Α-pinene Ozonolysis Research Articles

Optical Properties of Dispersed Aerosols in the Near Ultraviolet (355 nm): Measurement Approach and Initial Data

An aerosol albedometer combining cavity ring-down spectroscopy (CRDS) with integrating sphere nephelometry was developed for use at λ = 355 nm. The instrument measures extinction and scattering coefficients of dispersed particulate matter in the near ultraviolet (UV) spectral region. Several samples have been analyzed, including: ammonium sulfate, secondary organic aerosols (SOA) resulting from the ozonolysis of α-pinene and photooxidation of toluene, redispersed soil dust samples, biomass burning aerosols, and ambient aerosols. When particle size and number density were experimentally controlled, extinction coefficients and scattering coefficients were found to have a linear relationship with particle number concentration, in good agreement with light scattering theory. For ammonium sulfate and pinene samples, extinction cross sections for size-selected (D(p) = 300 nm) samples were within the range of 1.65-2.60 × 10(-9) cm(2) with the largest value corresponding to ammonium sulfate and the lowest value for pinene SOA. The scattering cross sections of pinene and ammonium sulfate aerosols were indistinguishable from the extinction cross sections, indicating that these particle types had minimal light absorption at 355 nm. However, soil dusts and biomass burning aerosols showed significant absorption with single scatter albedo (SSA) between 0.74 and 0.84. Ambient aerosols also had transient absorption at 355 nm that correlated well with a particle-soot absorption photometer (PSAP) measuring visible light absorption.

Modeling the gas-particle partitioning of secondary organic aerosol: the importance of liquid-liquid phase separation

Abstract. The partitioning of semivolatile organic compounds between the gas phase and aerosol particles is an important source of secondary organic aerosol (SOA). Gas-particle partitioning of organic and inorganic species is influenced by the physical state and water content of aerosols, and therefore ambient relative humidity (RH), as well as temperature and organic loading levels. We introduce a novel combination of the thermodynamic models AIOMFAC (for liquid mixture non-ideality) and EVAPORATION (for pure compound vapor pressures) with oxidation product information from the Master Chemical Mechanism (MCM) for the computation of gas-particle partitioning of organic compounds and water. The presence and impact of a liquid-liquid phase separation in the condensed phase is calculated as a function of variations in relative humidity, organic loading levels, and associated changes in aerosol composition. We show that a complex system of water, ammonium sulfate, and SOA from the ozonolysis of α-pinene exhibits liquid-liquid phase separation over a wide range of relative humidities (simulated from 30% to 99% RH). Since fully coupled phase separation and gas-particle partitioning calculations are computationally expensive, several simplified model approaches are tested with regard to computational costs and accuracy of predictions compared to the benchmark calculation. It is shown that forcing a liquid one-phase aerosol with or without consideration of non-ideal mixing bears the potential for vastly incorrect partitioning predictions. Assuming an ideal mixture leads to substantial overestimation of the particulate organic mass, by more than 100% at RH values of 80% and by more than 200% at RH values of 95%. Moreover, the simplified one-phase cases stress two key points for accurate gas-particle partitioning calculations: (1) non-ideality in the condensed phase needs to be considered and (2) liquid-liquid phase separation is a consequence of considerable deviations from ideal mixing in solutions containing inorganic ions and organics that cannot be ignored. Computationally much more efficient calculations relying on the assumption of a complete organic/electrolyte phase separation below a certain RH successfully reproduce gas-particle partitioning in systems in which the average oxygen-to-carbon (O:C) ratio is lower than ~0.6, as in the case of α-pinene SOA, and bear the potential for implementation in atmospheric chemical transport models and chemistry-climate models. A full equilibrium calculation is the method of choice for accurate offline (box model) computations, where high computational costs are acceptable. Such a calculation enables the most detailed predictions of phase compositions and provides necessary information on whether assuming a complete organic/electrolyte phase separation is a good approximation for a given aerosol system. Based on the group-contribution concept of AIOMFAC and O:C ratios as a proxy for polarity and hygroscopicity of organic mixtures, the results from the α-pinene system are also discussed from a more general point of view.

