Secondary Organic Aerosol Growth Research Articles

SOA formation from photooxidation of naphthalene and methylnaphthalenes with m-xylene and surrogate mixtures

SOA formation is not well predicted in current models in urban area. The interaction among multiple anthropogenic volatile organic compounds is essential for the SOA formation in the complex urban atmosphere. Secondary organic aerosol (SOA) from the photooxidation of naphthalene, 1-methylnaphthalene, and 2-methylnaphthalene as well as individual polycyclic aromatic hydrocarbons (PAHs) mixed with m-xylene or an atmospheric surrogate mixture was explored in the UCR CE-CERT environmental chamber under urban relevant low NOx and extremely low NOx (H2O2) conditions. Addition of m-xylene suppressed SOA formation from the individual PAH precursor. A similar suppression effect on SOA formation was observed during the surrogate mixture photooxidation suggesting the importance of gas-phase chemical reactivity to SOA formation. The SOA growth rate for different PAH-m-xylene mixtures was strongly correlated with initial [HO2]/[RO2] ratio but negatively correlated with initial m-xylene/NO ratio. Decreasing SOA formation was observed for increasing m-xylene/PAHs ratios and increasing initial m-xylene/NO ratio. The SOA chemical composition characteristics such as f44 versus f43, H/C ratio, O/C ratio, and the oxidation state of the carbon OS¯c were consistent with a continuously aging with the SOA exhibiting characteristics of both individual precursors. SOA formation from PAHs was also suppressed within an atmospheric surrogate mixture compared to the SOA formed from individual PAHs, indicating that atmospheric reactivity directly influences SOA formation from PAHs.

Growth Kinetics and Size Distribution Dynamics of Viscous Secondary Organic Aerosol.

Low bulk diffusivity inside viscous semisolid atmospheric secondary organic aerosol (SOA) can prolong equilibration time scale, but its broader impacts on aerosol growth and size distribution dynamics are poorly understood. Here, we present quantitative insights into the effects of bulk diffusivity on the growth and evaporation kinetics of SOA formed under dry conditions from photooxidation of isoprene in the presence of a bimodal aerosol consisting of Aitken (ammonium sulfate) and accumulation (isoprene or α-pinene SOA) mode particles. Aerosol composition measurements and evaporation kinetics indicate that isoprene SOA is composed of several semivolatile organic compounds (SVOCs), with some reversibly reacting to form oligomers. Model analysis shows that liquid-like bulk diffusivities can be used to fit the observed evaporation kinetics of accumulation mode particles but fail to explain the growth kinetics of bimodal aerosol by significantly under-predicting the evolution of the Aitken mode. In contrast, the semisolid scenario successfully reproduces both evaporation and growth kinetics, with the interpretation that hindered partitioning of SVOCs into large viscous particles effectively promotes the growth of smaller particles that have shorter diffusion time scales. This effect has important implications for the growth of atmospheric ultrafine particles to climatically active sizes.

Isoprenoid emission variation of Norway spruce across a European latitudinal transect

Norway spruce (Picea abies) is one of the dominant tree species in the European boreal zone with the capacity to grow over large areas within Europe. It is an important emitter of biogenic volatile organic compounds (BVOCs), which can act as precursors of photochemical smog and ozone and contribute to the formation and growth of secondary organic aerosols (SOA) in the atmosphere.Isoprenoid emissions were measured from Norway spruce trees at seven different sites, distributed from Ljubljana in Slovenia to Piikkiö in Finland. Four of the sites were part of a network of genetically identical spruce trees and contained two separate provenances. The remaining three sites were part of other networks which have been used to conduct studies in the European boreal zone.There were minimal differences in the standardized emission rates between sites and across latitudes. The emission profile differed between provenances and sites, but there were not any distinct patterns which could be connected to a change in latitude. By using genetically identical trees and comparing the emission rates between sites and with genetically different trees, it was observed that the emission patterns were mostly influenced by genetics. But in order to confirm this possible stability of the relative emission profile based on genetics, more studies need to be performed.The effects of branch height, season and variation between years on observed emission pattern variations were also investigated. There were indications of potential influences of all three factors. However, due to different experimental setups between measurement campaigns, it is difficult to draw any robust conclusions.

Modeling Photosensitized Secondary Organic Aerosol Formation in Laboratory and Ambient Aerosols.

Photosensitized reactions involving imidazole-2-carboxaldehyde (IC) have been experimentally observed to contribute to secondary organic aerosol (SOA) growth. However, the extent of photosensitized reactions in ambient aerosols remains poorly understood and unaccounted for in atmospheric models. Here we use GAMMA 4.0, a photochemical box model that couples gas-phase and aqueous-phase aerosol chemistry, along with recent laboratory measurements of the kinetics of IC photochemistry, to analyze IC-photosensitized SOA formation in laboratory and ambient settings. Analysis of the laboratory results of Aregahegn et al. (2013) suggests that photosensitized production of SOA from limonene, isoprene, α-pinene, β-pinene, and toluene by 3IC* occurs at or near the surface of the aerosol particle. Reactive uptake coefficients were derived from the experimental data using GAMMA 4.0. Simulations of aqueous aerosol SOA formation at remote ambient conditions including IC photosensitizer chemistry indicate less than 0.3% contribution to SOA growth from direct reactions of 3IC* with limonene, isoprene, α-pinene, β-pinene, and toluene, and an enhancement of less than 0.04% of SOA formation from other precursors due to the formation of radicals in the bulk aerosol aqueous phase. Other, more abundant photosensitizer species, such as humic-like substances (HULIS), may contribute more significantly to aqueous aerosol SOA production.

