Secondary Organic Aerosol Formation Research Articles

Characterization of emissions from rubber modified asphalt and their impact on environmental burden: Insights into composition variability and hazard assessment

Rubber modified asphalt (RMA) is a promising avenue for recycling waste tires but faces concerns over hazardous fumes emission during production and construction. This study employs a specialized apparatus to analyze RMA's emission behavior, focusing on crumb rubber size variations under thermal conditions. Ozone Formation Potential (OFP) and Secondary Organic Aerosol Formation Potential (SOAFP) were quantified to evaluate the environmental burden. Results indicate distinct periods of emission behavior for different pollutants, with H2S emissions primarily occurring within the initial 150 min while volatile organic compounds (VOCs) dominate within the first 270 min. The size of rubber particles and thermal exposure duration influence the VOCs microscopic emission characteristics and environmental burdens. Polycyclic aromatic hydrocarbons (PAHs) emerge as the primary contributors to OFP and SOAFP, accounting for nearly 65 % and 25 %−60 %, respectively. High molecular weight aliphatic hydrocarbons (ALHs) also significantly contribute to SOAFP, with PAHs dominating throughout, while ALHs peak during the middle stage. H2S emissions likely stem from rubber, while early VOC emissions originate from rubber, transitioning to petroleum asphalt during the middle and late stages. Asphalt fractions influence emission behavior and property evolution. These findings inform emission suppression strategies and highlight the need for tailored approaches to mitigate emissions effectively.

Insights into the catalytic effect of atmospheric organic trace species on the hydration of Criegee intermediates

The bimolecular reactions between Criegee intermediates (CIs) and atmospheric trace species have been extensively investigated, with a particular focus on the reaction with water, while the catalytic role of atmospheric organic compounds in hydration reactions was often neglected. In this study, we employed quantum chemical calculations and Born-Oppenheimer molecular dynamics (BOMD) simulations to investigate the catalytic effects of atmospheric organic amines, organic acids, and alcohols on the hydration reactions of CIs in the gas phase and at the gas-liquid interface. The catalytic reactions were found to follow a cyclic catalytic structure and a stepwise reaction mechanism. Gas-phase studies revealed that organic acids exhibited stronger catalytic effects compared to amines and alcohols, and the catalytic efficiency of amines and alcohols was similar to those of single water molecule. In addition, the catalytic reaction barriers of organic acids and alcohols were positively correlated with their gas-phase acidity (R2 = 0.94 to 0.97). A negative correlation was observed between the catalytic reaction barrier of amines and their gas-phase basicity (R2 = 0.84 to 0.90) and proton affinity (R2 = 0.84 to 0.92). At the gas-liquid interface, organic acids promoted the formation of hydroxyethyl hydroperoxide (HEHP, CH3CH(OH)(OOH)), organic acid ions, and H3O+, whereas the catalytic hydration of CIs by organic amines resulted in the formation of CH3CH(OH)OO and amine ions. Both HEHP and CH3CH(OH)OO can be further decomposed to form OH and HO2, or participate in new particles formation as precursors. This study complements the research gap on the reaction of CIs with water, providing valuable insights into the atmospheric sources of HEHP and HOx as well as the formation of secondary organic aerosols (SOAs).

Secondary Organic Aerosol Formation from Aqueous Ethylamine Oxidation Mediated by Particulate Nitrate Photolysis

Secondary Organic Aerosol Formation from Aqueous Ethylamine Oxidation Mediated by Particulate Nitrate Photolysis

Comparison of NMHC measurements between 2010 and 2020 in Wuxi City, Yangtze River Delta region: Levels, compositions, sources, and impacts