Oligomer Formation Pathways in Secondary Organic Aerosol from MS and MS/MS Measurements with High Mass Accuracy and Resolving Power

Secondary organic aerosol (SOA) is formed when organic molecules react with oxidants in the gas phase to form particulate matter. Recent measurements have shown that more than half of the mass of laboratory-generated SOA consists of high molecular weight oligomeric compounds. In this work, the formation mechanisms of oligomers produced in the laboratory by ozonolysis of α-pinene, an important SOA precursor in ambient air, are studied by MS and MS/MS measurements with high accuracy and resolving power to characterize monomer building blocks and the reactions that couple them together. The distribution of oligomers in an SOA sample is complex, typically yielding over 1000 elemental formulas that can be assigned from an electrospray ionization mass spectrum. Despite this complexity, MS/MS spectra can be found that give strong evidence for specific oligomer formation pathways that have been postulated but not confirmed. These include aldol and gem-diol reactions of carbonyls as well as peroxyhemiacetal formation from hydroperoxides. The strongest evidence for carbonyl reactions is in the formation of hydrated products. Less compelling evidence is found for dehydrated products and secondary ozonide formation. The number of times that a monomer building block is observed as a fragmentation product in the MS/MS spectra is shown to be independent of the monomer vapor pressure, suggesting that oligomer formation is not driven by equilibrium partitioning of a monomer between the gas and particle phases, but rather by reactive uptake where a monomer collides with the particle surface and rapidly forms an oligomer.

Predicting secondary organic aerosol formation from terpenoid ozonolysis with varying yields in indoor environments

The ozonolysis of terpenoids generates secondary organic aerosol (SOA) indoors. Models of varying complexity have been used to predict indoor SOA formation, and many models use the SOA yield, which is the ratio of the mass of produced SOA and the mass of consumed reactive organic gas. For indoor simulations, the SOA yield has been assumed as a constant, even though it depends on the concentration of organic particles in the air, including any formed SOA. We developed two indoor SOA formation models for single terpenoid ozonolysis, with yields that vary with the organic particle concentration. The models have their own strengths and were in agreement with published experiments for d-limonene ozonolysis. Monte Carlo analyses were performed, which simulated different residential and office environments to estimate ranges of SOA concentrations and yields for d-limonene and α-pinene ozonolysis occurring indoors. Results indicate that yields are highly variable indoors and are most influenced by background organic particles for steady-state formation and indoor ozone concentration for transient peak formation. Additionally, a review of ozonolysis yields for indoor-relevant terpenoids in the literature revealed much uncertainty in their values at low concentrations typical of indoors. The results in this study suggest important factors that govern indoor secondary organic aerosol (SOA) formation and yields, in typical residential and office spaces. This knowledge informs the development and comparison of control strategies to reduce indoor-generated SOA. The ranges of SOA concentrations predicted indoors allow the quantification of the effects of sorptive interactions of semi-volatile organic compounds or reactive oxygen species with SOA, filter loading owing to SOA formation, and impacts of SOA on health, if links are established.

Photochemical Aging of α-Pinene Secondary Organic Aerosol: Effects of OH Radical Sources and Photolysis

This study addresses photochemical aging of secondary organic aerosol (SOA) produced from α-pinene ozonolysis. The SOA is aged via hydroxyl radical (OH) reactions with first-generation vapors and UV photolysis. OH radicals are created through tetramethylethylene ozonolysis, HOOH photolysis, or HONO photolysis, sources that vary in OH concentration and the presence or absence of UV illumination. Aging strongly influences observed SOA mass concentrations, but the behavior is complex. In the dark or with high concentrations of OH, vapors are functionalized, lowering their volatility, resulting in an increase in OA by a factor of 2-3. However, with lower concentrations of OH under UV illumination SOA mass concentrations decrease over time. We attribute this decrease to evaporation driven by photolysis of the highly functionalized second-generation products. The photolysis rates are rapid, a few percent of the NO(2) photolysis frequency, and can thus be highly competitive with other aging mechanisms in the atmosphere.

