Design and characterization of a novel vehicle-mounted dual-reactor smog chamber for controlled and real-world atmospheric process simulations.

Abstract. The effect of vapor-wall deposition on secondary organic aerosol (SOA) formation has gained significant attention; however, uncertainties in experimentally derived SOA mass yields due to uncertainties in particle-wall deposition remain. Different approaches have been used to correct for particle-wall deposition in SOA formation studies, each having its own set of assumptions in determining the particle-wall loss rate. In volatile and intermediate-volatility organic compound (VOC and IVOC) systems in which SOA formation is governed by kinetically limited growth, the effect of vapor-wall deposition on SOA mass yields can be constrained by using high surface area concentrations of seed aerosol to promote the condensation of SOA-forming vapors onto seed aerosol instead of the chamber walls. However, under such high seed aerosol levels, the presence of significant coagulation may complicate the particle-wall deposition correction. Here, we present a model framework that accounts for coagulation in chamber studies in which high seed aerosol surface area concentrations are used. For the α-pinene ozonolysis system, we find that after accounting for coagulation, SOA mass yields remain approximately constant when high seed aerosol surface area concentrations ( ≥ 8000 µm2 cm−3) are used, consistent with our prior study (Nah et al., 2016) showing that α-pinene ozonolysis SOA formation is governed by quasi-equilibrium growth. In addition, we systematically assess the uncertainties in the calculated SOA mass concentrations and yields between four different particle-wall loss correction methods over the series of α-pinene ozonolysis experiments. At low seed aerosol surface area concentrations (< 3000 µm2 cm−3), the SOA mass yields at peak SOA growth obtained from the particle-wall loss correction methods agree within 14 %. However, at high seed aerosol surface area concentrations ( ≥ 8000 µm2 cm−3), the SOA mass yields at peak SOA growth obtained from different particle-wall loss correction methods can differ by as much as 58 %. These differences arise from assumptions made in the particle-wall loss correction regarding the first-order particle-wall loss rate. This study highlights the importance of accounting for particle-wall deposition accurately during SOA formation chamber experiments and assessing the uncertainties associated with the application of the particle-wall deposition correction method when comparing and using SOA mass yields measured in different studies.

In order to investigate the atmospheric oxidation processes and the formation of secondary organic aerosol (SOA), an indoor environmental reaction smog chamber are constructed and characterized. The system consists of the collapsible ∼830 L FEP Teflon film main reactor, in which the atmospheric chemical reactions take place and the formation of SOA occurs under the simulated atmospheric conditions, and the diverse on-line gas- and particle-phase instrumentation, such as the proton transfer reaction mass spectrometer, the synchrotron radiation photoionization mass spectrometer, the aerosol laser time-of-flight mass spectrometer, and other traditional commercial instruments. The initial characterization experiments are described, concerning the temperature and ultraviolet light intensity, the reactivity of the pure air, the wall loss rates of gaseous compounds and particulate matter. And the initial evaluation experiments for SOA yields from the ozonolysis of α-pinene and for mass spectra of the products resulting from the photooxidation of OH initiated isoprene are also presented, which indicate the applicability of this facility on the studies of gas-phase chemical mechanisms as well as the formation of SOA expected in the atmosphere.

Amines are recognized as key compounds in new particle formation (NPF) and secondary organic aerosol (SOA) formation. In addition, ozonolysis of α-pinene contributes substantially to the formation of biogenic SOAs in the atmosphere. In the present study, ozonolysis of α-pinene in the presence of dimethylamine (DMA) was investigated in a flow tube reactor. Effects of amines on SOA formation and chemical composition were examined. Enhancement of NPF and SOA formation was observed in the presence of DMA. Chemical characterization of gas- and particle-phase products by high-resolution mass spectrometric techniques revealed the formation of nitrogen containing compounds. Reactions between ozonolysis reaction products of α-pinene, such as pinonaldehyde or pinonic acid, and DMA were observed. Possible reaction pathways are suggested for the formation of the reaction products. Some of the compounds identified in the laboratory study were also observed in aerosol samples (PM1) collected at the SMEAR II station (Hyytiälä, Finland) suggesting that DMA might affect the ozonolysis of α-pinene in ambient conditions.

