Toluene Secondary Organic Aerosol Research Articles

Investigation of dark condition nitrate radical- and ozone-initiated aging of toluene secondary organic aerosol: Importance of nitrate radical reactions with phenolic products

To investigate the reaction mechanisms during the NO3- and O3-initiated aging of aromatic secondary organic aerosol (SOA), the gases and particles formed from the OH-initiated oxidation of toluene were exposed to NO3 radicals and O3 in a laboratory chamber. Hydroxyl radicals for the oxidation of toluene were produced under light conditions through H2O2 photolysis and dark conditions through tetramethylethylene ozonolysis. Aerodyne aerosol mass spectrometer results demonstrated an increase in SOA and nitrate aerosol concentrations only after N2O5 injection, but no clear change after O3 injection. The results of proton transfer reaction-quadrupole interface-time of flight mass spectrometer showed that the signal of m/z 109.07 decreased and the signals of m/z 123.05 and m/z 154.05 increased after N2O5 injection, suggesting that gaseous cresols formed from toluene oxidation are rapidly degraded and gaseous nitrocresols and methylbenzoquinones are newly formed. The results of liquid chromatography-mass spectrometry analysis showed that nitrocresols and nitrosalicylic alcohols were the major products formed after N2O5 injection in the particle phase. To confirm the contribution of cresols on aging, NO3 oxidation of o-cresol was carried out, which resulted in the formation of similar products, i.e. gaseous nitrocresols and particulate nitrosalicylic alcohols. Yield curve analysis using two product model estimated that cresol accounted for ~62% of the increase in SOA during NO3-initiated aging of toluene SOA.

A new aerosol flow reactor to study secondary organic aerosol

Abstract. Gas-particle equilibrium partitioning is a fundamental concept used to describe the growth and loss of secondary organic aerosol (SOA). However, recent literature has suggested that gas-particle partitioning may be kinetically limited, preventing volatilization from the aerosol phase as a result of the physical state of the aerosol (e.g. glassy, viscous). Experimental measurements of diffusion constants within viscous aerosol are limited and do not represent the complex chemical composition observed in SOA (i.e. multicomponent mixtures). Motivated by the need to address fundamental questions regarding the effect of the physical state and chemical composition of a particle on gas-particle partitioning, we present the design and operation of a newly built 0.3 m3 continuous-flow reactor (CFR), which can be used as a tool to gain considerable insights into the composition and physical state of SOA. The CFR was used to generate SOA from the photo-oxidation of α-pinene, limonene, β-caryophyllene and toluene under different experimental conditions (i.e. relative humidity, VOC and VOC∕NOx ratios). Up to 102 mg of SOA mass was collected per experiment, allowing the use of highly accurate compositional- and single-particle analysis techniques, which are not usually accessible due to the large quantity of organic aerosol mass required for analysis. A suite of offline analytical techniques was used to determine the chemical composition and physical state of the generated SOA, including attenuated total reflectance infrared spectroscopy; carbon, hydrogen, nitrogen, and sulfur (CHNS) elemental analysis; 1H and 1H-13C nuclear magnetic resonance spectroscopy (NMR); ultra-performance liquid chromatography ultra-high-resolution mass spectrometry (UHRMS); high-performance liquid chromatography ion-trap mass spectrometry (HPLC-ITMS); and an electrodynamic balance (EDB). The oxygen-to-carbon (O∕C) and hydrogen-to-carbon (H∕C) ratios of generated SOA samples (determined using a CHNS elemental analyser) displayed good agreement with literature values and were consistent with the characteristic Van Krevelen diagram trajectory, with an observed slope of −0.41. The elemental composition of two SOA samples formed in separate replicate experiments displayed excellent reproducibility, with the O∕C and H∕C ratios of the SOA samples observed to be within error of the analytical instrumentation (instrument accuracy ±0.15 % to a reference standard). The ability to use a highly accurate CHNS elemental analyser to determine the elemental composition of the SOA samples allowed us to evaluate the accuracy of reported SOA elemental compositions using UHRMS (a commonly used technique). In all of the experiments investigated, the SOA O∕C ratios obtained for each SOA sample using UHRMS were lower than the O∕C ratios obtained from the CHNS analyser (the more accurate and non-selective technique). The average difference in the ΔO∕C ratios ranged from 19 % to 45 % depending on the SOA precursor and formation conditions. α-pinene SOA standards were generated from the collected SOA mass using semi-preparative HPLC-ITMS coupled to an automated fraction collector, followed by 1H NMR spectroscopy. Up to 35.8±1.6 % (propagated error of the uncertainty in the slope of the calibrations graphs) of α-pinene SOA was quantified using this method; a considerable improvement from most previous studies. Single aerosol droplets were generated from the collected SOA samples and trapped within an EDB at different temperatures and relative humidities to investigate the dynamic changes in their physiochemical properties. The volatilization of organic components from toluene and β-caryophyllene SOA particles at 0 % relative humidity was found to be kinetically limited, owing to particle viscosity. The unconventional use of a newly built CFR, combined with comprehensive offline chemical characterization and single-particle measurements, offers a unique approach to further our understanding of the relationship between SOA formation conditions, chemical composition and physiochemical properties.