Wavelength Dependence of Refractive Index of Secondary Organic Aerosols Generated during the Ozonolysis and Photooxidation of α-Pinene

Wavelength Dependence of Refractive Index of Secondary Organic Aerosols Generated during the Ozonolysis and Photooxidation of α-Pinene

Use of denuder/filter apparatus to investigate terpene ozonolysis

A denuder/filter apparatus was used to collect the gaseous and particulate reaction products from ozonlysis of α-pinene, limonene and α-terpineol in an effort to develop sampling techniques for characterizing indoor environment chemistry. Carboxylic acids found in the particulate phase were derivatized to 2,2,2-trifuoroethylamides by reaction with 3-ethyl-1-[3-(dimethylamino)propyl]carbodiimide hydrochloride (EDC) and 2,2,2-trifluoroethylamine hydrochloride (TFEA). Carbonyl compounds collected in both gas phase and particulate phase were derivatized to their respective oximes by reaction with O-(2,3,4,5,6-pentafluoro-benzyl)hydroxylamine hydrochloride (PFBHA). The ozonolysis of α-pinene yielded the carboxylic acids: cis-pinonic acid and pinic acid and the proposed carboxylic acids methanetricarboxylic acid and terpenylic acid; the carbonyls: 4-oxopentanal, norpinonaldehyde, pinon aldehyde and the proposed carbonyl methylidenepropanedial. The ozonolysis of limonene yielded the carboxylic acids: limonic acid and pinic acid and the carbonyls: 1-(4-methylcyclohex-3-en-1-yl)ethanone (4AMCH), glyoxal, methyl glyoxal, 4-oxopentanal and 6-oxo-3-(prop-1-en-2-yl)heptanal (IPOH). The ozonolysis of α-terpineol yielded the proposed carboxylic acids: terpenylic acid and homoterpenylic acid and the carbonyls: (5E)-6-hydroxyhept-5-en-2-one, methyl glyoxal and 4-oxopentanal.

Characterisation of tracers for aging of α-pinene secondary organic aerosol using liquid chromatography/negative ion electrospray ionisation mass spectrometry

Environmental contextAmbient fine aerosol from forested sites contains secondary organic aerosol from the oxidation of monoterpenes that are emitted by the vegetation, mainly by conifers. These biogenic aerosols can have varying lifetimes in the atmosphere because they contain first-generation oxidation products of α-pinene as well as aged products formed through further photooxidation, fragmentation, hydrolysis, and dimerisation reactions. We focus on the structural characterisation of secondary organic aerosol products that are simulated in a smog chamber experiment and can serve as potential tracers for aging processes in biogenic aerosols. AbstractSecondary organic aerosol (SOA) from the oxidation of α-pinene is a very complex and dynamic mixture containing products with a different chemical nature and physicochemical properties that are dependent on chemical evolution or aging processes. In this study, we focus on the chemical characterisation of major products that are formed upon α-pinene ozonolysis SOA and subsequent aging through OH-initiated reactions in the absence of NOx, which include known as well as unknown tracers. The mass spectrometric data obtained for selected unknown compounds that show an increased relative abundance upon aging are interpreted in detail and tentative structures for them are proposed taking into account their formation through photooxidation of α-pinene. Known tracers for α-pinene SOA aging that were identified include norpinic acid, 10-hydroxypinonic acid, diaterpenylic acid acetate, and diesters formed by esterification of pinic acid with terpenylic acid or 10-hydroxypinonic acid. Novel tracers for α-pinene SOA aging that were tentatively identified include dinorpinic acid and 8-hydroxypinonic acid. In addition, reaction mechanisms are proposed to explain the formation of the observed α-pinene SOA tracers.

Using Elemental Ratios to Predict the Density of Organic Material Composed of Carbon, Hydrogen, and Oxygen

A governing equation was developed to predict the density ρ(org) of organic material composed of carbon, oxygen, and hydrogen using the elemental ratios O:C and H:C as input parameters: ρ(org) = 1000 [(12 + 1(H:C) + 16(O:C)]/[7.0 + 5.0(H:C) + 4.15(O:C)] valid for 750 < ρ(org) < 1900 kg m(-3). Comparison of the actual to predicted ρ(org) values shows that the developed equation has an accuracy of 12% for more than 90% of the 31 atmospherically relevant compounds used in the training set. The equation was further validated for secondary organic material (SOM) produced by isoprene photo-oxidation and by α-pinene ozonolysis. Depending on the conditions of SOM production, ρ(org/SOM) ranged from 1230 to 1460 kg m(-3), O:C ranged from 0.38 to 0.72, and H:C ranged from 1.40 to 1.86. Atmospheric chemistry models that simulate particle production and growth can employ the developed equation to simulate particle physical properties. The equation can also extend atmospheric measurements presented as van Krevelen diagrams to include estimates of the material density of particles and their components. Use of the equation, however, is restricted to particle components having negligible quantities of additional elements, most notably nitrogen.