Vehicular evaporative emissions make an increasing contribution to anthropogenic sources of volatile organic compounds (VOCs), thus contributing to secondary organic aerosol (SOA) formation. However, few studies have been conducted on SOA formation from vehicle evaporative VOCs under complex pollution conditions with the coexistence of NOx, SO2, and NH3. In this study, the synergistic effects of SO2 and NH3 on SOA formation from gasoline evaporative VOCs with NOx were examined using a 30 m3 smog chamber with the aid of a series of mass spectrometers. Compared with the systems involving SO2 or NH3 alone, SO2 and NH3 coexistence had a greater promotion effect on SOA formation, which was larger than the cumulative effect of the two promotions alone. Meanwhile, contrasting effects of SO2 on the oxidation state (OSc) of SOA in the presence or absence of NH3 were observed, and SO2 could further increase the OSc with the coexistence of NH3. The latter was attributed to the synergistic effects of SO2 and NH3 coexistence on SOA formation, wherein N-S-O adducts can be formed from the reaction of SO2 with N-heterocycles generated in the presence of NH3. Our study contributes to the understanding of SOA formation from vehicle evaporative VOCs under highly complex pollution conditions and its atmospheric implications.

Abstract. Gasoline direct injection (GDI) vehicles have recently been identified as a significant source of carbonaceous aerosol, of both primary and secondary origin. Here we investigated primary emissions and secondary organic aerosol (SOA) from four GDI vehicles, two of which were also retrofitted with a prototype gasoline particulate filter (GPF). We studied two driving test cycles under cold- and hot-engine conditions. Emissions were characterized by proton transfer reaction time-of-flight mass spectrometry (gaseous non-methane organic compounds, NMOCs), aerosol mass spectrometry (sub-micron non-refractory particles) and light attenuation measurements (equivalent black carbon (eBC) determination using Aethalometers) together with supporting instrumentation. Atmospheric processing was simulated using the PSI mobile smog chamber (SC) and the potential aerosol mass oxidation flow reactor (OFR). Overall, primary and secondary particulate matter (PM) and NMOC emissions were dominated by the engine cold start, i.e., before thermal activation of the catalytic after-treatment system. Trends in the SOA oxygen to carbon ratio (O : C) for OFR and SC were related to different OH exposures, but divergences in the H : C remained unexplained. SOA yields agreed within experimental variability between the two systems, with a tendency for higher values in the OFR than in the SC (or, vice versa, lower values in the SC). A few aromatic compounds dominated the NMOC emissions, primarily benzene, toluene, xylene isomers/ethylbenzene and C3-benzene. A significant fraction of the SOA was explained by those compounds, based on comparison of effective SOA yield curves with those of toluene, o-xylene and 1,2,4-trimethylbenzene determined in our OFR, as well as others from literature. Remaining discrepancies, which were smaller in the SC and larger in the OFR, were up to a factor of 2 and may have resulted from diverse reasons including unaccounted precursors and matrix effects. GPF retrofitting significantly reduced primary PM through removal of refractory eBC and partially removed the minor POA fraction. At cold-started conditions it did not affect hydrocarbon emission factors, relative chemical composition of NMOCs or SOA formation, and likewise SOA yields and bulk composition remained unaffected. GPF-induced effects at hot-engine conditions deserve attention in further studies.

Secondary organic aerosol (SOA) are important components in atmospheric processes and significantly impact human health. The complexity of SOA composition and formation processes has hampered efforts to fully characterize their impacts, and to predict how those impacts will be affected by changes in climate and human activity. Here, we explore SOA formation in the laboratory by coupling an environmental chamber with a suite of analytical tools, including a gas-phase mass spectrometry technique that is well suited for tracking the hydrocarbon oxidation processes that drive SOA formation. Focusing on the oxidation of isoprene by the nitrate radical, NO₃, we find that reactions of peroxy radicals (RO₂) to form ROOR dimers is an important process in SOA formation. The other gas-phase products of these RO₂ reactions differ from what is expected from studies of simpler radicals, indicating that more studies are necessary to fully constrain RO₂ chemistry. Finally, we examine the role of heterogeneous oxidation as a sink of organic aerosol and a source of oxygenated volatile organic compounds in the free troposphere.