Characterization of single scattering albedo and chemical components of aged toluene secondary organic aerosol

Secondary organic aerosol (SOA) can influence the radiative balance of the atmosphere via its optical properties. The single-scattering albedo (SSA) and complex refractive index (RI) are the basic optical parameters of the aerosol particles. Toluene SOA particles were formation and aging with extreme amounts of OH radicals without NOx in flow reactor chamber in this study, cavity-enhanced aerosol single-scattering albedometer, UV–Vis spectrometer, and liquid chromatography-mass spectrometry (LC-MS) were utilized to measure the optical properties and components of the aged toluene SOA, respectively. Experimental results demonstrated that the retrieved real part of RI for aged toluene SOA was 1.452 ± 0.002, which is consistent with the reported data. The measured SSA of aged toluene SOA was 0.78 ± 0.02, slightly lower than that of organic aerosols associated with biomass burning (BBOA), and the k-value (imaginary part of RI, corresponding to the absorption extent of SOA particles) was 0.024 ± 0.002, larger than that of fresh toluene SOA, indicating that the absorbing ability of SOA increased with increasing oxidation level. The obtained UV absorption and electrospray ionization mass spectrum shown that carboxylic acids are identified as the principal constituents of aged toluene SOA, which are responsible for the decreased SSA and increased k-value measured by the albedometer when compared to the fresh SOA. As the rate of production of SOA is greater than that of BBOA, the aged SOA particles may contribute remarkably to the radiative balance of the atmosphere. These would provide experimental basis for refine the radiative forcing estimates of anthropogenic SOA for certain regions.

Estimating Secondary Organic Aerosol Production from Toluene Photochemistry in a Megacity of China.

The production of secondary organic aerosols (SOA) from toluene photochemistry in Shanghai, a megacity of China, was estimated by two approaches, the parametrization method and the tracer-based method. The temporal profiles of toluene, together with other fifty-six volatile organic compounds (VOCs), were characterized. Combing with the vapor wall loss corrected SOA yields derived from chamber experiments, the estimated toluene SOA by the parametrization method as embodied in the two-product model contributes up to ∼40% of the total SOA budget during summertime. 2,3-Dihydroxy-4-oxopentanoic acid (DHOPA), a unique product from the OH-initiated oxidation of toluene in the presence of elevated NOx, was used as a tracer to back calculate the toluene SOA concentrations. By taking account for the effect of gas-particle partitioning processes on the fraction of DHOPA in the particle phase, the estimated toluene SOA concentrations agree within ∼33% with the estimates by the parametrization method. The agreement between these two independent approaches highlight the need to update current model frameworks with recent laboratory advances for a more accurate representation of SOA formation in regions with substantial anthropogenic emissions.

Formation of oxidized organic compounds from Cl-initiated oxidation of toluene

The formation of secondary organic aerosol (SOA) from toluene can impact urban air quality and therefore human health. Most SOA studies have focused on OH chemistry; however recent work suggests that chlorine atoms (Cl) may affect tropospheric chemistry more than previously assumed. This work focuses on SOA formation from Cl-initiated oxidation of toluene under different conditions. The fast reaction between Cl and toluene enabled complete consumption of toluene in environmental chamber experiments and aging of the toluene SOA. A high resolution time-of-flight chemical ionization mass spectrometer was used to observe several generations of gas-phase products. The presence of nitric oxides (NOx) appears to delay the formation of later generation products. Data from an aerosol chemical speciation monitor suggest that all SOA formed had high oxidation state, and that the bulk organic composition was different for SOA from Cl-dominated reactions compared to SOA from OH-dominated reactions. Addition of oxidant after all toluene had been consumed did not result in a significant change in the organic aerosol oxidation state, suggesting that the system may have reached an oxidative end-point in the particle phase.