Relating cloud condensation nuclei activity and oxidation level ofα-pinene secondary organic aerosols

[1] During a series of smog chamber experiments, the effects of chemical and photochemical aging on the ability of organic aerosols generated from ozonolysis of α-pinene to act as cloud condensation nuclei (CCN) were investigated. In particular, the study focused on the relation between oxygenation and the CCN-derived single hygroscopicity parameter κ for different experimental conditions: varying precursor concentrations (10–40 ppb), different OH sources (photolysis of HONO either with or without the addition of NO or ozonolysis of tetramethylethylene), and exposure to light. Oxygenation was described by the contribution of the aerosol mass spectrometer (AMS) mass fragment m/z 44 to the total organic signal (f44) and the oxygen to carbon molar ratio (O/C), likewise determined with AMS. CCN activity, described by the hygroscopicity parameter κ, was determined with a CCN counter. It was found that f44 increases with decreasing precursor concentration and with chemical aging, whereas neither of these affects CCN activity. Overall, κ is largely independent of O/C in the range 0.3 < O/C < 0.6 (0.07 < f44 < 0.12), although an empirical unweighted least squares fit was determined: κ = (0.071 ± 0.02) · (O/C) + (0.0785 ± 0.009) for particles with diameter in the range 59–200 nm. Growth kinetics of activating secondary organic aerosols were found to be comparable to those of ammonium sulfate and were not influenced by chemical aging.

Volatility of secondary organic aerosol during OH radical induced ageing

Abstract. The aim of this study was to investigate oxidation of SOA formed from ozonolysis of α-pinene and limonene by hydroxyl radicals. This paper focuses on changes of particle volatility, using a Volatility Tandem DMA (VTDMA) set-up, in order to explain and elucidate the mechanism behind atmospheric ageing of the organic aerosol. The experiments were conducted at the AIDA chamber facility of Karlsruhe Institute of Technology (KIT) in Karlsruhe and at the SAPHIR chamber of Forchungzentrum Jülich (FZJ) in Jülich. A fresh SOA was produced from ozonolysis of α-pinene or limonene and then aged by enhanced OH exposure. As an OH radical source in the AIDA-chamber the ozonolysis of tetramethylethylene (TME) was used while in the SAPHIR-chamber the OH was produced by natural light photochemistry. A general feature is that SOA produced from ozonolysis of α-pinene and limonene initially was rather volatile and becomes less volatile with time in the ozonolysis part of the experiment. Inducing OH chemistry or adding a new portion of precursors made the SOA more volatile due to addition of new semi-volatile material to the aged aerosol. The effect of OH chemistry was less pronounced in high concentration and low temperature experiments when lower relative amounts of semi-volatile material were available in the gas phase. Conclusions drawn from the changes in volatility were confirmed by comparison with the measured and modelled chemical composition of the aerosol phase. Three quantified products from the α-pinene oxidation; pinonic acid, pinic acid and methylbutanetricarboxylic acid (MBTCA) were used to probe the processes influencing aerosol volatility. A major conclusion from the work is that the OH induced ageing can be attributed to gas phase oxidation of products produced in the primary SOA formation process and that there was no indication on significant bulk or surface reactions. The presented results, thus, strongly emphasise the importance of gas phase oxidation of semi- or intermediate-volatile organic compounds (SVOC and IVOC) for atmospheric aerosol ageing.

Ultrahigh-resolution FT-ICR mass spectrometry characterization of α-pinene ozonolysis SOA

Abstract Secondary organic aerosol (SOA) of α-pinene ozonolysis with and without hydroxyl radical scavenging hexane was characterized by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Molecular formulas for more than 900 negative ions were identified over the mass range of 100–850 u. Hydroxyl radicals formed during the ozonolysis of α-pinene might be expected to alter the composition of SOA, however a majority of the molecular formulas were identified in all three experiments and with a few exceptions they had similar relative abundances. Thus, the detailed composition of SOA was only slightly influenced by the presence or absence of hydroxyl radical scavenging hexane. The negative-ion mass spectra of the SOA contained four groups of peaks with increasing mass spectral complexity corresponding to increasing molecular weight. The mean values of O:C decreased from 0.55 to 0.42 with increasing molecular weight, but the mean value of H:C, approximately 1.5, did not change with increasing molecular weight. The molecular formulas with the highest relative abundances in Groups I and II contained 5–7 and 7–10 oxygen atoms and 3–4 and 5–7 double bond equivalents, respectively. The molecular formulas with the highest relative abundances in Groups III and IV contained 10–13 and 13–16 oxygen atoms and 7–9 and 9–11 double bond equivalents, respectively. Observations of the oxygen content and the double bond equivalents of the SOA products suggest a complex mixture of accretion reaction mechanisms, without an easily confirmable dominating pathway.

