning. The oxygen-to‑carbon ratio (O/C) for SOA and OA were 0.68–0.75 and 0.20–0.65, respectively, indicating a higher oxidation state in the areas influenced by biogenic emissions. Finally, the phase state of SOA was examined by calculating the glass transition temperature (Tg) based on its molecular composition. It was found that semi-solid state characterized SOA in the YRD, which could potentially impact their chemical transformation and lifetimes along with those of their precursors.

Synthesis and Characterization of Organic Peroxides from Monoterpene-Derived Criegee Intermediates in Secondary Organic Aerosol.

Ozonolysis of alkenes is known to produce reactive intermediates─stabilized Criegee intermediates (SCIs), and their subsequent bimolecular reactions with various carboxylic acids can form α-acyloxyalkyl hydroperoxides (AAHPs), which is considered a major class of organic peroxides in secondary organic aerosol (SOA). Despite their atmospheric and health importance, the molecular-level identification of organic peroxides in atmospheric aerosols is highly challenging, preventing further assessment of their environmental fate. Here, we synthesize 20 atmospherically relevant AAHPs through liquid-phase ozonolysis, in which two types of monoterpene-derived SCIs from either α-pinene or 3-carene are scavenged by 10 different carboxylic acids to form AAHPs with diverse structures. These AAHPs are identified individually by liquid chromatography coupled with high-resolution mass spectrometry. AAHPs were previously thought to decompose quickly in an aqueous environment such as cloud droplets, but we demonstrate here that AAHPs hydrolysis rates are highly compound-dependent with rate constants differing by 2 orders of magnitude. In contrast, the aqueous-phase formation rate constants between SCI and various carboxylic acids vary only within a factor of 2-3. Finally, we identified two of the 20 synthesized AAHPs in α-pinene SOA and two in 3-carene SOA, contributing ∼0.3% to the total SOA mass. Our results improve the current molecular-level understanding of organic peroxides and are useful for a more accurate assessment of their environmental fate and health impact.

Contribution of intermediate-volatility organic compounds from on-road transport to secondary organic aerosol levels in Europe

Abstract. Atmospheric organic compounds with an effective saturation concentration (C∗) at 298 K between 103 and 106 µg m−3 are called intermediate-volatility organic compounds (IVOCs), and they have been identified as important secondary organic aerosol (SOA) precursors. In this work, we simulate IVOCs emitted from on-road diesel and gasoline vehicles over Europe with a chemical transport model (CTM), utilizing a new approach in which IVOCs are treated as lumped species that preserve their chemical characteristics. This approach allows us to assess both the overall contribution of IVOCs to SOA formation and the role of specific compounds. For the simulated early-summer period, the highest concentrations of SOA formed from the oxidation of on-road IVOCs (SOA-iv) are predicted for major European cities, like Paris, Athens, and Madrid. In these urban environments, on-road SOA-iv can account for up to a quarter of the predicted total SOA. Over Europe, unspeciated cyclic alkanes in the IVOC range are estimated to account for up to 72 % of the total on-road SOA-iv mass, with compounds with 15 to 20 carbons being the most prominent precursors. The sensitivity of the predicted SOA-iv concentrations to the selected parameters of the new lumping scheme is also investigated. Active multigenerational aging of the secondary aerosol products has the most significant effect as it increases the predicted SOA-iv concentrations by 67 %.

CAMx–UNIPAR simulation of secondary organic aerosol mass formed from multiphase reactions of hydrocarbons under the Central Valley urban atmospheres of California