Secondary organic aerosol of PM2.5 in a mountainous forest area in southeastern China: Molecular compositions and tracers implication

Secondary organic aerosol (SOA) plays an important role in global climate change and air quality. PM2.5 (particles with aerodynamic diameters ≤2.5 μm) samples were collected at a mountainous forest site (Mt. Wuyi) in southeastern China between November 2015 and July 2016. Fourteen PM2.5-bound SOA tracers, including isoprene, α/β‑pinene, β‑caryophyllene, and toluene, were measured using the gas-chromatography–mass-spectrometry method. The total concentrations of the isoprene, α/β‑pinene, β‑caryophyllene, and toluene SOA tracers were 45.28 ± 65.52, 30.66 ± 24.44, 5.99 ± 7.25, and 0.62 ± 0.72 ng m−3, respectively. The isoprene SOA tracers exhibited the highest concentration (145.97 ± 53.78 ng m−3) and accounted for 76 ± 9% of the total concentration of SOA tracers in summer. In fall-winter, the mass fraction of 2‑methylglyceric acid was significantly enhanced because of the lower temperature and higher NOx level. As later-generation products of α/β‑pinene tracers, high proportions of 3‑hydroxyglutaric acid and 3‑methyl‑1,2,3 butanetricarboxylic acid were observed on Mt. Wuyi, suggesting that the aerosols were highly oxidized. Biomass burning events affected by local and regional sources were identified by analyzing typical SOA tracers. Significant positive correlation (R2 = 0.74) was found between the β‑caryophyllene tracer and levoglucosan. The average concentration of secondary organic carbon (SOC) as estimated from SOA tracers was 1.46 μgC m−3. The isoprene SOC accounted for 70% of the total SOC in summer, whereas the β‑caryophyllene SOC was the predominant component in winter. Meanwhile, the estimated toluene SOC accounted for 11.6% of the total SOC during the study period. The study helps understanding the characteristics and the formation of SOA in a mountainous forest area of southeastern China.

Predicting the glass transition temperature and viscosity of secondary organic material using molecular composition

Abstract. Secondary organic aerosol (SOA) accounts for a large fraction of submicron particles in the atmosphere. SOA can occur in amorphous solid or semi-solid phase states depending on chemical composition, relative humidity (RH), and temperature. The phase transition between amorphous solid and semi-solid states occurs at the glass transition temperature (Tg). We have recently developed a method to estimate Tg of pure compounds containing carbon, hydrogen, and oxygen atoms (CHO compounds) with molar mass less than 450 g mol−1 based on their molar mass and atomic O : C ratio. In this study, we refine and extend this method for CH and CHO compounds with molar mass up to ∼ 1100 g mol−1 using the number of carbon, hydrogen, and oxygen atoms. We predict viscosity from the Tg-scaled Arrhenius plot of fragility (viscosity vs. Tg∕T) as a function of the fragility parameter D. We compiled D values of organic compounds from the literature and found that D approaches a lower limit of ∼ 10 (±1.7) as the molar mass increases. We estimated the viscosity of α-pinene and isoprene SOA as a function of RH by accounting for the hygroscopic growth of SOA and applying the Gordon–Taylor mixing rule, reproducing previously published experimental measurements very well. Sensitivity studies were conducted to evaluate impacts of Tg, D, the hygroscopicity parameter (κ), and the Gordon–Taylor constant on viscosity predictions. The viscosity of toluene SOA was predicted using the elemental composition obtained by high-resolution mass spectrometry (HRMS), resulting in a good agreement with the measured viscosity. We also estimated the viscosity of biomass burning particles using the chemical composition measured by HRMS with two different ionization techniques: electrospray ionization (ESI) and atmospheric pressure photoionization (APPI). Due to differences in detected organic compounds and signal intensity, predicted viscosities at low RH based on ESI and APPI measurements differ by 2–5 orders of magnitude. Complementary measurements of viscosity and chemical composition are desired to further constrain RH-dependent viscosity in future studies.