Field observation analyses of volatile organic compounds (VOCs) have gained significant attention due to their potential explaining atmospheric temporal trends. This study measured non-methane hydrocarbons (NMHCs) in Wuxi City, located in the Yangtze River Delta (YRD) of China, in 2010 and 2020. The aim was to gain a better understanding of the ten-year change of VOCs in terms of their mixing ratios, sources, role in ozone, secondary organic aerosol (SOA) formation, and health risks. The average NMHC level 2020 was 20.67 ppbv, which indicated a 20% drop from 2010. A notable shift was observed in the chemical composition of NMHCs. The contribution of alkanes increased from 45% to 62% in 2020, while that of the aromatics decreased from 25% in 2010 to 21% in 2020. Ratio analysis and receptor modelling for 2010 and 2020 were used to identify the source changes of VOC species. The source apportionment model showed that the contribution of vehicle exhaust decreased from 34.5% to 20.9% from 2010 to 2020, and that of the solvent increased from 15.1% to 25.3%. The chemical reactivity results suggested that aromatics played significant roles in photochemical reactions in Wuxi City. The ozone formation potential (OFP) and SOA potential of VOCs also showed decreasing trends from 2010 to 2020. The total OFP of alkenes decreased by 34.0%, from 30.6 to 20.2 ppbvO3/ppbv. The total non-carcinogenic risk value for the key VOC species was 0.034 in 2010 and 0.024 in 2020. Although the carcinogenic risks for benzene have decreased significantly, the value is still above the acceptable carcinogenic risk level. The results of this study demonstrate the effectiveness of air pollution control measures in Wuxi City and highlight the positive impacts on reducing secondary pollution and health risks in this region over one decade.

Measurement report: Size-resolved secondary organic aerosol formation modulated by aerosol water uptake in wintertime haze

Measurement report: Size-resolved secondary organic aerosol formation modulated by aerosol water uptake in wintertime haze

A Nature-Inspired Design for Sequestering Polycyclic Aromatic Hydrocarbons in Asphalt-Surfaced Areas

Asphalts for pavement and roofing are known to emit volatile organic compounds (VOCs), contributing to air pollution, including the formation of ozone and secondary organic aerosols, which further worsen air quality. These emissions become more pronounced with higher sun intensity and higher temperature, accelerating the loss of essential components and the aging of bitumen. Consequently, the durability and functionality of bitumen are compromised. In this study, we investigate the efficacy of nitrogen-carrying functional groups in biochar at retaining VOCs in bitumen and prolonging the service life of asphalt surfaces. Biochar derived by hydrothermal liquefaction of red microalgae, rich in N-functional groups, is compared with low-N biochar obtained through acid-washing. Laboratory tests demonstrate that bitumen modified with high-N biochar exhibits greater resistance to aging after 200 h of ultraviolet radiation exposure compared to bitumen modified with low-N biochar. The values of an aging index based on the crossover modulus and an aging index based on the crossover frequency indicate greater susceptibility to aging in neat bitumen compared to biochar-modified bitumen, and bitumen modified with high-N biochar showed the lowest aging index. Compared to neat bitumen, measurements of carbonyl and sulfoxide as aging indicators showed an improvement of 12.9% for high-N biochar in slowing bitumen aging, while low-N biochar provided only a 3.1% improvement. Dynamic vapor sorption analysis showed 35% less mass loss in bitumen with high-N biochar compared to bitumen with low-N biochar. These improvements can be attributed to the increased retention of VOCs in bitumen facilitated by the N-functional groups in high-N biochar. Modeling with density functional theory shows the mechanisms by which biochar rich in N-functional groups exhibits enhanced adsorption of VOCs. This modeling highlights the importance of biochar's nitrogen functional groups in biochar's electronic structure and molecular structure in retaining VOCs in the bitumen matrix. The study outcomes promote sustainability and resource conservation in the construction industry and align with goals of carbon neutrality.

The role of naphthalene and its derivatives in the formation of secondary organic aerosol in the Yangtze River Delta region, China

Abstract. Naphthalene (Nap) and its derivatives, including 1-methylnaphthalene (1-MN) and 2-methylnaphthalene (2-MN), serve as prominent intermediate volatile organic compounds (IVOCs) and contribute to the formation of secondary organic aerosol (SOA). In this study, the Community Multiscale Air Quality (CMAQ) model coupled with detailed emissions and reactions of these compounds was utilized to examine their roles in the formation of SOA and other secondary pollutants in the Yangtze River Delta (YRD) region during summer. Significant underestimations of Nap and MN concentrations (by 79 % and 85 %) were observed at the Taizhou site based on the model results using the default emissions. Constrained by the observations, anthropogenic emissions of Nap and MN in the entire region were multiplied by 5 and 7, respectively, to better capture the evolution of pollutants. The average concentration of Nap reached 25 ppt (parts per trillion) in the YRD, with Nap contributing 4.1 % and 8.1 % (up to 12.6 %) of total aromatic emissions and aromatic-derived secondary organic carbon (SOC), respectively. The concentrations of 1-MN and 2-MN were relatively low, averaging 2 and 5 ppt, respectively. Together, they accounted for only 2.4 % of the aromatic-derived SOC. The impacts of Nap and MN oxidation on ozone and radicals were insignificant at regional scales but were not negligible when considering daily fluctuations in locations with high emissions of Nap and MN. This study highlights the significant roles of Nap and MN in the formation of SOA, which may pose environmental risks and result in adverse health effects.

