Smog Chamber Research Articles

Rate coefficients for the gas‐phase OH + furan (C4H4O) reaction between 273 and 353 K

AbstractRate coefficients, k1, for the gas‐phase OH radical reaction with the heterocyclic ether C4H4O (1,4‐epoxybuta‐1,3‐diene, furan) were measured over the temperature range 273–353 K at 760 Torr (syn. air). Experiments were performed using: (i) the photochemical smog chamber THALAMOS (thermally regulated atmospheric simulation chamber, IMT NE, Douai‐France) equipped with Fourier Transform Infrared (FTIR) and Selected Ion Flow Tube Mass Spectrometry (SIFT‐MS) detection methods and (ii) a photochemical reactor coupled with FTIR spectroscopy (PCR, University of Crete, Greece). k1(273–353 K) was measured using a relative rate (RR) method, in which the loss of furan was measured relative to the loss of reference compounds with well‐established OH reaction rate coefficients. k1(273–353 K) was found to be well represented by the Arrhenius expression (1.30 ± 0.12) × 10−11 exp[(336 ± 20)/T] cm3 molecule−1 s−1, with k1(296 K) measured to be (4.07 ± 0.32) × 10−11 cm3 molecule−1 s−1. The k1(296 K) and pre‐exponential quoted error limits are 2σ and include estimated systematic errors in the reference rate coefficients. The observed negative temperature dependence is consistent with a reaction mechanism involving the OH radical association to a furan double bond. Quantum mechanical molecular calculations show that OH addition to the α‐carbon (ΔHr(296 K) = −121.5 kJ mol−1) is thermochemically favored over the β‐carbon (ΔHr(296 K) = −52.9 kJ mol−1) addition. The OH‐furan adduct was found to be stable over the temperature range of the present measurements. Maleic anhydride (C4H2O3) was identified as a minor reaction product, 3% lower‐limit yield, demonstrating a non‐ring‐opening active reaction channel. The present results are critically compared with results from previous studies of the OH + furan reaction rate coefficient. The infrared spectrum of furan was measured as part of this study and its estimated climate metrics are reported.

Aging effects on residential biomass burning emissions under quasi-real atmospheric conditions

Emissions from biomass burning (BB) vastly contribute to the atmospheric trace gases and particles, which affect air quality and human health. After emission, the chemical evolution changes the mass and composition of organic aerosol (OA) in the diluted and aged plume. In this study, we used a quasi-real atmospheric smog chamber system to conduct aging experiments and investigated the multiphase oxidation of primary organic aerosol (POA) and the formation of secondary organic aerosols (SOA) in residential biomass burning plumes. We found that the emissions in the gas and particle phases were interlinked during the plume evolution. During photochemical aging, more oxidized OA was produced, and SOA formation increased by a factor of 2 due to functionalization reactions of gaseous precursors such as furans, phenols, and carbonyls. On the other hand, dark aging resulted in a lower OA mass enhancement by a factor of 1.2, with weaker oxidation from gaseous reactions. Dark aging experiments resulted in the generation of substantial quantities of nitrogen-containing organic compounds in both gas and particulate phases, while photochemical aging led to a notable increase in the concentration of gaseous carboxylic acids. Our observations show that the properties of SOA are influenced by exposure to sunlight radiation and oxidants such as OH or NO3 radicals. These results reflect the aging process of BB plumes in real-world atmospheric conditions and highlight the importance of considering various aging mechanisms.

Deposition of secondary organic aerosol in human lung model: Effect of photochemically aged aerosol on human respiratory system