Effect of relative humidity on the composition of secondary organic aerosol from the oxidation of toluene

Abstract. The effect of relative humidity (RH) on the chemical composition of secondary organic aerosol (SOA) formed from low-NOx toluene oxidation in the absence of seed particles was investigated. SOA samples were prepared in an aerosol smog chamber at < 2 % RH and 75 % RH, collected on Teflon filters, and analyzed with nanospray desorption electrospray ionization high-resolution mass spectrometry (nano-DESI–HRMS). Measurements revealed a significant reduction in the fraction of oligomers present in the SOA generated at 75 % RH compared to SOA generated under dry conditions. In a separate set of experiments, the particle mass concentrations were measured with a scanning mobility particle sizer (SMPS) at RHs ranging from < 2 to 90 %. It was found that the particle mass loading decreased by nearly an order of magnitude when RH increased from < 2 to 75–90 % for low-NOx toluene SOA. The volatility distributions of the SOA compounds, estimated from the distribution of molecular formulas using the “molecular corridor” approach, confirmed that low-NOx toluene SOA became more volatile on average under high-RH conditions. In contrast, the effect of RH on SOA mass loading was found to be much smaller for high-NOx toluene SOA. The observed increase in the oligomer fraction and particle mass loading under dry conditions were attributed to the enhancement of condensation reactions, which produce water and oligomers from smaller compounds in low-NOx toluene SOA. The reduction in the fraction of oligomeric compounds under humid conditions is predicted to partly counteract the previously observed enhancement in the toluene SOA yield driven by the aerosol liquid water chemistry in deliquesced inorganic seed particles.

Dithiothreitol activity by particulate oxidizers of SOA produced from photooxidation of hydrocarbons under varied NO<sub><i>x</i></sub> levels

Abstract. When hydrocarbons (HCs) are atmospherically oxidized, they form particulate oxidizers, including quinones, organic hydroperoxides, and peroxyacyl nitrates (PANs). These particulate oxidizers can modify cellular materials (e.g., proteins and enzymes) and adversely modulate cell functions. In this study, the contribution of particulate oxidizers in secondary organic aerosols (SOAs) to the oxidative potential was investigated. SOAs were generated from the photooxidation of toluene, 1,3,5-trimethylbenzene, isoprene, and α-pinene under varied NOx levels. Oxidative potential was determined from the typical mass-normalized consumption rate (reaction time t = 30 min) of dithiothreitol (DTTt), a surrogate for biological reducing agents. Under high-NOx conditions, the DTTt of toluene SOA was 2–5 times higher than that of the other types of SOA. Isoprene DTTt significantly decreased with increasing NOx (up to 69 % reduction by changing the HC ∕ NOx ratio from 30 to 5). The DTTt of 1,3,5-trimethylbenzene and α-pinene SOA was insensitive to NOx under the experimental conditions of this study. The significance of quinones to the oxidative potential of SOA was tested through the enhancement of DTT consumption in the presence of 2,4-dimethylimidazole, a co-catalyst for the redox cycling of quinones; however, no significant effect of 2,4-dimethylimidazole on modulation of DTT consumption was observed for all SOA, suggesting that a negligible amount of quinones was present in the SOA of this study. For toluene and isoprene, mass-normalized DTT consumption (DTTm) was determined over an extended period of reaction time (t = 2 h) to quantify their maximum capacity to consume DTT. The total quantities of PANs and organic hydroperoxides in toluene SOA and isoprene SOA were also measured using the Griess assay and the 4-nitrophenylboronic acid assay, respectively. Under the NOx conditions (HC ∕ NOx ratio: 5–36 ppbC ppb−1) applied in this study, the amount of organic hydroperoxides was substantial, while PANs were found to be insignificant for both SOAs. Isoprene DTTm was almost exclusively attributable to organic hydroperoxides, while toluene DTTm was partially attributable to organic hydroperoxides. The DTT assay results of the model compound study suggested that electron-deficient alkenes, which are abundant in toluene SOA, could also modulate DTTm.