Abstract. The UNIfied Partitioning-Aerosol phase Reaction (UNIPAR) model was integrated into the Comprehensive Air quality Model with extensions (CAMx) to process secondary organic aerosol (SOA) formation by capturing multiphase reactions of hydrocarbons (HCs) in regional scales. SOA growth was simulated using a wide range of anthropogenic HCs, including 10 aromatics and linear alkanes with different carbon lengths. The atmospheric processes of biogenic HCs (isoprene, terpenes, and sesquiterpene) were simulated for major oxidation paths (ozone, OH radicals, and nitrate radicals) to predict day and night SOA formation. The UNIPAR model streamlined the multiphase partitioning of the lumping species originating from semi-explicitly predicted gas products and their heterogeneous chemistry to form non-volatile oligomeric species in both organic aerosol and inorganic aqueous phase. The CAMx–UNIPAR model predicted SOA formation at four ground urban sites (San Jose, Sacramento, Fresno, and Bakersfield) in California, United States, during wintertime 2018. Overall, the simulated mass concentrations of the total organic matter, consisting of primary organic aerosol and SOA, showed a good agreement with the observations. The simulated SOA mass in the urban areas of California was predominated by alkane and terpene oxidation products. During the daytime, low-volatility products originating from the autoxidation of long-chain alkanes considerably contributed to the SOA mass. In contrast, a significant amount of nighttime SOA was produced by the reaction of terpene with ozone or nitrate radicals. The spatial distributions of anthropogenic SOA associated with aromatic and alkane HCs were noticeably affected by the southward wind direction, owing to the relatively long lifetime of their atmospheric oxidation, whereas those of biogenic SOA were nearly insensitive to wind direction. During wintertime 2018, the impact of inorganic aerosol hygroscopicity on the total SOA budget was not evident because of the small contribution of aromatic and isoprene products, which are hydrophilic and reactive in the inorganic aqueous phase. However, an increased isoprene SOA mass was predicted during the wet periods, although its contribution to the total SOA was little.

Characteristics of atmospheric non-methane hydrocarbon compounds (NMHCs) and their sources in urban typical secondary transformation in Beijing, China

Non-methane hydrocarbon compounds (NMHCs) paly the leading role in the formation of ozone (O3) and secondary organic aerosols (SOA), which can affect severely global climate change, air quality, and human health. NMHCs pollution became a meaningful and crucial research topic in Beijing. From the Eleventh Five-Year Plan to the present, volatile organic compounds (VOCs) have received widespread and great attention in environmental governance, especially the NMHCs. Due to successive stages to control air pollution, the concentration of NMHCs has dropped gradually nearly three years in Beijing. In this study, 54 NMHCs was measured from March 1 to March 30 in 2021. The mean concentration of NMHCs was 33.54 ± 16.69 ppbv during the whole observation period. The mean concentration of NMHCs was 40.69 ± 17.09 ppbv during the haze days, which was greater than non-haze days (26.68 ± 12.75 ppbv). Alkenes, alkanes, aromatics, and acetylene accounted for 34.22%, 33.02%, 32.60%, and 016% in total ozone formation potential (OFP), respectively. Aromatics accounted for 96.61% in total secondary organic aerosol potential (SOAP). All the sources of NMHCs (except for fuel evaporation) made non-negligible contribution to O3 formation. Solvent usage and gasoline exhaust contributed 52.19%, which were the largest contributor to SOAP. Therefore, Beijing should focus on the NMHCs pollution caused by the local emission (especially solvent usage and gasoline exhaust) to control and solve secondary pollution further in this study.

Linking gas, particulate, and toxic endpoints to air emissions in the Community Regional Atmospheric Chemistry Multiphase Mechanism (CRACMM)

