Measurements of secondary organic aerosol formed from OH-initiated photo-oxidation of isoprene using online photoionization aerosol mass spectrometry

Isoprene is a significant source of atmospheric organic aerosol; however, the secondary organic aerosol (SOA) formation and involved chemical reaction pathways have remained to be elucidated. Recent works have shown that the photo-oxidation of isoprene leads to form SOA. In this study, the chemical composition of SOA from the OH-initiated photo-oxidation of isoprene, in the absence of seed aerosols, was investigated through the controlled laboratory chamber experiments. Thermal desorption/tunable vacuum-ultraviolet photoionization time-of-flight aerosol mass spectrometry (TD-VUV-TOF-PIAMS) was used in conjunction with the environmental chamber to study SOA formation. The mass spectra obtained at different photon energies and the photoionization efficiency (PIE) spectra of the SOA products can be obtained in real time. Aided by the ionization energies (IE) either from the ab initio calculations or the literatures, a number of SOA products were proposed. In addition to methacrolein, methyl vinyl ketone, and 3-methyl-furan, carbonyls, hydroxycarbonyls, nitrates, hydroxynitrates, and other oxygenated compounds in SOA formed in laboratory photo-oxiadation experiments were identified, some of them were investigated for the first time. Detailed chemical identification of SOA is crucial for understanding the photo-oxidation mechanisms of VOCs and the eventual formation of SOA. Possible reaction mechanisms will be discussed.     

Nitrogen-containing organic compounds and oligomers in secondary organic aerosol formed by photooxidation of isoprene

Electrospray ionization high-resolution mass spectrometry (ESI HR-MS) was used to probe molecular structures of oligomers in secondary organic aerosol (SOA) generated in laboratory experiments on isoprene photooxidation at low- and high-NO(x) conditions. Approximately 80-90% of the observed products are oligomers and up to 33% by number are nitrogen-containing organic compounds (NOC). We observe oligomers with maximum 8 monomer units in length. Tandem mass spectrometry (MS(n)) confirms NOC compounds are organic nitrates and elucidates plausible chemical building blocks contributing to oligomer formation. Most organic nitrates are comprised of methylglyceric acid units. Other important multifunctional C(2)-C(5) monomer units are identified including methylglyoxal, hydroxyacetone, hydroxyacetic acid, and glycolaldehyde. Although the molar fraction of NOC in the high-NO(x) SOA is high, the majority of the NOC oligomers contain only one nitrate moiety resulting in a low average N:C ratio of 0.019. Average O:C ratios of the detected SOA compounds are 0.54 under the low-NO(x) conditions and 0.83 under the high-NO(x) conditions. Our results underscore the importance of isoprene photooxidation as a source of NOC in organic particulate matter.     

Products and mechanism of secondary organic aerosol formation from reactions of n-alkanes with OH radicals in the presence of NOx

Secondary organic aerosol (SOA) formation from reactions of n-alkanes with OH radicals in the presence of NOx was investigated in an environmental chamber using a thermal desorption particle beam mass spectrometer for particle analysis. SOA consisted of both first- and higher-generation products, all of which were nitrates. Major first-generation products were sigma-hydroxynitrates, while higher-generation products consisted of dinitrates, hydroxydinitrates, and substituted tetrahydrofurans containing nitrooxy, hydroxyl, and carbonyl groups. The substituted tetrahydrofurans are formed by a series of reactions in which sigma-hydroxycarbonyls isomerize to cyclic hemiacetals, which then dehydrate to form substituted dihydrofurans (unsaturated compounds) that quickly react with OH radicals to form lower volatility products. SOA yields ranged from approximately 0.5% for C8 to approximately 53% for C15, with a sharp increase from approximately 8% for C11 to approximately 50% for C13. This was probably due to an increase in the contribution of first-generation products, as well as other factors. For example, SOA formed from the C10 reaction contained no first-generation products, while for the C15 reaction SOA was approximately 40% first-generation and approximately 60% higher-generation products, respectively. First-generation sigma-hydroxycarbonyls are especially important in SOA formation, since their subsequent reactions can rapidly form low volatility compounds. In the atmosphere, substituted dihydrofurans created from sigma-hydroxycarbonyls will primarily react with O3 or NO3 radicals, thereby opening reaction pathways not normally accessible to saturated compounds.     