Prediction of delivery of organic aerosols onto air-liquid interface cells in vitro using an electrostatic precipitator

To better characterize biological responses to atmospheric organic aerosols, the efficient delivery of aerosol to in vitro lung cells is necessary. In this study, chamber generated secondary organic aerosol (SOA) entered the commercialized exposure chamber (CULTEX® Radial Flow System Compact) where it interfaced with an electrostatic precipitator (ESP) (CULTEX® Electrical Deposition Device) and then deposited on a particle collection plate. This plate contained human lung cells (BEAS-2B) that were cultured on a membrane insert to produce an air-liquid interface (ALI). To augment in vitro assessment using the ESP exposure device, the particle dose was predicted for various sampling parameters such as particle size, ESP deposition voltage, and sampling flowrate. The dose model was evaluated against the experimental measured mass of collected airborne particles. The high flowrate used in this study increased aerosol dose but failed to achieve cell stability. For example, RNA in the ALI BEAS-2B cells in vitro was stable at 0.15L/minute but decayed at high flowrates. The ESP device and the resulting model were applied to in vitro studies (i.e., viability and IL-8 expression) of toluene SOA using ALI BEAS-2B cells with a flowrate of 0.15L/minute, and no cellular RNA decay occurred.

Role of Aerosol Liquid Water in Secondary Organic Aerosol Formation from Volatile Organic Compounds.

A key mechanism for atmospheric secondary organic aerosol (SOA) formation occurs when oxidation products of volatile organic compounds condense onto pre-existing particles. Here, we examine effects of aerosol liquid water (ALW) on relative SOA yield and composition from α-pinene ozonolysis and the photooxidation of toluene and acetylene by OH. Reactions were conducted in a room-temperature flow tube under low-NOx conditions in the presence of equivalent loadings of deliquesced (∼20 μg m-3 ALW) or effloresced (∼0.2 μg m-3 ALW) ammonium sulfate seeds at exactly the same relative humidity (RH = 70%) and state of wall conditioning. We found 13% and 19% enhancements in relative SOA yield for the α-pinene and toluene systems, respectively, when seeds were deliquesced rather than effloresced. The relative yield doubled in the acetylene system, and this enhancement was partially reversible upon drying the prepared SOA, which reduced the yield by 40% within a time scale of seconds. We attribute the high relative yield of acetylene SOA on deliquesced seeds to aqueous partitioning and particle-phase reactions of the photooxidation product glyoxal. The observed range of relative yields for α-pinene, toluene, and acetylene SOA on deliquesced and effloresced seeds suggests that ALW plays a complicated, system-dependent role in SOA formation.

Oxidative potential of secondary organic aerosols produced from photooxidation of different hydrocarbons using outdoor chamber under ambient sunlight

The oxidative potential of various secondary organic aerosols (SOA) was measured using dithiothreitol (DTT) assay to understand how organic aerosols react with cellular materials. SOA was produced via the photooxidation of four different hydrocarbons (toluene, 1,3,5-trimethylbenzene, isoprene and α-pinene) in the presence of NOx using a large outdoor photochemical smog chamber. The DTT consumption rate was normalized by the aerosol mass, which is expressed as DTTmass. Toluene SOA and isoprene SOA yielded higher DTTmass than 1,3,5-trimethylbenzene SOA or α-pinene SOA. In order to discover the correlation between the molecular structure and oxidative potential, the DTT responses of selected model compounds were also measured. Among them, conjugated aldehydes, quinones, and H2O2 showed considerable DTT response. To investigate the correlation between DTT response and cell responses in vitro, the expression of biological markers, i.e. IL-6, IL-8, and HMOX-1 were studied using small airway epithelial cells. Higher cellular expression of IL-8 was observed with toluene SOA exposure compared to 1,3,5-trimethylbenzene SOA exposure, which aligned with the results from DTT assay. Our study also suggests that within the urban atmosphere, the contribution of toluene SOA and isoprene SOA to the oxidative potential of ambient SOA will be more significant than that of α-pinene SOA.

Molecular characterization of brown carbon (BrC) chromophores in secondary organic aerosol generated from photo-oxidation of toluene.