Elemental composition and oxidation of chamber organic aerosol

Abstract. Recently, graphical representations of aerosol mass spectrometer (AMS) spectra and elemental composition have been developed to explain the oxidative and aging processes of secondary organic aerosol (SOA). It has been shown previously that oxygenated organic aerosol (OOA) components from ambient and laboratory data fall within a triangular region in the f44 vs. f43 space, where f44 and f43 are the ratios of the organic signal at m/z 44 and 43 to the total organic signal in AMS spectra, respectively; we refer to this graphical representation as the "triangle plot." Alternatively, the Van Krevelen diagram has been used to describe the evolution of functional groups in SOA. In this study we investigate the variability of SOA formed in chamber experiments from twelve different precursors in both "triangle plot" and Van Krevelen domains. Spectral and elemental data from the high-resolution Aerodyne aerosol mass spectrometer are compared to offline species identification analysis and FTIR filter analysis to better understand the changes in functional and elemental composition inherent in SOA formation and aging. We find that SOA formed under high- and low-NOx conditions occupy similar areas in the "triangle plot" and Van Krevelen diagram and that SOA generated from already oxidized precursors allows for the exploration of areas higher on the "triangle plot" not easily accessible with non-oxidized precursors. As SOA ages, it migrates toward the top of the triangle along a path largely dependent on the precursor identity, which suggests increasing organic acid content and decreasing mass spectral variability. The most oxidized SOA come from the photooxidation of methoxyphenol precursors which yielded SOA O/C ratios near unity. α-pinene ozonolysis and naphthalene photooxidation SOA systems have had the highest degree of mass closure in previous chemical characterization studies and also show the best agreement between AMS elemental composition measurements and elemental composition of identified species within the uncertainty of the AMS elemental analysis. In general, compared to their respective unsaturated SOA precursors, the elemental composition of chamber SOA follows a slope shallower than −1 on the Van Krevelen diagram, which is indicative of oxidation of the precursor without substantial losss of hydrogen, likely due to the unsaturated nature of the precursors. From the spectra of SOA studied here, we are able to reproduce the triangular region originally constructed with ambient OOA compents with chamber aerosol showing that SOA becomes more chemically similar as it ages. Ambient data in the middle of the triangle represent the ensemble average of many different SOA precursors, ages, and oxidative processes.

Effect of Hydrophilic Organic Seed Aerosols on Secondary Organic Aerosol Formation from Ozonolysis of α-Pinene

Gas-particle partitioning theory is widely used in atmospheric models to predict organic aerosol loadings. This theory predicts that secondary organic aerosol (SOA) yield of an oxidized volatile organic compound product will increase as the mass loading of preexisting organic aerosol increases. In a previous work, we showed that the presence of model hydrophobic primary organic aerosol (POA) had no detectable effect on the SOA yields from ozonolysis of α-pinene, suggesting that the condensing SOA compounds form a separate phase from the preexisting POA. However, a substantial faction of atmospheric aerosol is composed of polar, hydrophilic organic compounds. In this work, we investigate the effects of model hydrophilic organic aerosol (OA) species such as fulvic acid, adipic acid, and citric acid on the gas-particle partitioning of SOA from α-pinene ozonolysis. The results show that only citric acid seed significantly enhances the absorption of α-pinene SOA into the particle-phase. The other two seed particles have a negligible effect on the α-pinene SOA yields, suggesting that α-pinene SOA forms a well-mixed organic aerosol phase with citric acid and a separate phase with adipic acid and fulvic acid. This finding highlights the need to improve the thermodynamics treatment of organics in current aerosol models that simply lump all hydrophilic organic species into a single phase, thereby potentially introducing an erroneous sensitivity of SOA mass to emitted OA species.