Abstract. Chemical mechanisms describe the atmospheric transformations of organic and inorganic species and connect air emissions to secondary species such as ozone, fine particles, and hazardous air pollutants (HAPs) like formaldehyde. Recent advances in our understanding of several chemical systems and shifts in the drivers of atmospheric chemistry warrant updates to mechanisms used in chemical transport models such as the Community Multiscale Air Quality (CMAQ) modeling system. This work builds on the Regional Atmospheric Chemistry Mechanism version 2 (RACM2) and develops the Community Regional Atmospheric Chemistry Multiphase Mechanism (CRACMM) version 1.0, which demonstrates a fully coupled representation of chemistry leading to ozone and secondary organic aerosol (SOA) with consideration of HAPs. CRACMMv1.0 includes 178 gas-phase species, 51 particulate species, and 508 reactions spanning gas-phase and heterogeneous pathways. To support estimation of health risks associated with HAPs, nine species in CRACMM cover 50 % of the total cancer and 60 % of the total non-cancer emission-weighted toxicity estimated for primary HAPs from anthropogenic and biomass burning sources in the US, with the coverage of toxicity higher (> 80 %) when secondary formaldehyde and acrolein are considered. In addition, new mechanism species were added based on the importance of their emissions for the ozone, organic aerosol, or atmospheric burden of total reactive organic carbon (ROC): sesquiterpenes, furans, propylene glycol, alkane-like low- to intermediate-volatility organic compounds (9 species), low- to intermediate-volatility oxygenated species (16 species), intermediate-volatility aromatic hydrocarbons (2 species), and slowly reacting organic carbon. Intermediate- and lower-volatility organic compounds were estimated to increase the coverage of anthropogenic and biomass burning ROC emissions by 40 % compared to current operational mechanisms. Autoxidation, a gas-phase reaction particularly effective in producing SOA, was added for C10 and larger alkanes, aromatic hydrocarbons, sesquiterpenes, and monoterpene systems including second-generation aldehydes. Integrating the radical and SOA chemistry put additional constraints on both systems and enabled the implementation of previously unconsidered SOA pathways from phenolic and furanone compounds, which were predicted to account for ∼ 30 % of total aromatic hydrocarbon SOA under typical atmospheric conditions. CRACMM organic aerosol species were found to span the atmospherically relevant range of species carbon number, number of oxygens per carbon, and oxidation state with a slight high bias in the number of hydrogens per carbon. In total, 11 new emitted species were implemented as precursors to SOA compared to current CMAQv5.3.3 representations, resulting in a bottom-up prediction of SOA, which is required for accurate source attribution and the design of control strategies. CRACMMv1.0 is available in CMAQv5.4.

Secondary Organic Aerosol Formation from Semi-Volatile and Intermediate Volatility Organic Compounds in the Fall in Beijing

Intermediate volatility organic compounds (IVOCs) and semi-volatile organic compounds (SVOCs) have recently been proposed as important precursors of secondary organic aerosol (SOA). In the present work, 97 volatile organic compounds (VOCs) and 80 intermediate volatility and semi-volatile organic compounds (IVOCs and SVOCs) were measured by online gas chromatography-mass spectrometer/flame ionization detection (GC-MS/FID), and offline thermal desorption gas chromatography-mass spectrometer (TD-GC-MS), respectively. The average concentration of speciated VOCs, IVOCs, and SVOCs were 22.36 ± 9.02 μg m−3, 1.01 ± 0.32 μg m−3, and 0.10 ± 0.17 μg m−3. Alkanes and polycyclic aromatic hydrocarbons (PAHs) are the main compounds of total S/IVOCs. With the increase in molecular weight, the concentrations decreased in the gas phase, while increasing in the particle phase. Vehicular emission is the most significant source according to the carbon preference index (CPI) and the carbon of the most abundant alkane (Cmax). The yield method was used to estimate SOA from the oxidation of VOCs and S/IVOCs. The estimated SOA mass from IVOCs and SVOCs (0.70 ± 0.57 μg m−3) was comparable to that of VOCs (0.62 ± 0.61 μg m−3), and the oxidation of PAHs and alkanes took up 28.70 ± 8.26% and 51.97 ± 20.77% of the total SOA estimation, respectively. Compared to previous work, our study provided detailed molecular information of ambient S/IVOC species and elucidated their importance on SOA formation. Despite their low concentration, S/IVOCs species are important SOA precursors which shared comparable contribution compared with VOCs.