Abstract. Stabilized Criegee intermediates (SCIs) and organic peroxy radicals (RO2) are critical in atmospheric oxidation processes and secondary organic aerosol (SOA) formation. However, the influence of temperature on their corresponding reaction mechanisms in SOA formation is unclear. Through utilizing formic acid as a SCI scavenger and regulating the ratio of hydroperoxyl radials (HO2) to RO2 ([HO2]/[RO2]) from ∼ 0.3 to ∼ 1.9 using different concentrations of CO, the roles of RO2 and SCIs in SOA formation were investigated from 248 to 298 K, particularly for dimer formation in β-pinene ozonolysis. The SOA yield increased by 21 % from 298 to 273 K, while it decreased by 40 % from 273 to 248 K. Both changing [HO2]/[RO2] and scavenging SCIs significantly affect SOA yield and composition. SCI reactions accounted for more than 40 % of dimer and SOA mass formation for all temperatures. Increasing [HO2]/[RO2] inhibited dimer and SOA formation, and this inhibition became larger with decreasing temperature. Compared to low [HO2]/[RO2] (0.30–0.34), the dimer abundance at high [HO2]/[RO2] (1.53–1.88) decreased by about 31 % at 298 K and 70 % at 248 K. [HO2]/[RO2] has a specific impact on SCI-controlled dimers at lower temperatures by especially influencing the C9–SCI reactions with RO2. The dimers formed from C9–SCI reactions with RO2 were estimated to decrease by 61 % at high [HO2]/[RO2] compared to low [HO2]/[RO2] at 248 K. The high reactivity and substantial contribution to SOA of β-pinene-derived SCIs at lower temperatures observed in this study suggest that monoterpene-derived SCI reactions should be accounted for in describing colder regions of the atmosphere.

Criegee intermediates (CIs), which are active species in the troposphere, play an important role in the formation of secondary organic aerosols (SOA). In this study, matrix isolation technology combined with a vacuum Fourier transform infrared spectrometer (MIFT-IR) and smog chamber method were used to study the typical green leaf volatiles (E-4-hexen-1-ol, E4H1O) ozonolysis process. The infrared characteristic peak resulting from the O-O stretching vibration of CH3CHOO was identified at 882 cm-1. And the characteristic infrared peaks of CH2OHCH2CH2CHOO were not detected, possibly due to the presence of extremely rapid unimolecular reaction channels. To investigate the subsequent atmospheric reaction process of these two CIs, additional smog chamber experiments with the E4H1O-O3 system were conducted to investigate the impact on SOA formation mechanisms. The ordered oligomers derived from the continuous oligomerization of RO2 radicals with several CIs were identified as the primary components of SOA without the addition of sulfur dioxide (SO2). The addition of SO2 in the concentration range of 14-159 ppb, acting as a scavenger for CIs, led to the disappearance of the oligomers, while the yield of SOA continued to increase. The reasons for the increased mass concentration of SOA may be a change in the chemical composition. The escalating concentrations of SO2 underwent reactions with CIs (or OH radicals) to generate H2SO4, subsequently elevating the acidity of the particles. The acid particles resulted in the changes in SOA composition, leading to the production of organic sulfates (OSs), thereby contributing to the increase in SOA yield. A number of OSs were detected in the presence of SO2, which may result from the heterogeneous reaction of oxygen-containing species with sulfuric acid under acidic conditions. Additionally, non-sulfur-containing molecular structures of emerging CxHyOz products in the particle phase were also identified. Our findings provided detailed molecular insights into the mechanism of E4H1O ozonolysis and its impact on SOA formation from the perspective of Criegee chemistry.

Secondary organic aerosol formation from the gas phase reaction of hydroxyl radicals with m-, o- and p-cresol

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

Abstract. Recent studies have shown that low volatility gas-phase species can be lost onto the smog chamber wall surfaces. Although this loss of organic vapors to walls could be substantial during experiments, its effect on secondary organic aerosol (SOA) formation has not been well characterized and quantified yet. Here the potential impact of chamber walls on the loss of gaseous organic species and SOA formation has been explored using the Generator for Explicit Chemistry and Kinetics of the Organics in the Atmosphere (GECKO-A) modeling tool, which explicitly represents SOA formation and gas–wall partitioning. The model was compared with 41 smog chamber experiments of SOA formation under OH oxidation of alkane and alkene series (linear, cyclic and C12-branched alkanes and terminal, internal and 2-methyl alkenes with 7 to 17 carbon atoms) under high NOx conditions. Simulated trends match observed trends within and between homologous series. The loss of organic vapors to the chamber walls is found to affect SOA yields as well as the composition of the gas and the particle phases. Simulated distributions of the species in various phases suggest that nitrates, hydroxynitrates and carbonylesters could substantially be lost onto walls. The extent of this process depends on the rate of gas–wall mass transfer, the vapor pressure of the species and the duration of the experiments. This work suggests that SOA yields inferred from chamber experiments could be underestimated up a factor of 2 due to the loss of organic vapors to chamber walls.