Effect of the OH Radical Scavenger Hydrogen Peroxide on Secondary Organic Aerosol Formation from α-Pinene Ozonolysis

Hydrogen peroxide (HOOH) is a potentially valuable hydroxyl radical (OH) scavenger in secondary organic aerosol experiments focused on ozonolysis yields. Here, we present results for α-pinene ozonolysis. The OH scavenging produces solely HO2 radicals and the resulting high [HO2]/[RO2] ratio causes an increase in aerosol formation from α-pinene ozonolysis, compared to experiments performed with butanol OH scavengers. The majority of the increase comes in the 100 μg m−3 volatility range, suggesting that instead of more volatile products formed under higher RO2 conditions, less volatile, multifunctional hydroperoxides form under the high-HO2 conditions here. This dependence on the [HO2]/[RO2] ratio can be parameterized in a similar fashion to the way high- and low-NO x yields are currently treated in models.

Hydrogen peroxide generation from α- and β-pinene and toluene secondary organic aerosols

Abstract In-particle reactions and reactivity may play a role in aerosol aging as well as health effects associated with airborne particles. One of the main hypotheses for the species causing the observed health effects are reactive oxygen species including hydrogen peroxide (H2O2). Secondary organic aerosol (SOA), the focus of this study, comprises a major fraction of ambient fine mode particle mass. SOA were generated via dark ozonolysis of α-pinene and β-pinene, as well as photochemical oxidation of α-pinene, β-pinene, and toluene. SOA particles generate a considerable amount of H2O2 in the aqueous phase. For the same particle mass, α-pinene and β-pinene SOA have higher H2O2 generation ability than toluene SOA. H2O2 levels were sensitive to the pH of the particle extraction solutions, decreasing as the pH was increased. SOA samples aged for 20 h in room air lost a significant fraction of the H2O2 compared to fresh samples. The H2O2 is likely from decomposition or hydrolysis of hydroxyhydroperoxides, peroxic acids and related species for α- and β-pinene SOA, and from redox cycling of quinoid compounds for toluene SOA. This study provides the first quantitative measurement of H2O2 for a range of SOA particle types.

Volatility of secondary organic aerosol from the ozonolysis of monoterpenes

Abstract The volatility of secondary organic aerosol (SOA) produced from the ozonolysis of α-pinene, β-pinene, and limonene, at low and intermediate RH, and at low and high NOx conditions was investigated using a thermodenuder (TD). More than 90% of the α-pinene and β-pinene SOA volume (for 200 nm particles) and approximately 75% of the limonene SOA evaporated at 70 °C for a centerline residence time of approximately 16 s in the heated zone. Practically all the SOA in all systems evaporated at approximately 90 °C. The relative humidity during the formation of SOA had a small effect on its volatility (changes in the evaporated fraction were less than 10%). NOx concentrations had a significant impact on the volatility of α-pinene and β-pinene SOA (reductions of the evaporated fraction by approximately 30%), but a negligible effect on the volatility of limonene SOA. High NOx levels resulted in more volatile SOA than low NOx conditions due to the presence of relatively volatile nitrate containing species at high NOx. The behavior of the SOA in the thermodenuder can be reproduced using an aerosol dynamics model based on the volatility basis-set approach and SOA yield parameters derived in previous smog chamber studies if appropriate values of the mass accommodation coefficient and heat of vaporization (ΔHvap) are chosen. Use of either a very low effective accommodation coefficient (0.002–0.01) and a heat of vaporization depending on the saturation concentration, or an effective accommodation coefficient of 0.05 for the initial stages of the evaporation and 1 afterward, with a low volatility-independent value of the ΔHvap, is needed for the simulation of the SOA evaporation.

Secondary Organic Material Produced by the Dark Ozonolysis of α-Pinene Minimally Affects the Deliquescence and Efflorescence of Ammonium Sulfate

The hygroscopic phase transitions and growth factors of mixed particles having as components ammonium sulfate and secondary organic material (SOM) were measured. The SOM was generated by the dark ozonolysis of α-pinene, and organic particle mass concentrations of 1.63 and 12.2 μg m−3 were studied. The hygroscopic properties were investigated using a 1×3 tandem differential mobility analyzer (1×3-TDMA). The 1×3-TDMA takes advantage of the hysteresis between solid-to-aqueous and aqueous-to-solid phase transitions to determine the efflorescence and deliquescence relative humidities (ERH and DRH, respectively) of materials. Overall, the influence of the SOM produced by the dark ozonolysis of α-pinene on the ERH and DRH of ammonium sulfate was small, shifting for example the DRH from 80% for pure ammonium sulfate to 77% for organic volume fractions of 0.96. The ERH likewise shifted by only a small amount across this composition range, specifically from 31 to 29%. The SOM produced at the lower organic particle mass concentrations shifted ERH and DRH even less, indicating an influence of SOM chemical composition on phase transitions. The hygroscopic growth factors of the mixed particles were adequately modeled across the range of studied RH (50 to 83%) using volume-averaged growth factors of the pure materials. The results for ERH, DRH, and the growth factors were all consistent with a model of phase separation between the inorganic and organic phases in individual particles, at least for the studied RH values (<83%) and for SOM prepared by α-pinene ozonolysis.