Quantification of primary and secondary organic aerosol sources by combined factor analysis of extractive electrospray ionisation and aerosol mass spectrometer measurements (EESI-TOF and AMS)

Abstract. Source apportionment studies have struggled to quantitatively link secondary organic aerosols (SOAs) to their precursor sources due largely to instrument limitations. For example, aerosol mass spectrometer (AMS) provides quantitative measurements of the total SOA fraction but lacks the chemical resolution to resolve most SOA sources. In contrast, instruments based on soft ionisation techniques, such as extractive electrospray ionisation mass spectrometry (EESI, e.g. the EESI time-of-flight mass spectrometer, EESI-TOF), have demonstrated the resolution to identify specific SOA sources but provide only a semi-quantitative apportionment due to uncertainties in the dependence of instrument sensitivity on molecular identity. We address this challenge by presenting a method for positive matrix factorisation (PMF) analysis on a single dataset which includes measurements from both AMS and EESI-TOF instruments, denoted “combined PMF” (cPMF). Because each factor profile includes both AMS and EESI-TOF components, the cPMF analysis maintains the source resolution capability of the EESI-TOF while also providing quantitative factor mass concentrations. Therefore, the bulk EESI-TOF sensitivity to each factor can also be directly determined from the analysis. We present metrics for ensuring that both instruments are well represented in the solution, a method for optionally constraining the profiles of factors that are detectable by one or both instruments, and a protocol for uncertainty analysis. As a proof of concept, the cPMF analysis was applied to summer and winter measurements in Zurich, Switzerland. Factors related to biogenic and wood-burning-derived SOAs are quantified, as well as POA sources such as wood burning, cigarette smoke, cooking, and traffic. The retrieved EESI-TOF factor-dependent sensitivities are consistent with both laboratory measurements of SOA from model precursors and bulk sensitivity parameterisations based on ion chemical formulae. The cPMF analysis shows that, with the standalone EESI-TOF PMF, in which factor-dependent sensitivities are not accounted for, some factors are significantly under- or overestimated. For example, when factor-dependent sensitivities are not considered in the winter dataset, the SOA fraction is underestimated by ∼25 % due to the high EESI-TOF sensitivity to components of primary biomass burning such as levoglucosan. In the summer dataset, where both SOA and total OA are dominated by monoterpene oxidation products, the uncorrected EESI-TOF underestimates the fraction of daytime SOA relative to nighttime SOA (in which organonitrates and less oxygenated CxHyOz molecules are enhanced). Although applied here to an AMS and EESI-TOF pairing, cPMF is suitable for the general case of a multi-instrument dataset, thereby providing a framework for exploiting semi-quantitative, high-resolution instrumentation for quantitative source apportionment.

Real-world emission characteristics of semivolatile/intermediate-volatility organic compounds originating from nonroad construction machinery in the working process

Detailed emission characterization of semivolatile/intermediate-volatility organic compounds (S/IVOCs) originating from nonroad construction machines (NRCMs) remains lacking in China. Twenty-one NRCMs were evaluated with a portable emission measurement system in the working process. Gas phase S/IVOCs were collected by Tenax TA tubes and analyzed via thermal desorption-gas chromatography–mass spectrometry (TD–GC–MS). Particle phase S/IVOCs were collected by quartz filters and analyzed via GC–MS. The average emission factors (EFs) for fuel-based total (gas + particle phase) IVOCs and SVOCs of the assessed NRCMs were 221.45 ± 194.60 and 11.68 ± 10.67 mg/kg fuel, respectively. Compared to excavators, the average IVOC and SVOC EFs of loaders were 1.32 and 1.55 times higher, respectively. Compared to the working mode, the average IVOC EFs under the moving mode (only moving forward or backward) were 1.28 times higher. The IVOC and SVOC EFs for excavators decreased by 69.06% and 38.37%, respectively, from China II to China III. These results demonstrate the effectiveness of emission control regulations. In regard to individual NRCMs, excavators and loaders were affected differently by emission standards. The volatility distribution demonstrated that IVOCs and SVOCs were dominated by gas- and particle-phase compounds, respectively. The mode of operation also affected S/IVOC gas-particle partitioning. Combined with previous studies, the mechanical type significantly affected the volatility distribution of IVOCs. IVOCs from higher volatile fuels are more distributed in the high-volatility interval. The total secondary organic aerosol (SOA) production potential was 104.36 ± 79.67 mg/kg fuel, which originated from VOCs (19.98%), IVOCs (73.87%), and SVOCs (6.15%). IVOCs were a larger SOA precursor than VOCs and SVOCs. In addition, normal (n-) alkanes were suitably correlated with IVOCs, which may represent a backup solution to quantify IVOC EFs. This work provides experimental data support for the refinement of the emission characteristics and emission inventories of S/IVOCs originating from NRCMs.