Atmospheric brown carbon (BrC) is a significant contributor to light absorption and climate forcing. However, little is known about a fundamental relationship between the chemical composition of BrC and its optical properties. In this work, light-absorbing secondary organic aerosol (SOA) was generated in the PNNL chamber from toluene photo-oxidation in the presence of NOx (Tol-SOA). Molecular structures of BrC components were examined using nanospray desorption electrospray ionization (nano-DESI) and liquid chromatography (LC) combined with UV/Vis spectroscopy and electrospray ionization (ESI) high-resolution mass spectrometry (HRMS). The chemical composition of BrC chromophores and the light absorption properties of toluene SOA (Tol-SOA) depend strongly on the initial NOx concentration. Specifically, Tol-SOA generated under high-NOx conditions (defined here as initial NOx/toluene of 5/1) appears yellow and mass absorption coefficient of the bulk sample (MACbulk@365 nm = 0.78 m(2) g(-1)) is nearly 80 fold higher than that measured for the Tol-SOA sample generated under low-NOx conditions (NOx/toluene < 1/300). Fifteen compounds, most of which are nitrophenols, are identified as major BrC chromophores responsible for the enhanced light absorption of Tol-SOA material produced in the presence of NOx. The integrated absorbance of these fifteen chromophores accounts for 40-60% of the total light absorbance by Tol-SOA at wavelengths between 300 nm and 500 nm. The combination of tandem LC-UV/Vis-ESI/HRMS measurements provides an analytical platform for predictive understanding of light absorption properties by BrC and their relationship to the structure of individual chromophores. General trends in the UV/Vis absorption by plausible isomers of the BrC chromophores were evaluated using theoretical chemistry calculations. The molecular-level understanding of BrC chemistry is helpful for better understanding the evolution and behavior of light absorbing aerosols in the atmosphere.

Simulated impact of NOx on SOA formation from oxidation of toluene and m-xylene

Despite the crucial role of aromatic-derived secondary organic aerosol (SOA) in deteriorating air quality, its formation mechanism is not well understood, and the dependence of aromatic SOA formation on nitrogen oxides (NOx) is not captured fully by most SOA formation models. In this study, NOx-dependent mechanisms of toluene and m-xylene SOA formation are updated using the gas-phase Caltech Atmospheric Chemistry Mechanism (CACM) coupled to a gas/aerosol partitioning model. The updated models were optimized by comparison to eighteen chamber experiments performed under both high- and low-NOx conditions at the University of California – Riverside. Correction factors for vapor pressures imply uncharacterized association chemistry, likely in the aerosol phase. Difficulty of the presented model lies in predicting O3 production well, with overprediction (typically 20–40%), particularly under low NOx conditions (up to one fold). Mean normalized biases for other species (NO2 and SOA) and conditions are smaller (up to ±50%). The newly developed model can predict strong decreases of m-xylene SOA yield with increasing NOx. Simulated SOA speciation implies the importance of ring-opening products in governing SOA formation (up to ∼40–60% for both aromatics). Speciation distributions under varied NOx levels imply that competition between hydroperoxide radical and NO for reaction with a bicyclic peroxide radical as the most commonly accepted mechanism may not be the only factor influencing SOA formation. The reaction of aromatic peroxy radicals with NO competing with self-cyclization (a new mechanism updated in this study) might also affect NOx-dependence of SOA formation. Different simulated importance of a phenolic route in governing SOA formation between toluene and m-xylene suggests that the number of methyl groups on the aromatic ring is important in SOA formation chemistry.

Simulation of aromatic SOA formation using the lumping model integrated with explicit gas-phase kinetic mechanisms and aerosol-phase reactions

Abstract. The Unified Partitioning-Aerosol phase Reaction (UNIPAR) model has been developed to predict the secondary organic aerosol (SOA) formation through multiphase reactions. The model was evaluated with aromatic SOA data produced from the photooxidation of toluene and 1,3,5-trimethylbenzene (135-TMB) under various concentrations of NOx and SO2 using an outdoor reactor (University of Florida Atmospheric PHotochemical Outdoor Reactor (UF-APHOR) chamber). When inorganic species (sulfate, ammonium and water) are present in aerosol, the prediction of both toluene SOA and 135-TMB SOA, in which the oxygen-to-carbon (O : C) ratio is lower than 0.62, are approached under the assumption of a complete organic/electrolyte-phase separation below a certain relative humidity. An explicit gas-kinetic model was employed to express gas-phase oxidation of aromatic hydrocarbons. Gas-phase products are grouped based on their volatility (6 levels) and reactivity (5 levels) and exploited to construct the stoichiometric coefficient (αi,j) matrix, the set of parameters used to describe the concentrations of organic compounds in multiphase. Weighting of the αi,j matrix as a function of NOx improved the evaluation of NOx effects on aromatic SOA. The total amount of organic matter (OMT) is predicted by two modules in the UNIPAR model: OMP by a partitioning process and OMAR by aerosol-phase reactions. The OMAR module predicts multiphase reactions of organic compounds, such as oligomerization, acid-catalyzed reactions, and organosulfate (OS) formation. The model reasonably simulates SOA formation under various aerosol acidities, NOx concentrations, humidities and temperatures. Furthermore, the OS fractions in the SOA predicted by the model were in good agreement with the experimentally measured OS fractions.