Transitions from functionalization to fragmentation reactions of laboratory secondary organic aerosol (SOA) generated from the OH oxidation of alkane precursors

Functionalization (oxygen addition) and fragmentation (carbon loss) reactions governing secondary organic aerosol (SOA) formation from the OH oxidation of alkane precursors were studied in a flow reactor in the absence of NO(x). SOA precursors were n-decane (n-C10), n-pentadecane (n-C15), n-heptadecane (n-C17), tricyclo[5.2.1.0(2,6)]decane (JP-10), and vapors of diesel fuel and Southern Louisiana crude oil. Aerosol mass spectra were measured with a high-resolution time-of-flight aerosol mass spectrometer, from which normalized SOA yields, hydrogen-to-carbon (H/C) and oxygen-to-carbon (O/C) ratios, and C(x)H(y)+, C(x)H(y)O+, and C(x)H(y)O(2)+ ion abundances were extracted as a function of OH exposure. Normalized SOA yield curves exhibited an increase followed by a decrease as a function of OH exposure, with maximum yields at O/C ratios ranging from 0.29 to 0.74. The decrease in SOA yield correlates with an increase in oxygen content and decrease in carbon content, consistent with transitions from functionalization to fragmentation. For a subset of alkane precursors (n-C10, n-C15, and JP-10), maximum SOA yields were estimated to be 0.39, 0.69, and 1.1. In addition, maximum SOA yields correspond with a maximum in the C(x)H(y)O+ relative abundance. Measured correlations between OH exposure, O/C ratio, and H/C ratio may enable identification of alkane precursor contributions to ambient SOA.     

Effect of acidity on secondary organic aerosol formation from isoprene

The effect of particle-phase acidity on secondary organic aerosol (SOA) formation from isoprene is investigated in a laboratory chamber study, in which the acidity of the inorganic seed aerosol was controlled systematically. The observed enhancement in SOA mass concentration is closely correlated to increasing aerosol acidity (R2 = 0.979). Direct chemical evidence for acid-catalyzed particle-phase reactions was obtained from the SOA chemical analyses. Aerosol mass concentrations for the 2-methyltetrols, as well as the newly identified sulfate esters, both of which serve as tracers for isoprene SOA in ambient aerosols, increased significantly with enhanced aerosol acidity. Aerosol acidities, as measured in nmol of H+ m(-3), employed in the present study are in the same range as those observed in tropospheric aerosol collected from the eastern U.S.     

Impact of propene on secondary organic aerosol formation from m-xylene

Propene is widely used in smog chamber experiments to increase the hydroxyl radical (OH) level based on the assumption that the formation of secondary organic aerosol (SOA) from parent hydrocarbon is unaffected. A series of m-xylene/NO(x) photooxidation experiments were conducted in the presence of propene in the University of California CE-CERT atmospheric chamber facility. The experimental data are compared with previous m-xylene/N0(x) photooxidation work performed in the same chamber facility in the absence of propene (Song et al. Environ. Sci. Technol. 2005, 39, 3143-3149). The result shows that, for similar initial conditions, experiments with propene have lower reaction rates of m-xylene than those without propene, which indicates that propene reduces OH in the system. Furthermore, experiments with propene showed more than 15% reduction in SOA yield compared to experiments in the absence of propene. Additional experiments of m-xylene/ NO(x) with CO showed similar trends of suppressing OH and SOA formation. These results indicate that SOA from m-xylene/NO(x) photooxidation is strongly dependent on the OH level present, which provides evidence for the critical role of OH in SOA formation from aromatic hydrocarbons.     