Source appointment of volatile organic compounds and evaluation of anthropogenic monoterpene emission estimates in Atlanta, Georgia

Emissions of monoterpenes from volatile chemical products (VCPs) have been shown to contribute substantially to secondary organic aerosol (SOA) formation in a number of cities across the US. In the southeast US (SE US), monoterpenes are the dominant precursor to SOA production. Previous studies have assumed that monoterpenes are primarily biogenic in origin. We examine that assumption here using a total of nine months of volatile organic compound (VOC) observations spanning across 2020 and 2021 which are made via proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) in Atlanta, Georgia. The dataset is resolved via non-negative matrix factorization (NNMF) into two biogenic, four anthropogenic, and two secondary factors. NNMF results show that VCP sources contribute to 0.28 ± 0.17 ppb of monoterpenes, or about 26% of all monoterpenes in the summer and 53% in the winter. Interannual comparison suggest minimum impact of the COVID-19 pandemic on atmospheric VOC composition in Atlanta during the second half of 2020. Comparison of NNMF anthropogenic monoterpenes-to-benzene ([Manthro/B]) and anthropogenic-to-total monoterpenes ([Manthro/MT]) ratios with emission ratios in the National Emission Inventory 2016v1 modeling platform (NEI16) and Fuel-Based Inventory of Vehicle Emissions and Volatile Chemical Products (FIVE-VCP) suggests that NEI16 underestimates anthropogenic monoterpene emissions by as much as 70% in Atlanta. FIVE-VCP estimates higher anthropogenic monoterpene emissions than NEI16 and provides better agreement with observations, especially during winter months. Anthropogenic monoterpenes may impact as much as 17% of total summertime SOA formation in Atlanta and the SE US, with potential additional influence of limonene from anthropogenic monoterpene sources due to its higher reactivity and SOA yield potential.

Measurement report: Effects of anthropogenic emissions and environmental factors on the formation of biogenic secondary organic aerosol (BSOA) in a coastal city of southeastern China

Abstract. To better understand the formation of biogenic secondary organic aerosol (BSOA), aerosol samples with a 4 h time resolution were collected during summer and winter in the southeast of China, along with online measurements of trace gases, aerosol chemical compositions, and meteorological parameters. The samples were analyzed by gas chromatography–mass spectrometry for PM2.5-bound secondary organic aerosol (SOA) tracers, including isoprene (SOAI), α/β-pinene (SOAM), β-caryophyllene (SOAC), and toluene (ASOA). The average concentrations of total SOA tracers in winter and summer were 38.8 and 111.9 ng m−3, respectively, with the predominance of SOAM (70.1 % and 45.8 %), followed by SOAI (14.0 % and 45.6 %), ASOA (11.0 % and 6.2 %) and SOAC (4.9 % and 2.3 %). Compared to those in winter, the majority of BSOA tracers in summer showed significant positive correlations with Ox (O3+NO2) (r = 0.443–0.808), HONO (r = 0.299–0.601), ultraviolet (UV) (r = 0.382–0.588) and temperature (T) (r = 0.529–0.852), indicating the influence of photochemical oxidation under relatively clean conditions. However, in winter, BSOA tracers were significantly correlated with PM2.5 (r = 0.407–0.867), NO3- (r = 0.416–0.884), SO42- (r = 0.419–0.813), and NH3 (r = 0.440–0.757), attributed to the contributions of anthropogenic emissions. Major BSOA tracers in both seasons were linearly correlated with aerosol acidity (pH) (r = 0.421–0.752), liquid water content (LWC) (r = 0.403–0.876) and SO42- (r = 0.419–0.813). The results indicated that acid-catalyzed reactive uptake onto sulfate aerosol particles enhanced the formation of BSOA. In summer, the clean air mass originated from the ocean, and chlorine depletion was observed. We also found that concentrations of the total SOA tracers were correlated with HCl (R2=0.545) and chlorine ions (r = 0.280–0.639) in PM2.5, reflecting the contribution of Cl-initiated volatile organic compound (VOC) oxidations to the formation of SOA. In winter, the northeast dominant wind direction brought continental polluted air mass to the monitoring site, affecting the transformation of BSOA tracers. This implied that anthropogenic emissions, atmospheric oxidation capacity and halogen chemistry have significant effects on the formation of BSOA in the southeast coastal area.