Ultrafine particles (UFP) of Secondary Organic Aerosol (SOA) penetrate deep into the human respiratory system and exert fatal effects on human health. However, there is little data on the potential deposited doses of UFP-generated SOA in the human respiratory tract. This study is to estimate the fraction of aerosol deposition using a multiple-path-particle-dosimetry (MPPD) model. For relevancy of real life, the model employed measured concentrations of toluene-derived fresh and aged SOA produced within serially connected smog chamber and PAM-OFR (Potential Aerosol Mass-Oxidation Flow Reactor) under atmospheric environmental conditions (NOx and relative humidity). The number concentrations and chemical composition of fresh and aged aerosols produced within the chambers were measured using Scanning Mobility Particle Sizer (SMPS) and High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS), while the morphology of individual particles was analyzed using Scanning Electron Microscopy (SEM). The number concentration of aged SOA-w/s was more than double compared to that of fresh SOA-w/s (maximum reached after 10 h) with its size less than 100 nm. The O:C ratio for aged SOA-w/s were 0.96 and 1.15 depending on RH (0.96 at 3% RH and 1.15 at 50% RH), and individual spherical particles containing water were present in agglomerates with its size of less than 1 µm. In all inhalable fresh and aged SOA produced in the two chambers, 5–22% of aerosol is deposited in the Head airways, 4–8% in the tracheobronchial, and 8–34% in the alveolar regions. The predominant deposition of the aged aerosol occurred in the alveoli (in the generation 20th lobe), and the deposition faction in the alveoli was 2–3 times higher in the children group than the adults group. This study presented a quantitative exposure assessment of SOA generated under a realistic simulation and suggested the possibility of evaluating long-term exposure to SOA and potential health effects by determining the potential inhalable aerosol doses and the fraction of deposition in the human respiratory system.

Combined Smog Chamber/Oxidation Flow Reactor Study on Aging of Secondary Organic Aerosol from Photooxidation of Aromatic Hydrocarbons.

Secondary organic aerosol (SOA) is a significant component of atmospheric fine particulate matter (PM2.5), and their physicochemical properties can be significantly changed in the aging process. In this study, we used a combination consisting of a smog chamber (SC) and oxidation flow reactor (OFR) to investigate the continuous aging process of gas-phase organic intermediates and SOA formed from the photooxidation of toluene, a typical aromatic hydrocarbon. Our results showed that as the OH exposure increased from 2.6 × 1011 to 6.3 × 1011 molecules cm-3 s (equivalent aging time of 2.01-4.85 days), the SOA mass concentration (2.9 ± 0.05-28.7 ± 0.6 μg cm-3) and corrected SOA yield (0.073-0.26) were significantly enhanced. As the aging process proceeds, organic acids and multiple oxygen-containing oxidation products are continuously produced from the photochemical aging process of gas-phase organic intermediates (mainly semi-volatile and intermediate volatility species, S/IVOCs). The multigeneration oxidation products then partition to the aerosol phase, while functionalization of SOA rather than fragmentation dominated in the photochemical aging process, resulting in much higher SOA yield after aging compared to that in the SC. Our study indicates that SOA yields as a function of OH exposure should be considered in air quality models to improve SOA simulation, and thus accurately assess the impact on SOA properties and regional air quality.

Atmospheric chemistry of 1,1-difluoroacetone, CHF2C(O)CH3: Kinetics, products and mechanisms of the Cl atom and OH radical initiated oxidation

Smog chamber techniques were used to study the Cl atom and OH radical initiated oxidation of 1,1-difluoroacetone (CF2HC(O)CH3) in 700 Torr of air or N2 diluent at 297 K. Using relative rate methods k(Cl + CF2HC(O)CH3) = (5.0 ± 0.8) × 10−14 cm3 molecule-1 s−1 and k(OH + CF2HC(O)CH3) = (2.6 ± 0.7) × 10−14 cm3molecule-1s−1 were determined. The atmospheric lifetime of CF2HC(O)CH3 with respect to reaction with OH radicals is estimated at 1.2 years. Atmospheric oxidation yields COF2, CO and CO2. The data suggests that Cl atoms primarily attack the –CF2H group, whereas OH radicals also attack the –CH3 group.