Modeling the formation of traditional and non-traditional secondary organic aerosols from in-use, on-road gasoline and diesel vehicles exhaust

Abstract. The formation of secondary organic aerosol (SOA) from both ozonolysis and hydroxyl radical (OH)-initiated oxidation of α-pinene under conditions of high nitric oxide (NO) concentrations with varying relative humidity (RH) and aerosol acidity was investigated in the University of North Carolina dual outdoor smog chamber facility. SOA formation from ozonolysis of α-pinene was enhanced relative to that from OH-initiated oxidation in the presence of initially high-NO conditions. However, no effect of RH on SOA mass was evident. Ozone (O3)-initiated oxidation of α-pinene in the presence of ammonium sulfate (AS) seed coated with organic aerosol from OH-initiated oxidation of α-pinene showed reduced nucleation compared to ozonolysis in the presence of pure AS seed aerosol. The chemical composition of α-pinene SOA was investigated by ultra-performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS), with a focus on the formation of carboxylic acids and high-molecular weight dimers. A total of eight carboxylic acids and four dimers were identified, constituting between 8 and 12% of the total α-pinene SOA mass. OH-initiated oxidation of α-pinene in the presence of nitrogen oxides (NOx) resulted in the formation of highly oxidized carboxylic acids, such as 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA) and diaterpenylic acid acetate (DTAA). The formation of dimers was observed only in SOA produced from the ozonolysis of α-pinene in the absence of NOx, with increased concentrations by a factor of two at higher RH (50–90%) relative to lower RH (30–50%). The increased formation of dimers correlates with an observed increase in new particle formation at higher RH due to nucleation. Increased aerosol acidity was found to have a negligible effect on the formation of the dimers. SOA mass yield did not influence the chemical composition of SOA formed from α-pinene ozonolysis with respect to carboxylic acids and dimers. The results support the formation of the high-molecular weight dimers through gas-phase reactions of the stabilized Criegee Intermediate (sCI) formed from the ozonolysis of α-pinene. The high molecular weight and polar nature of dimers formed in the gas phase may explain increased particle number concentration as a result of homogenous nucleation. Since three of these dimers (i.e. pinyl-diaterpenyl dimer (MW 358), pinyl-diaterebyl dimer (MW 344) and pinonyl-pinyl dimer (MW 368)) have been observed in both laboratory-generated and ambient fine organic aerosol samples, we conclude that the dimers observed in this study can be used as tracers for the O3-initiated oxidation of α-pinene, and are therefore indicative of enhanced anthropogenic activities, and that the high molecular weight and low volatility dimers result in homogenous nucleation under laboratory conditions, increasing the particle number concentration.

Recent studies suggest that semivolatile organic compounds (SVOCs) are important precursors to secondary organic aerosol (SOA) in urban atmospheres. However, knowledge of the chemical composition of SVOCs is limited by current analytical techniques, which are typically unable to resolve a large number of constitutional isomers. Using a combination of gas chromatography and soft photoionization mass spectrometry, we characterize the unresolved complex mixture (UCM) of semivolatile aliphatic hydrocarbons observed in Pasadena, California (~16 km NE of downtown Los Angeles), and Bakersfield, California, during the California Research at the Nexus of Air Quality and Climate Change 2010. To the authors' knowledge, this work represents the most detailed characterization of the UCM in atmospheric samples to date. Knowledge of molecular structures, including carbon number, alkyl branching, and number of rings, provides important constraints on the rate of atmospheric processing, as the relative amounts of branched and linear alkanes are shown to be a function of integrated exposure to hydroxyl radicals. Emissions of semivolatile branched alkanes from fossil fuel‐related sources are up to an order of magnitude higher than those of linear alkanes, and the gas‐phase OH rate constants of branched alkanes are ~30% higher than their linear isomers. Based on a box model considering gas/particle partitioning, emissions, and reaction rates, semivolatile branched alkanes are expected to play a more important role than linear alkanes in the photooxidation of the UCM and subsequent transformations into SOA. Detailed speciation of semivolatile compounds therefore provides essential understanding of SOA sources and formation processes in urban areas.

Insights into the formation and properties of secondary organic aerosol at a background site in Yangtze River Delta region of China: Aqueous-phase processing vs. photochemical oxidation