Chemical Structure Regulates the Formation of Secondary Organic Aerosol and Brown Carbon in Nitrate Radical Oxidation of Pyrroles and Methylpyrroles.

Nitrogen-containing heterocyclic volatile organic compounds (VOCs) are important components of wildfire emissions that are readily reactive toward nitrate radicals (NO3) during nighttime, but the oxidation mechanism and the potential formation of secondary organic aerosol (SOA) and brown carbon (BrC) are unclear. Here, NO3 oxidation of three nitrogen-containing heterocyclic VOCs, pyrrole, 1-methylyrrole (1-MP), and 2-methylpyrrole (2-MP), was investigated in chamber experiments to determine the effect of precursor structures on SOA and BrC formation. The SOA chemical compositions and the optical properties were analyzed using a suite of online and offline instrumentation. Dinitro- and trinitro-products were found to be the dominant SOA constituents from pyrrole and 2-MP, but not observed from 1-MP. Furthermore, the SOA from 2-MP and pyrrole showed strong light absorption, while that from 1-MP were mostly scattering. From these results, we propose that NO3-initiated hydrogen abstraction from the 1-position in pyrrole and 2-MP followed by radical shift and NO2 addition leads to light-absorbing nitroaromatic products. In the absence of a 1-position hydrogen, NO3 addition likely dominates the 1-MP chemistry. We also estimate that the total SOA mass and light absorption from pyrrole and 2-MP are comparable to those from phenolic VOCs and toluene in biomass burning, underscoring the importance of considering nighttime oxidation of pyrrole and methylpyrroles in air quality and climate models.

An experimental study of the reactivity of terpinolene and <i>β</i>-caryophyllene with the nitrate radical

Abstract. Biogenic volatile organic compounds (BVOCs) are intensely emitted by forests and crops into the atmosphere. They can rapidly react with the nitrate radical (NO3) during the nighttime to form a number of functionalized products. Among them, organic nitrates (ONs) have been shown to behave as reservoirs of reactive nitrogen and consequently influence the ozone budget and secondary organic aerosols (SOAs), which are known to have a direct and indirect effect on the radiative balance and thus on climate. Nevertheless, BVOC + NO3 reactions remain poorly understood. Thus, the primary purpose of this study is to furnish new kinetic and mechanistic data for one monoterpene (C10H16), terpinolene, and one sesquiterpene (C15H24), β-caryophyllene, using simulation chamber experiments. These two compounds have been chosen in order to complete the few experimental data existing in the literature. Rate constants have been measured using both relative and absolute methods. They have been measured to be (6.0 ± 3.8) ×10-11 and (1.8 ± 1.4) ×10-11 cm3 molec.−1 s−1 for terpinolene and β-caryophyllene respectively. Mechanistic studies have also been conducted in order to identify and quantify the main reaction products. Total organic nitrates and SOA yields have been determined. Both terpenes appear to be major ON precursors in both gas and particle phases with formation yields of 69 % for terpinolene and 79 % for β-caryophyllene respectively. They are also major SOA precursors, with maximum SOA yields of around 60 % for terpinolene and 90 % for β-caryophyllene. In order to support these observations, chemical analyses of the gas-phase products were performed at the molecular scale using a proton transfer reaction–time-of-flight–mass spectrometer (PTR-ToF-MS) and FTIR. Detected products allowed proposing chemical mechanisms and providing explanations through peroxy and alkoxy reaction pathways.