Morphology-dependent gas-sensing sensitivity of γ-Al2O3 for methacrolein

Methacrolein (MACR) is a key precursor in the formation of secondary organic aerosols and a significant occupational chemical hazard, posing risks to both the environment and health. In this work, three types of γ-Al2O3 were synthesized via hydrothermal methods, including nanorods, nanosheets, and a mixed morphology. Characterization results revealed that rod-like γ-Al2O3 has the largest specific surface area and the highest oxygen vacancy content. The possible formation mechanism of γ-Al2O3 samples with different morphologies was discussed. Further study indicated that the morphology of γ-Al2O3 significantly affects its sensitivity in the cataluminescence (CTL) sensing of MACR, with rod-like γ-Al2O3 exhibiting the highest sensitivity, whereas sheet-like γ-Al2O3 showed the lowest sensitivity. Thus, a CTL sensor based on rod-like γ-Al2O3 for MACR detection was developed, demonstrating outstanding performance in terms of sensitivity, selectivity, reproducibility, and stability. This sensor was applied to the analysis of real samples, and the results were compared with those obtained by gas chromatography. The results obtained by the two methods were consistent, with relative error ranged from −4.0 % to −4.9 %. The sensing mechanism was further elucidated via density functional theory calculations, in situ Fourier transform infrared spectroscopy and gas chromatography-mass spectrometry. This work broadens the horizons for applying material science principles to enhance the performance of gas sensors, thereby contributing to design high-performance CTL sensors for air quality and occupational safety monitoring.

Secondary Organic Aerosol Formation from Ambient Air in Summer in Urban Beijing: Contribution of S/IVOCs and Impacts of Heat Waves

Secondary Organic Aerosol Formation from Ambient Air in Summer in Urban Beijing: Contribution of S/IVOCs and Impacts of Heat Waves

Temperature-dependent emissions dominate aerosol and ozone formation in Los Angeles.

Despite declines in transportation emissions, urban North America and Europe still face unhealthy air pollution levels. This has challenged conventional understanding of the sources of their volatile organic compound (VOC) precursors. Using airborne flux measurements to map emissions of a wide range of VOCs, we demonstrate that biogenic terpenoid emissions contribute ~60% of emitted VOC OH reactivity, ozone, and secondary organic aerosol formation potential in summertime Los Angeles and that this contribution strongly increases with temperature. This implies that control of nitrogen oxides is key to reducing ozone formation in Los Angeles. We also show some anthropogenic VOC emissions increase with temperature, which is an effect not represented in current inventories. Air pollution mitigation efforts must consider that climate warming will strongly change emission amounts and composition.

Seasonal and height dynamics of volatile organic compounds in rubber plantation: Impacts on ozone and secondary organic aerosol formation