Heterogeneous reactions of methylglyoxal in acidic media: implications for secondary organic aerosol formation

Recent environmental chamber studies have suggested that acid-catalyzed particle-phase reactions of organic carbonyls contribute to the formation of secondary organic aerosol (SOA). We report the first measurements of uptake of methylglyoxal on liquid H2SO4 over the temperature range of 250-298 K and acidic range of 55-85 wt %. From the time-dependent uptake the effective Henry's law solubility constant (H*) was determined. Heterogeneous reactions of methylglyoxal are shown to decrease with acidity and involve negligible formation of sulfate esters. Hydration and polymerization likely explain the measured uptake of methylglyoxal on H2SO4 and the measurements do not support an acid-catalyzed uptake of methylglyoxal. The results imply that heterogeneous reactions of methylglyoxal contribute to organic aerosol formation in less acidic media and hydration and polymerization of methylglyoxal in the atmospheric aerosol-phase are dependent on the hygroscopicity, rather than the acidity of the aerosols.     

Formation of oligomers in secondary organic aerosol

The formation of oligomeric molecules, an important step in secondary organic aerosol production, is reported. Aerosols were produced by the reaction of alpha-pinene and ozone in the presence of acid seed aerosol and characterized by exact mass measurements and tandem mass spectrometry. Oligomeric products between 200 and 900 u were detected with both electrospray ionization and matrix-assisted laser desorption ionization. The exact masses and dissociation products of these ions were consistent with various combinations of the known primary products of this reaction ("monomers") with and/or without the expected acid-catalyzed decomposition products of the monomers. Oligomers as large as tetramers were detected. Both aldol condensations and gem-diol reactions are suggested as possible pathways for oligomer formation. Exact mass measurements also revealed reaction products that cannot be explained by simple oligomerization of monomers and monomer decomposition products, suggesting the existence of complex reaction channels. Chemical reactions leading to oligomer formation provide a reasonable answer to a difficult problem associated with secondary organic aerosol production in the atmosphere. It is unlikely that monomers alone play an important role in the formation and growth of nuclei in the atmosphere as their Kelvin vapor pressures are too high for them to significantly partition into the particle phase. Polymerization provides a mechanism by which partitioning to the particle phase becomes favored.     

Calculations of incremental secondary organic aerosol reactivity

The incremental secondary organic aerosol reactivity (ISOAR) of a species j is defined as the relative incremental change in secondary organic aerosol (SOA) formed per relative incremental change in the amount of species jemitted. The California Institute of Technology three-dimensional air quality model is used in conjunction with the Caltech Atmospheric Chemistry Mechanism (CACM) and the Model to Predict the Multiphase Partitioning of Organics to calculate spatially and temporally averaged ISOAR values for the South Coast Air Basin of California (SoCAB). The base case SOA concentrations are derived for September 9, 1993. The South Coast Air Quality Management District of California provided emission and meteorological data. ISOAR values are calculated for the lumped surrogate compounds considered by CACM: isoprene, low-yield monoterpenes, high-yield monoterpenes, high-yield aromatics, etc. This work presents basin-wide ISOAR values determined through regression analysis. In addition, ISOAR values are reported at individual locations within the SoCAB. Modeled data are compared with ISOAR values calculated using smog chamber data. Results indicate that long-chain alkanes present the highest ISOAR. On the other hand, short-chain organics present the lowest ISOAR.     

Effect of NOx on secondary organic aerosol concentrations

The secondary organic aerosol (SOA) module in PMCAMx, a three-dimensional chemical transport model, has been updated to incorporate NOx-dependent SOA yields. Under low-NOx conditions, the RO2 radicals react with other peroxy radicals to form a distribution of products with lower volatilities, resulting in higher SOA yields. At high-NOx conditions, the SOA yields are lower because aldehydes, ketones, and nitrates dominate the product distribution. Based on recent laboratory smog chamber experiments, high-NOx SOA parametrizations were created using the volatility basis-set approach.The organic aerosol (OA) concentrations in the Eastern US are simulated for a summer episode, and are compared to the available ambient measurements. Changes in NOx levels result in changes of both the oxidants (ozone, OH radical, etc.) and the SOA yields during the oxidation of the corresponding organic vapors. The NOx dependent SOA parametrization predicts a maximum average SOA concentration of 5.2 microg m(-3) and a domain average concentration of 0.6 microg m(-3). As the NOx emissions are reduced by 25%, the domain average SOA concentration does not significantly change, but the response is quite variable spatially. However, the predicted average SOA concentrations increase in northern US cities by around 3% but decrease in the rural southeast US by approximately 5%. A decrease of the average biogenic SOA by roughly 0.5 microg m(-3) is predicted for the southeast US for a 50% reduction in NOx emissions.     