Real refractive indices and volatility of secondary organic aerosol generated from photooxidation and ozonolysis of limonene, α-pinene and toluene

Abstract. Thermodenuding particles can provide insights into aerosol composition and may be a way to create particles in laboratory chambers that better mimic the atmosphere. The relative volatility of secondary organic aerosol (SOA) was investigated by evaporating organics from the particles using a thermodenuder (TD) at temperatures between ∼60 and 100 °C. Volatility was influenced by the parent hydrocarbon, oxidation chemistry and relative humidity (RH). For SOA generated from ozonolysis, limonene had lower volatility than α-pinene, and OH scavengers had no influence on volatility. For photooxidation, α-pinene SOA was slightly more volatile than limonene SOA. Increasing RH also modestly increased volatility, while toluene SOA was unaffected by heating to 98 °C. For both α-pinene and limonene, the concentration of NOx and the HC / NOx ratio had no discernible effect on SOA volatility. Refractive indices for the original and denuded particles were retrieved from polar nephelometer measurements using parallel and perpendicular polarized 532 nm light. Retrievals were performed with a genetic algorithm method using Mie–Lorenz scattering theory and measured particle size distributions. Retrieved refractive indices for the SOA before thermodenuding varied between 1.35 and 1.61 depending on several factors, including parent hydrocarbon, oxidation chemistry, and SOA generation temperature. For high NOx SOA, as particles shrink, their refractive index returns to the value of the corresponding size particles before heating (limonene) or slightly higher (α-pinene). For low NOx however, the resulting refractive index is 0.05 ± 0.02 lower than the corresponding size undenuded particles. Additionally, for α-pinene SOA from ozonolysis with OH radical scavenger, resulting refractive indices were higher by about 0.03 after heating. Consistent with no change in size, refractive indices of toluene SOA were unaffected by heating. Finally, refractive index data available to date are reviewed, leading to the suggestion that the most representative values for mr at λ =532 nm for biogenic and anthropogenic SOA are 1.44 and 1.55, respectively.

On the Mixing and Evaporation of Secondary Organic Aerosol Components

The physical state and chemical composition of an organic aerosol affect its degree of mixing and its interactions with condensing species. We present here a laboratory chamber procedure for studying the effect of the mixing of organic aerosol components on particle evaporation. The procedure is applied to the formation of secondary organic aerosol (SOA) from α-pinene and toluene photooxidation. SOA evaporation is induced by heating the chamber aerosol from room temperature (25 °C) to 42 °C over 7 h and detected by a shift in the peak diameter of the SOA size distribution. With this protocol, α-pinene SOA is found to be more volatile than toluene SOA. When SOA is formed from the two precursors sequentially, the evaporation behavior of the SOA most closely resembles that of SOA from the second parent hydrocarbon, suggesting that the structure of the mixed SOA resembles a core of SOA from the initial precursor coated by a layer of SOA from the second precursor. Such a core-and-shell configuration of the organic aerosol phases implies limited mixing of the SOA from the two precursors on the time scale of the experiments, consistent with a high viscosity of at least one of the phases.