Insight into the crucial reason causing the difference in secondary organic aerosol yields of monocyclic aromatic hydrocarbons with different methyl substituent numbers

The secondary organic aerosol (SOA) yield of toluene photooxidation was reported to substantially higher than that of trimethylbenzene due to the effect of the number of methyl substituents. However, the intrinsic mechanism for this disparity is not clear enough. In this study, a highly-sensitive thermal-desorption photoinduced associative ionization mass spectrometer (TD-PAI-MS) was used to real-time characterize the molecular composition and its evolution of the SOA generated from the photooxidation of toluene and 1,2,3-trimethylbenzene (1,2,3-TMB) in a smog chamber. In the new particle formation (NPF) stage, toluene generated more variety of nucleation precursors, such as benzaldehyde (MW 106) and benzoic acid (MW 122), resulting in a much higher nucleation rate and SOA number concentration. In the SOA growth/aging stage, the key SOA components of toluene were mainly dialdehydes, e.g., 2-oxopropanedial (MW 86) and 4-oxopent-2-enedial (MW 112), which played an important role in the formation of highly oxidized species (HOS) through oligomerization or cyclization reactions. In contrast, due to the presence of more methyl groups, 1,2,3-TMB was inclined to produce ketones, e.g., 2,3-butanedione (MW 86) and 3-methyl-4-oxopent-2-enal (MW 112), which would be cleaved into high-volatility low molecular compounds, e.g., acetic acid, through fragmentation. Taken together, relative to 1,2,3-TMB, the higher nucleation rate during NPF and the significant oligomerization/functionalization process during SOA growth are thought to be the major reasons resulting in the higher SOA yield of toluene. This work provides a reference for the insight into the different SOA yields of monocyclic aromatic hydrocarbons (MAHs) through further revealing the SOA formation mechanism during toluene and 1,2,3-TMB photooxidation.

A new smog chamber system for atmospheric multiphase chemistry study: design and characterization

Abstract. Multiphase chemistry is an important pathway for the formation of secondary organic aerosols (SOAs) in the atmosphere. In this study, an indoor 2 m3 Teflon chamber system (Aerosol multIphase chemistry Research chamber, AIR) was developed and characterized to specifically simulate atmospheric multiphase chemistry processes. The temperature and humidity controls, diurnal variation simulation, and seed particle generation unit in this chamber system were designed to meet the needs of simulating multiphase atmospheric chemical reactions. The AIR chamber is able to accurately control temperature (2.5–31 ± 0.15 ∘C) and relative humidity (RH <2 %–>95 % ± 0.75 %) over a relatively broad range. In addition, an RH regulation module inside the chamber was designed to simulate the diurnal variation of ambient atmospheric RH. The aerosol generation unit is able to generate pre-deliquescent seed particles with an organic coating across a wide range of phase states or morphologies. The organic coating thickness of the aerosols within the chamber can be precisely controlled through adjusting the condensation temperature, further helping to elucidate the roles of seed particles in multiphase chemical reactions. The inner walls of the AIR chamber are passivated to reduce the wall loss rates of reactive gases. Yield experiments of α-pinene ozonolysis with and without seed particles combined with a box model simulation demonstrate the high-quality performance of secondary aerosol formation simulation using the AIR chamber.

Estimation of secondary organic aerosol formation parameters for the volatility basis set combining thermodenuder, isothermal dilution, and yield measurements

Abstract. Secondary organic aerosol (SOA) is a major fraction of the total organic aerosol (OA) in the atmosphere. SOA is formed by the partitioning onto pre-existent particles of low-vapor-pressure products of the oxidation of volatile, intermediate-volatility, and semivolatile organic compounds. Oxidation of the precursor molecules results in a myriad of organic products, making the detailed analysis of smog chamber experiments difficult and the incorporation of the corresponding results into chemical transport models (CTMs) challenging. The volatility basis set (VBS) is a framework that has been designed to help bridge the gap between laboratory measurements and CTMs. The parametrization of SOA formation for the VBS has been traditionally based on fitting yield measurements of smog chamber experiments. To reduce the uncertainty in this approach, we developed an algorithm to estimate the SOA product volatility distribution, effective vaporization enthalpy, and effective accommodation coefficient combining SOA yield measurements with thermograms (from thermodenuders) and areograms (from isothermal dilution chambers) from different experiments and laboratories. The algorithm is evaluated with “pseudo-data” produced from the simulation of the corresponding processes, assuming SOA with known properties and introducing experimental error. One of the novel features of our approach is that the proposed algorithm estimates the uncertainty in the predicted yields for different atmospheric conditions (temperature, SOA concentration levels, etc.). The uncertainty in these predicted yields is significantly smaller than that of the estimated volatility distributions for all conditions tested.