Efflorescence transitions of ammonium sulfate particles coated with secondary organic aerosol

Ammonium sulfate particles were generated by atomization and introduced into a smog chamber where they were coated with secondary organic aerosol from ozonolysis of limonene or alpha-pinene. These mixed particles were then sampled with a humidified Tandem-DMA system where a monodisperse aerosol population was selected, humidified, and dried to observe the relative humidity (RH) at which the particles returned to the original dry diameter. The volume fraction of secondary organic aerosol (SOA) in the mixed particles ranged from 0.59 to 0.94 for limonene SOA and 0.54 to 0.72 for alpha-pinene SOA. Efflorescence RHs for our mixed aerosols were in the range of 28-34%, similar to our observation of 32% ERH for pure ammonium sulfate nanoparticles. These findings indicate that the effect of SOA on the ERH of inorganic salts in the atmosphere may be negligible.     

Kinetic mechanism for predicting secondary organic aerosol formation from the reaction of d-limonene with ozone

A semi-explicit mechanism of d-limonene was developed and tested against experimental results obtained from large outdoor Teflon film chambers at the University of North Carolina (UNC) smog chamber facility. The model couples gas-phase reactions with partitioning processes and possible particle-phase reactions. The model not only tracks the gas-phase ozonolysis reaction of d-limonene, but also provides a reasonable prediction of the secondary aerosol mass production under different conditions. Limononaldehyde was the major identified product, followed by limona-ketone, referred to here as keto-limonene, keto-limononaldehyde, limononic acid, and keto-limononic acid. Identified particle-phase products accounted for about 60% of the observed particle mass in the initial stages of the reaction. Model sensitivity was tested and discussed with respect to effects of temperature, humidity, water uptake, and reactant concentrations.     

Modeling secondary organic aerosol formation via multiphase partitioning with molecular data

A new model for atmospheric secondary organic aerosol (SOA) is presented for biogenic compounds. It is based to the extent possible on experimental molecular SOA data, and it is compatible with any existing gas-phase chemical kinetic mechanism. Six SOA precursors or groups of precursors are used to represent biogenic monoterpenes and sesquiterpenes. SOA formation is modeled using five SOA surrogates to represent classes of compounds with different partitioning properties, e.g., hydrophobicity, aqueous solubility, acid dissociation, and saturation vapor pressure. Model simulations are evaluated against smog chamber data for SOA yields and some adjustments are made to uncertain stoichiometric coefficients and saturation vapor pressure parameters to improve model performance. The model is applied undertypical atmospheric conditions to exemplify the effect of relative humidity on SOA formation and the relative contributions of hydrophilic and hydrophobic SOA.     

Impact of the hydrocarbon to NOx ratio on secondary organic aerosol formation

A series of m-xylene/NOx experiments were conducted in the new Bourns College of Engineering-Center for Environmental Research and Technology dual 90 m3 indoor smog chamber to elucidate the role of NOx on the secondary organic aerosol (SOA) formation potential of m-xylene. The results presented herein demonstrate a clear dependence of m-xylene SOA formation potential on NOx, particularly at atmospherically relevant organic aerosol concentration. Experiments with lower NOx levels generated considerably more organic aerosol mass than did experiments with higher NOx levels when reacted m-xylene was held constant. For example, SOA formation from approximately 150 microg m(-3) reacted m-xylene produced 0.6-9.3 microg m(-3) aerosol mass for NOx concentrations ranging from 286 to 10 ppb. The increase in SOA formation was not attributable to changes in ozone and nitrate concentration. A general discussion about possible influences of NOx on SOA formation for this system is included.     