Rubber trees emit a range of volatile organic compounds (VOCs), including isoprene, monoterpenes, and sesquiterpenes, as part of their natural metabolism. These VOCs can significantly influence air quality through photochemical reactions that produce ozone and secondary organic aerosols (SOAs). This study examines the impact of VOCs detected in a rubber tree plantation in Northeastern Thailand on air quality, highlighting their role in atmospheric reactions that lead to the formation of ozone and SOAs. VOCs were collected at varying heights and seasons using Tenax-TA tubes paired with an atmospheric sampler pump and identified by gas chromatography–mass spectrometry. In total, 100 VOCs were identified, including alkanes, alkenes, terpenes, aromatics, and oxygenated VOCs. Principal Coordinate Analysis (PCoA) revealed distinct seasonal VOC profiles, with hydrocarbons, peaking in summer and terpenes in the rainy season. The Linear Mixed-Effects (LME) model indicates that VOC concentrations are more influenced by seasonal changes than by sampling heights. Secondary organic aerosol potential (SOAP) and ozone formation potential (OFP) of selected VOC species were also determined. The total SOAP ranged from 67.24 μg/m3 in summer to 17.87 μg/m3 in winter, while the total OFP ranged from 377.87 μg/m3 in summer to 139.39 μg/m3 in winter. Additionally, positive matrix factorization (PMF) analysis identified four main VOC sources: gasoline combustion (18.3 %), microbial activity (38.6 %), monoterpene emissions during latex production (15.0 %), and industrial sources (28.1 %). These findings provide essential information for managing air pollution in rubber tree plantations. By adopting focused air quality management strategies, plantation operators can mitigate the adverse effects of VOCs, promoting a healthier and more sustainable future.

Analysis of PM2.5, black carbon, and trace metals measurements from the Kansas City Transportation and Local-Scale Air Quality Study (KC-TRAQS)

ABSTRACT Communities near transportation sources can be impacted by higher concentrations of particulate matter (PM) and other air pollutants. Few studies have reported on air quality in complex urban environments with multiple transportation sources. To better understand these environments, the Kansas City Transportation and Local-Scale Air Quality Study (KC-TRAQS) was conducted in three neighborhoods in Southeast Kansas City, Kansas. This area has several emissions sources including transportation (railyards, vehicles, diesel trucks), light industry, commercial facilities, and residential areas. Stationary samples were collected for 1-year (October 24, 2017, to October 31, 2018) at six sites using traditional sampling methods and lower-cost air sensor packages. This work examines PM less than 2.5 μm in diameter (PM2.5), black carbon (BC), and trace metals data collected during KC-TRAQS. PM2.5 filter samples showed the highest 24-h mean concentrations (9.34 μg/m3) at the sites located within 20–50 m of the railyard. Mean 24-h PM2.5 concentrations, ranging from 7.96 to 9.34 μg/m3, at all sites were lower than that of the nearby regulatory site (9.83 μg/m3). Daily maximum PM2.5 concentrations were higher at the KC-TRAQS sites (ranging from 25.31 to 43.76 μg/m3) compared to the regulatory site (20.50 μg/m3), suggesting short-duration impacts of localized emissions sources. Across the KC-TRAQS sites, 24-h averaged PM2.5 concentrations from the sensor package (P-POD) ranged from 3.24 to 5.69 µg/m3 showing that, out-of-the-box, the PM sensor underestimated the reference concentrations. KC-TRAQS was supplemented by elemental and organic carbon (EC/OC) and trace metal analysis of filter samples. The EC/OC data suggested the presence of secondary organic aerosol formation, with the highest mean concentrations observed at the site within 20 m of the railyard. Trace metals data showed daily, monthly, and seasonal variations for iron, copper, zinc, chromium, and nickel, with elevated concentrations occurring during the summer at most of the sites. Implications: This work reports on findings from a year-long air quality study in Southeast Kansas City, Kansas to understand micro-scale air quality in neighborhoods impacted by multiple emissions sources such as transportation sources (including a large railyard operation), light industry, commercial facilities, and residential areas. While dozens of studies have reported on air quality near roadways, this work will provide more information on PM2.5, black carbon, and trace metals concentrations near other transportation sources in particular railyards. This work can also inform additional field studies near railyards.

Organic Emissions of Volatile Chemical Products in Canada: Emission Inventories, Indoor-to-Outdoor Transfer, and Regional Impacts.

The contribution of volatile chemical products (VCPs) to ambient air pollution has increased following decades of regulating combustion sources. There is a research gap concerning the impact of indoor physicochemical phenomena on VCP emissions. In this work, a bottom-up speciated VCP emission inventory with indoor-outdoor resolution was developed for Canada, an industrialized country with low air pollution levels, whose major cities are among the largest urban areas in North America. VCPs were estimated to account for about 290 kilotons of gaseous organic emissions for a typical year in the 2010s, with more than 60% of emissions occurring indoors. Coatings and cleaners were the most emissive VCP categories. Oxygenated species and saturated aliphatics dominated the chemical profiles of most emissions. Less than 5% of VCP emissions were impacted by indoor physicochemical phenomena. VCP emissions were predicted to account for 0.8-3.2 s-1 of OH reactivity and 0.22-0.52 μg/m3 of secondary organic aerosol formation potential in major urban areas in Canada. Our predictions aligned with previous measurements concerning indoor and outdoor organic pollutant levels, underscoring the important air quality impacts of VCPs relative to other sources. Our results provide helpful insights for future research regarding VCP emissions, especially from indoor spaces.