Characterization of Chemical Components and Optical Properties of Toluene Secondary Organic Aerosol in Presence of Ferric Chloride Fine Particles

Iron ion is the common transition metal ion in atmospheric aerosol, which can affect the components and optics of secondary organic aerosol (SOA). In the current study, the atmospheric photooxidation of toluene to produce SOA in the presence of ferric chloride fine particles is simulated in a smog chamber; on-line and off-line mass spectrometry and spectroscopic instruments are used to characterize constituents and optics of SOA. Compare with SOA formed in the absence of fine particles, the laser desorption/ionization mass spectra of toluene SOA generated in the presence of ferric chloride fine particles show ion peaks of m/z = 163 and 178, the UV-Vis spectra of the extracting solution for toluene SOA have peaks near 400 and 700 nm, and the electrospray ionization mass spectra contain peaks at m/z = 248 and 300. Based on this spectral information, it is shown that gaseous methylcatechol formed from photooxidation of toluene may react with iron ion on the surface of fine particles by complexing and oxidation–reduction, resulting in methylbenzoquinone products and metallo-organic complex ions such as [Fe(III)(CH3C6H3OO)]+, [Fe(III)(CH3C6H3 OO)2]− and [Fe(III)(CH3C6H3OO)Cl2]−. These products have strong light absorption ability, resulting in an increase in the averaged mass absorption coefficient (<MAC>) in the 200~1000 nm range and the MAC at 365 nm (MAC365) for toluene SOA, while <MAC> and MAC365 progressively increase with an increasing concentration of ferric chloride fine particles. These results serve as experimental references for the study of the formation mechanism and optical properties of metallo-organic complexes in atmospheric aerosol particles in regions experiencing high levels of fine particles of metal and automobile exhaust pollution.

Formation of secondary organic aerosols from the ozonolysis of Cis-3-hexenyl acetate: The effect of acidic seed particles and SO2

Cis-3-hexenyl acetate (cis-HXAC) is a major green leaf volatile released by plants, and its atmospheric degradation by O3 may play an important role in the formation of secondary organic aerosol (SOA). In this study, indoor smog chamber experiments were carried out to investigate the effects of particle acidity and SO2 on the formation of secondary organic aerosols (SOA) from the ozonolysis of cis-HXAC. Particle formation and growth were characterized using a scanning mobility particle sizer, and the chemical composition of the particles was analyzed by thermal-desorption gas chromatography mass spectrometry, with the main products and reaction pathways of cis-HXAC ozonolysis being identified. The results revealed that acidic seed particles inhibited SOA formation compared to non-acidic seed particles, and SO2 was considered to play a catalytic role in cis-HXAC ozonolysis, showing a good positive correlation with SOA generation. The results of this study provide new information on the ozonolysis of cis-HXAC, confirm the important role of anthropogenic pollution, and help to further elucidate the potential of green leaf volatiles ozonolysis to generate SOA under complex pollution conditions.

Direct evaluation of the ozone production regime in smog chamber experiments

Understanding the atmospheric ozone (O3) production regime is necessary for development of strategies to effectively control the amount of atmospheric O3. We have developed an instrument to directly evaluate the O3 production regime by measuring incremental changes of O3 production rate after injection of nitric oxide and propene into sample air. In this study, we conduct smog-chamber experiments on the oxidation of nitrogen oxides (NOx) and volatile organic compounds (VOC) and use the above instrument to measure O3 production during air mass oxidation. We also perform box model simulations with two chemical mechanisms (one near-explicit and one lumped) to cross validate the measured and simulated O3 production regimes. Oxidation experiments are conducted under VOC-rich and NOx-rich conditions; and the simulation generally reproduced O3 concentrations, OH reactivity (OHR), and contribution of NOx to total OHR. The measured O3 production regime changed from VOC-limited to NOx-limited after 1–3 h of irradiation by xenon arc lamps under the VOC-rich condition, whereas the regime remains VOC-limited throughout our experiment under the NOx-rich condition. The simulated timing of the regime transition under the VOC-rich condition is slower than that of the measured data, which could be attributed to overestimation of the NOx concentration. Both the measured and simulated timing of the regime transition estimated from the sensitivity to injection of O3 precursors NOx and VOC agree well with that estimated from the radical budget. The O3 production regimes estimated by the new instrument and by simulations are consistent with each other, suggesting that both methods are useful for estimating O3 production regime.