Formation of aerosol particles from reactions of secondary and tertiary alkylamines: characterization by aerosol time-of-flight mass spectrometry

In ambient field studies conducted with aerosol time-of-flight mass spectrometry (ATOFMS), individual particle mass spectra commonly contain ion peaks at mass/charge (m/z) 86, 101, 102, and 118. Particles with mass spectra containing these peaks show a strong correlation with high relative humidity and low temperatures. In an effort to identify these peaks, a series of smog chamber studies were conducted probing the chemistry of secondary and tertiary alkylamines. Specifically, in separate studies, trimethylamine, di- and triethylamine, and di- and tripropylamine were reacted in a 1 m3 Teflon outdoor smog chamber with naturally occurring levels of gas phase oxidants in ambient air. The aerodynamic sizes and individual mass spectra of the resulting aerosol particles were acquired continuously using aerosol time-of-flight mass spectrometry (ATOFMS). Both oxidation and acid-base reactions between amines and acids commonly present in the atmosphere (i.e., nitric and sulfuric acid) appear to play roles in the formation and chemistry of organic nitrogen-containing particle phase species. Ion peaks in the individual particle mass spectra indicate the presence of alkyl ammonium salts, as well as other tentatively identified organic N-containing compounds formed by oxidation processes. Also, for the first time, tertiary alkylamine-N-oxides have been identified as alkylamine oxidation products in the aerosol particle phase. Smog chamber reactions involving triethylamine produce ATOFMS mass spectra with similar ion peak combinations as those observed in the spectra of particles commonly detected in ambient and vehicular source characterization studies. The results of this study suggest that amine chemistry involving gas-to-particle conversion and photooxidation processes may play a significant role in particle formation in regions with high amine concentrations.     

Hydroxydicarboxylic acids: markers for secondary organic aerosol from the photooxidation of alpha-pinene

Detailed organic analysis of fine (PM2.5) rural aerosol collected during summer at K-puszta, Hungary from a mixed deciduous/coniferous forest site shows the presence of polar oxygenated compounds that are also formed in laboratory irradiated alpha-pinene/NOx/air mixtures. In the present work, two major photooxidation products of alpha-pinene were characterized as the hydroxydicarboxylic acids, 3-hydroxyglutaric acid, and 2-hydroxy-4-isopropyladipic acid, based on chemical, chromatographic, and mass spectral data. Different types of volatile derivatives, including trimethylsilyl ester/ether, methyl ester trimethylsilyl ether, and ethyl ester trimethylsilyl ether derivatives were measured by gas chromatography/mass spectrometry (GC/MS), and their electron ionization (El) spectra were interpreted in detail. The proposed structures of the hydroxydicarboxylic acids were confirmed or supported with reference compounds. 2-Hydroxy-4-isopropyladipic acid formally corresponds to a further reaction product of pinic acid involving addition of a molecule of water and opening of the dimethylcyclobutane ring; this proposal is supported by a laboratory irradiation experiment with alpha-pinene/NOJ0 air. In addition, we report the presence of a structurally related minor alpha-pinene photooxidation product, which was tentatively identified as the C7 homolog of 3-hydroxyglutaric acid, 3-hydroxy-4,4-dimethylglutaric acid. The detection of 2-hydroxy-4-isopropyladipic acid in ambient aerosol provides an explanation for the relatively low atmospheric concentrations of pinic acid found during daytime in forest environments.     

Model representation of secondary organic aerosol in CMAQv4.7

Numerous scientific upgrades to the representation of secondary organic aerosol (SOA) are incorporated into the Community Multiscale Air Quality (CMAQ) modeling system. Additions include several recently identified SOA precursors: benzene, isoprene, and sesquiterpenes; and pathways: in-cloud oxidation of glyoxal and methylglyoxal, particle-phase oligomerization, and acid enhancement of isoprene SOA. NO(x)-dependent aromatic SOA yields are also added along with new empirical measurements of the enthalpies of vaporization and organic mass-to-carbon ratios. For the first time, these SOA precursors, pathways and empirical parameters are included simultaneously in an air quality model for an annual simulation spanning the continental U.S. Comparisons of CMAQ-modeled secondary organic carbon (OC(sec)) with semiempirical estimates screened from 165 routine monitoring sites across the U.S. indicate the new SOA module substantially improves model performance. The most notable improvement occurs in the central and southeastern U.S. where the regionally averaged temporal correlations (r) between modeled and semiempirical OC(sec) increase from 0.5 to 0.8 and 0.3 to 0.8, respectively, when the new SOA module is employed. Wintertime OC(sec) results improve in all regions of the continental U.S. and the seasonal and regional patterns of biogenic SOA are better represented.     