Emission of Intermediate Volatile Organic Compounds from Animal Dung and Coal Combustion and Its Contribution to Secondary Organic Aerosol Formation in Qinghai-Tibet Plateau, China.

Intermediate volatility organic compounds (IVOCs) are important precursors to secondary organic aerosols (SOAs), but they are often neglected in studies concerning SOA formation. This study addresses the significant issue of IVOCs emissions in the Qinghai-Tibetan plateau (QTP), where solid fuels are extensively used under incomplete combustion conditions for residential heating and cooking. Our field measurement data revealed an emission factor of the total IVOCs (EFIVOCs) ranging from 1.56 ± 0.03 to 9.97 ± 3.22 g/kg from various combustion scenarios in QTP. The markedly higher EFIVOCs in QTP than in plain regions can be attributed to oxygen-deficient conditions. IVOCs were dominated by gaseous phase emissions, and the primary contributors of gaseous and particulate phase IVOCs are the unresolved complex mixture and alkanes, respectively. Total IVOCs emissions during the heating and nonheating seasons in QTP were estimated to be 31.7 ± 13.8 and 6.87 ± 0.45 Gg, respectively. The estimated SOA production resulting from combined emissions of IVOCs and VOCs is nearly five times higher than that derived from VOCs alone. Results from this study emphasized the pivotal role of IVOCs emissions in air pollution and provided a foundation for compiling emission inventories related to solid fuel combustion and developing pollution prevention strategies.

Evaporation-Induced Transformations in Volatile Chemical Product-Derived Secondary Organic Aerosols: Browning Effects and Alterations in Oxidative Reactivity.

Volatile chemical products (VCPs) are increasingly recognized as significant sources of volatile organic compounds (VOCs) in urban atmospheres, potentially serving as key precursors for secondary organic aerosol (SOA) formation. This study investigates the formation and physicochemical transformations of VCP-derived SOA, produced through ozonolysis of VOCs evaporated from a representative room deodorant air freshener, focusing on the effects of aerosol evaporation on its molecular composition, light absorption properties, and reactive oxygen species (ROS) generation. Following aerosol evaporation, solutes become concentrated, accelerating reactions within the aerosol matrix that lead to a 42% reduction in peroxide content and noticeable browning of the SOA. This process occurs most effectively at moderate relative humidity (∼40%), reaching a maximum solute concentration before aerosol solidification. Molecular characterization reveals that evaporating VCP-derived SOA produces highly conjugated nitrogen-containing products from interactions between existing or transformed carbonyl compounds and reduced nitrogen species, likely acting as chromophores responsible for the observed brownish coloration. Additionally, the reactivity of VCP-derived SOA was elucidated through heterogeneous oxidation of sulfur dioxide (SO2), which revealed enhanced photosensitized sulfate production upon drying. Direct measurements of ROS, including singlet oxygen (1O2), superoxide (O2•-), and hydroxyl radicals (•OH), showed higher abundances in dried versus undried SOA samples under light exposure. Our findings underscore that drying significantly alters the physicochemical properties of VCP-derived SOA, impacting their roles in atmospheric chemistry and radiative balance.