The hygroscopic properties of biomass burning aerosol from Eucalyptus and cow dung under different combustion conditions

Aerosols hygroscopic growth is of current interest due to its effect on atmospheric light scattering and extinction. Knowledge of hygroscopic properties is essential for predicting the effect of aerosol on cloud formation, regional visibility, climate impact, and lung deposition. Previous studies have used surrogate components of complex aerosol; and the application to complex multi-component aerosol like biomass burning aerosol is limited. We report aerosol hygroscopicity parameter of biomass burning aerosol derived from Eucalyptus and cow dung in a humidified smog chamber using two techniques: (1) measuring extinction hygroscopic enhancement factor f(RH) of aerosol using a cavity ring down spectrometer and deriving the hygroscopicity parameter using empirical equations and (2) directly using a Cloud Condensation Nuclei Counter (CCNC). Based on repeated measurements of the same fuel under different burning conditions, quantified by the modified combustion efficiency (MCE), we found that aerosol hygroscopicity depends on both fuel types and to some extent on burning conditions. For similar MCE, cow dung has a consistently larger value of hygroscopicity compared to Eucalyptus. Hygroscopicity measurements ranged from 0.024 to 0.577 for MCE measurements that ranged from 0.73 to 0.99. Specifically, sub-saturated hygroscopicity parameter values for cow dung are 0.024–0.131 and Eucalyptus are 0.012–0.300, while supersaturated hygroscopicity parameter values for cow dung are 0.071–0.577 and Eucalyptus are 0.021–0.494. There is a clear increase in hygroscopicity with increasing MCE for supersaturated cow dung measurements using CCNC but the dependence of kappa on MCE is generally inconclusive.

Yields and molecular composition of gas phase and secondary organic aerosol from the photooxidation of the volatile consumer product benzyl alcohol: formation of highly oxygenated and hydroxy nitroaromatic compounds.

Recently, volatile chemical products (VCPs) have been increasingly recognized as important precursors for secondary organic aerosol (SOA) and ozone in urban areas. However, their atmospheric chemistry, physical transformation, and their impact on climate, environment and human health remain poorly understood. Here, the yields and chemical composition at the molecular level of gas and particle phase products originating from the photooxidation of one of these VCPs, benzyl alcohol (BnOH), is reported. The SOA was generated in the presence of seed aerosol from nebulized ammonium sulfate solution in a 14.5 m3 smog chamber operated in flow mode. More than 50 organic compounds containing nitrogen and/or up to seven oxygen atoms were identified by mass spectrometry. While a detailed non-targeted analysis has been made, our primary focus has been to examine highly oxygenated and nitro-aromatic compounds. The major components include ring-opening products with high oxygen to carbon ratio (e.g., malic acid, tartaric acids, arabic acid, trihydroxy-oxo-pentanoic acids, and pentaric acid), and ring-retaining products (e.g., benzaldehyde, benzoic acid, catechol, 3-nitrobenzyl alcohol, 4-nitrocatechol, 2-hydroxy-5-nitrobenzyl alcohol, 2-nitrophloroglucinol, 3,4-dihydroxy-5-nitrobenzyl alcohol). The presence of some of these products in the gas and particle phases simultaneously provides evidence of their gas/particle partitioning. These oxygenated oxidation products made dominant contributions to the SOA particle composition in both low and high NOx systems. Yields, organic mass to organic carbon ratio, and proposed reaction schemes for selected compounds are provided. The aerosol yield was 5.2% for BnOH/H2O2 at SOA concentration of 52.9 µg m-3 and ranged between 1.7-8.1 % for BnOH/NOx at SOA concentration of 40.0-119.5 µg m-3.

Synergistic Effects of SO2 and NH3 Coexistence on SOA Formation from Gasoline Evaporative Emissions.

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.