Formation of secondary organic aerosol tracers from anthropogenic and biogenic volatile organic compounds under varied NO and oxidant conditions

For source apportionment by tracer method of secondary organic aerosol (SOA), the ratios of aerosol tracer to total SOA mass ( f SOA ) were determined during the oxidation of toluene, naphthalene, α-pinene, and isoprene by a series of laboratory experiments. Seven anthropogenic SOA tracers maintaining an aromatic ring structure, including 4-nitrophthalic acid and 3,5-dinitrosalicylic, were newly investigated as a chamber study together with 21 traditional aerosol tracers of anthropogenic and biogenic SOA. Experiments of the OH-initiated oxidation of anthropogenic VOCs were conducted as a function of the initial VOC/NO x ratio. No significant dependence on the VOC/NO x ratio was observed for the f SOA of 2,3-dihydroxy-4-oxopentanoic acid from toluene and phthalic acid from naphthalene, whereas the f SOA of nitroaromatic compounds such as 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, and 4-nitrophthalic acid increased with decreasing VOC/NO x ratio. Among seven newly evaluated anthropogenic SOA tracers, we concluded that 3,5-dinitronsalicylic can be used as a toluene SOA tracer, whereas 4-nitrophthalic acid can be used as a naphthalene SOA tracer. Results of kinetic calculations suggest that naphthalene is a major source of 5-nitrosalicylic acid under urban and rural conditions of previous observation studies. The ozonolysis and NO 3 -initiated oxidation of biogenic VOCs were investigated in addition to OH-initiated oxidation of biogenic VOCs. As for biogenic SOA tracers such as pinic acid and 2-methyltetrols, the f SOA value measured for the NO 3 -intiated reaction was lower than that of the OH-initiated oxidation and the f SOA value measured for the ozonolysis was not necessarily close to that of the OH-initiated oxidation. These results suggest that daytime and nighttime biogenic SOA formation events are interpreted by using different sets of the f SOA values. • Ratios of SOA tracer to aerosol mass were measured for aerosol source analysis. • Twenty-eight SOA tracers including new ones formed from four VOCs were measured. • Anthropogenic SOA tracers were studied as a function of initial VOC/NO x ratio. • Biogenic SOA tracers were studied by changing the oxidant of SOA formation.

Impacts of biogenic emissions from urban landscapes on summer ozone and secondary organic aerosol formation in megacities

The impact of biogenic emissions on ozone and secondary organic aerosol (SOA) has been widely acknowledged; nevertheless, biogenic emissions emitted from urban landscapes have been largely ignored. We find that including urban isoprene in megacities like Beijing improves not only the modeled isoprene concentrations but also its diurnal cycle. Specifically, the mean bias of the simulated isoprene concentrations is reduced from 87% to 39% by adding urban isoprene emissions while keeping the diurnal cycle the same as that in non-urban or rural areas. Further adjusting the diurnal cycle of isoprene emissions to the urban profile steers the original early morning peak of the isoprene concentration to a double quasi-peak, i.e., bell shape, consistent with observations. The efficiency of ozone generation caused by isoprene emissions in urban Beijing is found to be twice as large as those in rural areas, indicative of vital roles of urban BVOC emissions in modulating the ozone formation. Our study also shows that in the future along with NOx emission reduction, isoprene emissions from urban landscapes will become more important for the formation of ozone in urban area, and their contributions may exceed that of isoprene caused by transport from rural areas. Finally, the impact of biogenic emissions on SOA is examined, revealing that biogenic induced SOA accounts for 16% of the total SOA in urban Beijing. The effect of isoprene on SOA (iSOA) is modulated through two pathways associated with the abundance of NOx emissions, and the effect can be amplified in future when NOx emissions are reduced. The findings of our study are not limited to Beijing but also apply to other megacities or densely populated regions, suggesting an urgent need to construct an accurate emission inventory for urban landscapes and evaluate their impact on ozone and SOA in air quality planning and management.