Dual roles of the inorganic aqueous phase on secondary organic aerosol growth from benzene and phenol

Abstract. Benzene, emitted from automobile exhaust and biomass burning, is ubiquitous in ambient air. Benzene is a precursor hydrocarbon (HC) that forms secondary organic aerosol (SOA), but its SOA formation mechanism is not well studied. To accurately predict the formation of benzene SOA, it is important to understand the gas mechanisms of phenol, which is one of the major products formed from the atmospheric oxidation of benzene. Laboratory data presented herein highlight the impact of the aqueous phase on SOA generated through benzene and phenol oxidation. The roles of the aqueous phase consist of (1) suppression of the aging of hydrocarbon and (2) conventional acid-catalyzed reactions in the inorganic phase. To explain this unusual effect, it is hypothesized that a persistent phenoxy radical (PPR) effectively forms via a heterogeneous reaction of phenol and phenol-related products in the presence of wet inorganic aerosol. These PPR species are capable of catalytically consuming ozone during an NOx cycle and negatively influencing SOA growth. In this study, explicit gas mechanisms were derived to produce the oxygenated products from the atmospheric oxidation of phenol or benzene. Gas mechanisms include the existing Master Chemical Mechanism (MCM v3.3.1), the reaction path for peroxy radical adducts originating from the addition of an OH radical to phenols forming low-volatility products (e.g., multi-hydroxy aromatics), and the mechanisms to form heterogeneous production of PPR. The simulated gas products were classified into volatility- and reactivity-based lumped species and incorporated into the Unified Partitioning Aerosol Reaction (UNIPAR) model that predicts SOA formation via multiphase reactions of phenol or benzene. The predictability of the UNIPAR model was examined using chamber data, which were generated for the photooxidation of phenol or benzene under controlled experimental conditions (NOx levels, humidity, and inorganic seed types). The SOA formation from both phenol and benzene still increased in the presence of wet inorganic seed because of the oligomerization of reactive organic species in the aqueous phase. However, model simulations show a significant suppression of ozone, the oxidation of phenol or benzene, and SOA growth compared with those without PPR mechanisms. The production of PPR is accelerated in the presence of acidic aerosol and this weakens SOA growth. In benzene oxidation, up to 53 % of the oxidation pathway is connected to phenol formation in the reported gas mechanism. Thus, the contribution of PPR to gas mechanisms is less than that of phenol. Overall, SOA growth in phenol or benzene is negatively related to NOx levels in the high-NOx region (HC ppbC / NOx ppb < 5). However, the simulation indicates that the significance of PPR rises with decreasing NOx levels. Hence, the influence of NOx levels on SOA formation from phenol or benzene is complex under varying temperature and seed type conditions. Adding the comprehensive reaction of phenolic compounds will improve the prediction of SOA formation from aromatic HCs due to the missing mechanisms in the current air quality model.

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.

Quantifying bimolecular reaction kinetics of isoprene hydroxy peroxy radical: From dry to highly humid atmospheric environment

Isoprene hydroxy peroxy radicals (ISOPOO), derived from isoprene oxidation by hydroxy radicals (OH), are key intermediates for ozone and secondary organic aerosol (SOA) formation in the atmosphere. Although ISOPOO-water complexes are ubiquitous, their impacts on ISOPOO chemistry remain obscure. Here the previously overlooked water effect on the bimolecular reaction kinetics of ISOPOO was investigated in an oxidative flow reactor. The major first-generation products of ISOPOO, isoprene hydroxy hydroperoxides (ISOPOOH), methacrolein (MACR), and methyl vinyl ketone (MVK), were measured simultaneously at various relative humidity (RH) with the help of a cold trap to avoid potential losses in direct gas sampling. We found that ISOPOO reactions were accelerated significantly under wet conditions, with a greater enhancement on 1,2-ISOPOO than 4,3-ISOPOO. 1,2-ISOPOOH yield appeared faster growth with RH than 4,3-ISOPOOH. MVK yield showed an upward-downward trend with RH, while MACR yield plateaued from 30% RH. To explain the enhancement in the ISOPOOH yield from 3% to 80% RH, the overall rate constants of 1,2-ISOPOO + HO2 and 4,3-ISOPOO + HO2 reactions at 80% RH should be 13 times and twice those at 3% RH, respectively. The empirical formulas were proposed for the first time to parameterize the water effect on ISOPOO + HO2 reactions. The updated kinetics of ISOPOO reactions were incorporated in a box model to simulate the RH-dependent ISOPOOH and C4 carbonyl yields under typical atmospheric conditions. High RH can enhance the ISOPOOH yield in urban, rural, and forest areas, and promote SOA formation correspondingly. Our findings shed light on the critical role of humidity in the reactions of ISOPOO and benefit evaluating the fate of isoprene and its impacts on air quality more accurately in the ambient atmosphere.