Light absorption and scattering properties of indole secondary organic aerosol prepared under various oxidant and relative humidity conditions

Secondary organic aerosol (SOA) from indole was produced in a smog chamber under different relative humidity (RH = <2%, 25% and 50%) and with different oxidants (O3, OH, OH + NOx, and NO3). The mass absorption coefficients were measured by extracting SOA in methanol and taking absorption spectra in the 200-700 nm range. Chromophoric compounds were tentatively identified by liquid chromatography – spectrophotometry – mass spectrometry. One of the strongest chromophores was nitroindole, produced in high abundance by both NO3 and OH + NOx oxidation. Indole SOA was also prepared in an oxidation flow reactor (OFR) using the same set of oxidants under variable RH conditions. Densities of the OFR-generated SOA particles ranged from 1.05 g/cm3 for indole + O3 SOA to 1.33 g/cm3 for indole + OH SOA. The real (n) and imaginary (k) refractive indices were quantified using a broadband cavity-enhanced spectrometer (BBCES) over the 360–425 nm spectral range. The values of k ranged from 10−2 to 10−1 at 405 nm, which is comparable to those for humic-like substances and at least an order of magnitude larger than k values of SOA produced from other biogenic and anthropogenic volatile organic compounds. The k values for the indole + NO3 SOA had a strong and non-monotonic dependence on RH, suggesting two competing reaction mechanisms for the chromophores, highlighting the complex effect of water on the absorption coefficient of SOA from heterocyclic aromatic precursors. Strong absorption of indole SOA may contribute to the degradation of visibility near its emission sources, which include animal husbandry facilities and stressed plants.Copyright © 2023 American Association for Aerosol Research

Experimental study on synchrotron radiation photoionization of secondary organic aerosol derived from styrene ozonolysis

AbstractSecondary organic aerosol (SOA) produced by ozonolysis of styrene and other alkene compounds is a major part of fine particles in urban atmospheres. The atmospheric ozonolysis process of styrene is simulated in a smog chamber, and the formed SOA particles are detected on‐line by a synchronous radiation vacuum ultraviolet photoionization mass spectrometer (VUV‐PIMS) in this study. Through molecular ion peaks in the photonionization mass spectra of SOA and the corresponding photoionization efficiency curve, combined with off‐line measurement verification of ultraviolet visible and infrared absorption spectra, it is determined that formaldehyde, formic acid, benzene, phenol, benzaldehyde, and benzoic acid are the main constituents of styrene SOA. These provide new information for studying the atmospheric ozonolysis oxidation mechanism of styrene. VUV‐PIMS can get over complicated sample preparation procedures, secondary pollution, and other shortcomings of the off‐line method and is a useful instrument to measure constituents and unveil the formation process of SOA particles.

SO2 enhances aerosol formation from anthropogenic volatile organic compound ozonolysis by producing sulfur-containing compounds

Abstract. Sulfur dioxide (SO2) can affect aerosol formation in the atmosphere, but the underlying mechanisms remain unclear. Here, we investigate aerosol formation and composition from the ozonolysis of cyclooctene with and without SO2 addition in a smog chamber. Liquid chromatography equipped with high-resolution tandem mass spectrometry measurements indicates that monomer carboxylic acids and corresponding dimers with acid anhydride and aldol structures are important components in particles formed in the absence of SO2. A 9.4–12.6-times increase in particle maximum number concentration is observed in the presence of 14–192 ppb SO2. This increase is largely attributed to sulfuric acid (H2SO4) formation from the reactions of stabilized Criegee intermediates with SO2. In addition, a number of organosulfates (OSs) are detected in the presence of SO2, which are likely products formed from the heterogeneous reactions of oxygenated species with H2SO4. The molecular structures of OSs are also identified based on tandem mass spectrometry analysis. It should be noted that some of these OSs have been found in previous field studies but were classified as compounds from unknown sources or of unknown structures. The observed OSs are less volatile than their precursors and are therefore more effective contributors to particle formation and growth, partially leading to the increase in particle volume concentration under SO2-presence conditions. Our results provide an in-depth molecular-level insight into how SO2 alters particle formation and composition.

Titanium Dioxide Promotes New Particle Formation: A Smog Chamber Study.