Application of the np+mP modeling approach for simulating secondary organic particulate matter formation from α-pinene oxidation

Abstract Simulations of the levels of organic particulate matter (OPM) in chemical transport models typically proceed by a two-product (2p) model approach, in which up to two lumped products are assumed to represent the condensable oxidation products of each hydrocarbon precursor. With the 2p approach, as well as with more detailed semi-explicit approaches, significant underpredictions of OPM levels are not uncommon, particularly at low OPM mass loadings in the atmosphere and in chamber studies. Here the recently developed np+mP OPM model approach was applied to evaluate OPM formation by α-pinene ozonolysis using: 1) product lumping based on carbon number and an estimate of molecular polarity, and 2) explicit inclusion of a low-volatility “polymeric” (P) compound. The np+mP approach allows for consideration of more than two products of type p (n > 2) per precursor, and consideration of further oxidation and/or reaction of those products to form m essentially non-volatile high molecular weight products of type P. Simulations were carried out for several different case types, namely 16p+0P, 8p+0P, 5p+0P, and 5p+1P in which one representative low-volatility compound was added. Predicted OPM levels were compared with levels predicted using alternative parameterizations (2p and volatility basis set) and with levels measured in chamber experiments conducted over a range of α-pinene oxidation conditions. The results from the 5p+1P case provided good agreement with available data from low, atmospherically-relevant mass loading experiments. Predicted O:C and H:C ratios also were compared with measured ratios, providing insight into differences and similarities between model compounds and the products they represent. The results will inform further development of OPM models, especially as regards oxidation product lumping and inclusion of low-volatility products.

Cloud condensation nuclei (CCN) activity and oxygen-to-carbon elemental ratios following thermodenuder treatment of organic particles grown by α-pinene ozonolysis

The effects of thermodenuder treatment on the cloud condensation nuclei (CCN) activity and elemental composition of organic particles grown by α-pinene ozonolysis were investigated. The secondary organic material (SOM) was produced in a continuous-flow chamber, with steady-state organic particle mass concentrations M(org) ranging from 1.4 to 37 μg m(-3). Particles exiting in the outflow were heated to temperatures T of up to 100 °C in a thermodenuder. The oxygen-to-carbon (O:C) and hydrogen-to-carbon (H:C) ratios were measured by on-line mass spectrometry. The observed elemental ratios were fit by a linear function, given by (H:C) = -0.8 (O:C) +1.8 for 0.38 < O:C < 0.50. This fit included the dependence on both M(org) and T, meaning that the single variable of post-thermodenuder M(org) was sufficient as an accurate predictor for O:C(M(org)(T)) and H:C(M(org)(T)). This result suggests that equilibrium partitioning theory largely governed the initial volatilization in the thermodenuder. By comparison, the CCN activity had a different dependence on thermodenuder treatment. At 25 °C, the CCN activity was independent of M(org), having an effective hygroscopicity parameter κ(org) of 0.103 ± 0.002. At 100 °C, however, κ(org) varied from 0.105 for M(org) = 1.4 μg m(-3) to 0.079 for M(org) = 37 μg m(-3), indicating that for high mass concentration the CCN activity decreased with heat treatment. The interpretation is that the oligomer fraction of the SOM increased at elevated T, both because of particle-phase reactions that produced oligomers under those conditions and because of the relative enrichment of lower-volatility oligomers in the SOM accompanying the evaporation of higher-volatility monomers from the SOM. Oligomers have high effective molecular weights and thereby significantly influence CCN activity. The production rates of different types of oligomers depend on the types and concentrations of functional groups present in the SOM, which in turn are strongly influenced by M(org). We conclude with a hypothesis, which is supported by a detailed molecular kinetic model, that the changes in κ(org) at high T were more significant at high compared to low M(org) because particle-phase SOM at high M(org) contained a mix of functional groups favorable to oligomerization, such as carbonyl groups.