Primary Sources and Secondary Formation of Organic Aerosols in Beijing, China

Ambient aerosol samples were collected at an urban site and an upwind rural site of Beijing during the CAREBEIJING-2008 (Campaigns of Air quality REsearch in BEIJING and surrounding region) summer field campaign. Contributions of primary particles and secondary organic aerosols (SOA) were estimated by chemical mass balance (CMB) modeling and tracer-yield method. The apportioned primary and secondary sources explain 73.8% ± 9.7% and 79.6% ± 10.1% of the measured OC at the urban and rural sites, respectively. Secondary organic carbon (SOC) contributes to 32.5 ± 15.9% of the organic carbon (OC) at the urban site, with 17.4 ± 7.6% from toluene, 9.7 ± 5.4% from isoprene, 5.1 ± 2.0% from α-pinene, and 2.3 ± 1.7% from β-caryophyllene. At the rural site, the secondary sources are responsible for 38.4 ± 14.4% of the OC, with the contributions of 17.3 ± 6.9%, 13.9 ± 9.1%, 5.6 ± 1.9%, and 1.7 ± 1.0% from toluene, isoprene, α-pinene, and β-caryophyllene, respectively. Compared with other regions in the world, SOA in Beijing is less aged, but the concentrations are much higher; between the sites, SOA is more aged and affected by regional transport at the urban site. The high SOA loading in Beijing is probably attributed to the high regional SOC background (~2 μg m(-3)). The toluene SOC concentration is high and comparable at the two sites, implying that some anthropogenic components, at least toluene SOA, are widespread in Beijing and represents a major factor in affecting the regional air quality. The aerosol gaseous precursor concentrations and temperature correlate well with SOA, both affecting SOA formation. The significant SOA enhancement with increasing water uptake and acidification indicates that the aqueous-phase reactions are largely responsible SOA formation in Beijing.

The SOA formation model combined with semiempirical quantum chemistry for predicting UV-Vis absorption of secondary organic aerosols

A new model for predicting the UV-visible absorption spectra of secondary organic aerosols (SOA) has been developed. The model consists of two primary parts: a SOA formation model and a semiempirical quantum chemistry method. The mass of SOA is predicted using the PHRCSOA (Partitioning Heterogeneous Reaction Consortium Secondary Organic Aerosol) model developed by Cao and Jang [Environ. Sci. Technol., 2010, 44, 727]. The chemical composition is estimated using a combination of the kinetic model (MCM) and the PHRCSOA model. The absorption spectrum is obtained by taking the sum of the spectrum of each SOA product calculated using a semiempirical NDDO (Neglect of Diatomic Differential Overlap)-based method. SOA was generated from the photochemical reaction of toluene or α-pinene at different NO(x) levels (low NO(x): 24-26 ppm, middle NO(x): 49 ppb, high NO(x): 104-105 ppb) using a 2 m(3) indoor Teflon film chamber. The model simulation reasonably agrees with the measured absorption spectra of α-pinene SOA but underestimates toluene SOA under high and middle NO(x) conditions. The absorption spectrum of toluene SOA is moderately enhanced with increasing NO(x) concentrations, while that of α-pinene SOA is not affected. Both measured and calculated UV-visible spectra show that the light absorption of toluene SOA is much stronger than that of α-pinene SOA.

Light absorption coefficient measurement of SOA using a UV–Visible spectrometer connected with an integrating sphere

Abstract A method for measuring an aerosol light absorption coefficient ( B a ) has been developed using a conventional UV–visible spectrometer equipped with an integrating sphere covering a wide range of wavelengths (280–800 nm). The feasibility of the proposed method was evaluated in both the transmittance mode (TUV-IS) and the reflective mode (RUV-IS) using the reference aerosol known for the cross-sectional area. The aerosol was collected on a conventional filter and measured for B a values. The resulting RUV-IS method was applied to measure light absorption of secondary organic aerosol (SOA). SOA was produced through photooxidation of different precursor hydrocarbons such as toluene, d -limonene and α -pinene in the presence of NO x (60–70 ppb) and inorganic seed aerosol using a 2-m 3 indoor Teflon film chamber. Of the three precursor hydrocarbons, the B a value of toluene SOA (0.574 m 2 g −1 at 350 nm) was the highest compared with B a values for α -pinene SOA (0.029 m 2 g −1 ) and d -limonene SOA (0.038 m 2 g −1 ). When d -limonene SOA or toluene SOA was internally mixed with neutral [(NH 4 ) 2 SO 4 ] or acidic inorganic seed (NH 4 HSO 4 :H 2 SO 4 = 1:1 by mole), the SOA showed 2–3 times greater B a values at 350 nm than the SOA with no seed. Aerosol aging with a light source for this study reduced B a values of SOA (e.g., on average 10% for toluene SOA and 30% for d -limonene SOA within 4 h). Overall, weak absorption appeared for chamber-generated SOA over wavelengths ranging from 280 to 550 nm, which fall into the sunlight spectrum.