Investigation of alpha-pinene + ozone secondary organic aerosol formation at low total aerosol mass

We present a method for measuring secondary organic aerosol (SOA) production at low total organic mass concentration (COA) using proton-transfer reaction mass spectrometry (PTR-MS). PTR-MS provides high time resolution measurements of gas-phase organic species and, coupled with particle measurements, allows for the determination of aerosol yield in real time. This approach facilitates the measurement of aerosol production at low COA; in fact aerosol mass fractions can be measured during alpha-pinene consumption as opposed to only at the completion of gas-phase chemistry. The high time resolution data are consistent with both the partitioning theory of Pankow (Atmos. Environ. 1994, 28,185 and 189) and the previous experimental measurements. Experiments including the effect of UV illumination and NOx reveal additional features of alpha-pinene + ozone product photochemistry and volatility. The high time resolution data also elucidate aerosol production from alpha-pinene ozonolysis at COA < 10 microg m(-3) and show that extrapolations of current partitioning models to conditions of low COA significantly underestimate SOA production under dark, low-NOx conditions. However, extrapolations of current models overestimate SOA production under illuminated, higher-NOx conditions typical of polluted regional air masses.     

Evidence for the existence of organosulfates from beta-pinene ozonolysis in ambient secondary organic aerosol

The formation of organosulfates from the gas-phase ozonolysis of beta-pinene in the presence of neutral or acidic sulfate particles was investigated in a series of indoor aerosol chamber experiments. The organosulfates were analyzed using high-performance liquid chromatography (LC) coupled to electrospray ionization-time-of-flight mass spectrometry (MS) in parallel to ion trap MS. Organosulfates were only found in secondary organic aerosol from beta-pinene ozonolysis in the presence of acidic sulfate seed particles. One of the detected organosulfates also occurred in ambient aerosol samples that were collected at a forest site in northeastern Bavaria, Germany. beta-Pinene oxide, an oxidation product in beta-pinene/O3 and beta-pinene/NO3 reactions, is identified as a possible precursor for the beta-pinene-derived organosulfate. Furthermore, several nitroxy-organosulfates originating from monoterpenes were found in the ambient samples. These nitroxy-organosulfates were only detected in the nighttime samples, suggesting a role for nighttime chemistry in their formation. Their LC/MS chromatographic peak intensities suggest that they represent an important fraction of the organic mass in ambient aerosols, especially at night.     

Semiempirical model for organic aerosol growth by acid-catalyzed heterogeneous reactions of organic carbonyls

Aerosol growth by heterogeneous reactions of diverse carbonyls in the presence and absence of acidified seed aerosols was studied in a 4 m long flow reactor (2.5 cm i.d.) and a 2-m3 indoor Teflon film chamber under darkness. The acid catalytic effects on heterogeneous aerosol production were observed for diverse carbonyls in various ranges of humidities and compositions of seed inorganic aerosols. Particle population data measured by a scanning mobility particle sizer were used to calculate organic aerosol growth. To accountforthe aerosol growth contributed by heterogeneous reactions, the increase in organic aerosol mass was normalized bythe organic mass predicted by partitioning or the square of predicted organic mass. The carbonyl heterogeneous reactions were accelerated in the presence of acid catalysts (H2SO4), leading to higher aerosol yields than in their absence. The experimental data from aerosol yields in the flow reactorwere semiempirically fitted to the model parameters to predict the organic aerosol growth. The model parameters consist of environmental characteristics and molecular structure information of organic carbonyls. Basicity constants of carbonyls were used to describe the proton affinity of carbonyls for the acid catalysts. Particle environmental factors, such as humidity, temperature, and inorganic seed composition, were expressed by excess acidity and the parameters obtained from an inorganic thermodynamic model. A stepwise regression analysis of the aerosol growth model for the experimental data revealed that either the chemical structure information of carbonyls or characteristic environmental parameters are statistically significant in the prediction of organic aerosol growth. It was concluded thatthis model approach is applicable to predict secondary organic aerosol formation by heterogeneous reaction.