TiO2 is a widely used material in building coatings. Many studies have revealed that TiO2 promotes the heterogeneous oxidation of SO2 and the subsequent sulfate formation. However, whether and how much TiO2 contributes to the gaseous H2SO4 and subsequent new particle formation (NPF) still remains unclear. Herein, we used a 1 m3 quartz smog chamber to investigate NPF in the presence of TiO2. The experimental results indicated that TiO2 could greatly promote NPF. The increases in particle formation rate (J) and growth rate due to the presence of TiO2 were quantified, and the promotion effect was attributed to the production of gaseous H2SO4. The promotion effect of TiO2 on SO2 oxidation and subsequent NPF decreased gradually due to the formation of surface sulfate but did not disappear completely, instead partly recovering after washing with water. Moreover, the promotion effect of TiO2 on NPF was observed regardless of differences in RH, and the most significant promotion effect of TiO2 associated with the strongest NPF occurred at an RH of 20%. Based on the experimental evidence, the environmental impact of TiO2 on gaseous H2SO4 and particle pollution in urban areas was estimated.

Evaluation of Ozone Formation Potential of Formaldehyde Using Smog Chamber Data

Formaldehyde (HCHO) is one of the important O3 precursors in the atmospheric environment, but the mechanism for HCHO photochemical reactions is not very clear now. In the present study, the effects of relative humidity (RH) and initial VOC/NOx ratio (RCN) on the HCHO‒NOx photochemical reaction process are studied in terms of smog chamber experiments. The MCM mechanism of formaldehyde is evaluated based on the experimental results. The measured maximum ozone concentration (O3-max) increases first and then decreases with the increase of RCN, and the RCN at the inflection point is 4.0 and 4.8 in the low (RH = 7.8%‒11.5%) and high RH (RH = 71.9%‒84.0%) experiments, respectively. The RH has no obvious effect on the measured O3-max values. The original MCM simulated O3 concentration reaches the maximum value much earlier than the experimental result, but can well simulate the incremental reactivity (IR) values in the experiments. The simulated incremental reactivity of HCHO at 6 h (IR6h) by MCM is influenced by other VOCs, and the simulated maximum IR6h is 1.9 ppb ppb-1, demonstrating that the contribution of HCHO to ozone is comparable to that of acetaldehyde in the atmospheric environment.

Evaluation of reaction between SO2 and CH2OO in MCM mechanism against smog chamber data from ethylene ozonolysis

Environmental context The process of ethylene ozonolysis is an essential source of CH2OO radicals, and the latter is an important oxidant for the atmospheric pollutant SO2. The accuracy of a widely used atmospheric chemistry model (Master Chemical Mechanism, MCM) in quantifying SO2 oxidation has not been evaluated. In this study, this accuracy was evaluated, and optimal parameters underpinned by data from smog chamber experiments. Rationale The oxidation of SO2 by CH2OO radicals in the ethylene-O3 system is one of the important pathways of sulfate aerosol formation, but the accuracy of Master Chemical Mechanism (MCM) simulation for this reaction was not evaluated, although the MCM has been widely used in previous studies. Methodology The oxidation of SO2 in the ethylene-O3 system was performed in detail under different conditions, which were used to evaluate the accuracy of MCM simulation for the reactions in this study. Results The experimental conditions of low RH and high initial SO2 concentration favour the SO2 oxidation in the ethylene ozonolysis, and the yield of CH2OO in the ethylene ozonolysis without irradiations was determined to be 0.43. The n-hexane (C6H14) oxidation intermediates can promote the SO2 oxidation rate by generating sulfur-containing organics in the aerosol water. The original MCM simulated SO2 consumption after 4-h reaction was more than 70% smaller than the measured results. By adjusting the yield of CH2OO and updating the reaction rate constants of CH2OO-related reactions (e.g. with SO2, H2O and organic acid), the difference between experiments and simulations decreased from 70% to 6.6%. Discussion The promotion effects of n-hexane on the oxidation of SO2 suggest that alkanes may be the precursors of sulfur-containing organics in the atmospheric environment. This study further confirms the effect of CH2OO on the oxidation of SO2 in the atmospheric environment and provides information on the performance of MCM simulation.