Constraining uncertainties in particle-wall deposition correction during SOA formation in chamber experiments

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

Ozone and Secondary Organic Aerosol Formation of Toluene/NOx Irradiations under Complex Pollution Scenarios

Toluene is one of the most important precursor contributors to ozone and secondary organic aerosol (SOA), both of which greatly affect the air quality and human health. In this study, the effects of toluene on ozone and SOA formation were investigated in the presence of NOx in the CAPS-ZJU (Complex Air Pollution Study-Zhejiang University) smog chamber. Three comparison groups of experiments were conducted under the gas-phase environments of toluene/NOx, toluene/isoprene/NOx, and toluene/ethylene/NOx. The ozone concentration and physical properties of SOA such as mass concentration, aerosol yield, effective density, extinction and scattering were measured simultaneously. A toluene-dependent mechanism of ozone formation was found at ratios of toluene and NOx between 3.1 and 11.3 with the initial NOx concentration about 30 ppb. With further increase of the toluene concentration, the maximum value of ozone concentration remained almost stabilized. The maximum SOA yields decreased with increase of toluene, while the SOA effective density was concentrated at 1.3–1.4 g cm–3. The presence of isoprene or ethylene can promote the formation of ozone and SOA. The SOA nucleation was delayed under different initial toluene concentrations and the yield was reduced at the same mass concentration. A linear increase of extinction and scattering was observed with the increase of SOA mass concentration in both the toluene/isoprene/NOx and toluene/ethylene/NOx systems. A rapid increase of single scattering albedo reflects the process of SOA nucleation and growth. In addition, organic aerosol oxidation products tend to carboxylic acids in toluene/isoprene/NOx system according to Van Krevelen.

Indoor secondary organic aerosols formation from ozonolysis of monoterpene: An example of d-limonene with ammonia and potential impacts on pulmonary inflammations.

Monoterpene is one class of biogenic volatile organic compounds (BVOCs) which widely presents in household cleaning products and air fresheners. It plays reactive role in secondary organic aerosols (SOAs) formation with ozone (O3) in indoor environments. Such ozonolysis can be influenced by the presence of gaseous pollutants such as ammonia (NH3). This study focuses on investigations of ozone-initiated formation of indoor SOAs with d-limonene, one of the most abundant indoor monoterpenes, in a large environmental chamber. The maximum total particle number concentration from the ozonolysis in the presence of NH3 was 60% higher than that in the absence of NH3. Both of the nuclei coagulation and condensation involve in the SOAs growth. The potential risks of pulmonary injury for the exposure to the secondary particles formed were presented with the indexes of tumor necrosis factor-α (TNF-α), interleukin-6 (IL-6) and interleukin-10 (IL-10) expression levels in bronchoalveolar lavage fluid (BALF) upon intratracheal instillation in mice lung for 6 and 12h. The results indicated that there was 22-39% stronger pulmonary inflammatory effect on the particles generated with NH3. This is a pilot study which demonstrates the toxicities of the indoor SOAs formed from the ozonolysis of a monoterpene.

Influence of seed aerosol surface area and oxidation rate on vapor wall deposition and SOA mass yields: a case study with <i>α</i>-pinene ozonolysis

Abstract. Laboratory chambers, invaluable in atmospheric chemistry and aerosol formation studies, are subject to particle and vapor wall deposition, processes that need to be accounted for in order to accurately determine secondary organic aerosol (SOA) mass yields. Although particle wall deposition is reasonably well understood and usually accounted for, vapor wall deposition is less so. The effects of vapor wall deposition on SOA mass yields in chamber experiments can be constrained experimentally by increasing the seed aerosol surface area to promote the preferential condensation of SOA-forming vapors onto seed aerosol. Here, we study the influence of seed aerosol surface area and oxidation rate on SOA formation in α-pinene ozonolysis. The observations are analyzed using a coupled vapor–particle dynamics model to interpret the roles of gas–particle partitioning (quasi-equilibrium vs. kinetically limited SOA growth) and α-pinene oxidation rate in influencing vapor wall deposition. We find that the SOA growth rate and mass yields are independent of seed surface area within the range of seed surface area concentrations used in this study. This behavior arises when the condensation of SOA-forming vapors is dominated by quasi-equilibrium growth. Faster α-pinene oxidation rates and higher SOA mass yields are observed at increasing O3 concentrations for the same initial α-pinene concentration. When the α-pinene oxidation rate increases relative to vapor wall deposition, rapidly produced SOA-forming oxidation products condense more readily onto seed aerosol particles, resulting in higher SOA mass yields. Our results indicate that the extent to which vapor wall deposition affects SOA mass yields depends on the particular volatility organic compound system and can be mitigated through the use of excess oxidant concentrations.

Organic Nitrate Contribution to New Particle Formation and Growth in Secondary Organic Aerosols from α-Pinene Ozonolysis.

The chemical kinetics of organic nitrate production during new particle formation and growth of secondary organic aerosols (SOA) were investigated using the short-lived radioactive tracer (13)N in flow-reactor studies of α-pinene oxidation with ozone. Direct and quantitative measurements of the nitrogen content indicate that organic nitrates accounted for ∼40% of SOA mass during initial particle formation, decreasing to ∼15% upon particle growth to the accumulation-mode size range (>100 nm). Experiments with OH scavengers and kinetic model results suggest that organic peroxy radicals formed by α-pinene reacting with secondary OH from ozonolysis are key intermediates in the organic nitrate formation process. The direct reaction of α-pinene with NO3 was found to be less important for particle-phase organic nitrate formation. The nitrogen content of SOA particles decreased slightly upon increase of relative humidity up to 80%. The experiments show a tight correlation between organic nitrate content and SOA particle-number concentrations, implying that the condensing organic nitrates are among the extremely low volatility organic compounds (ELVOC) that may play an important role in the nucleation and growth of atmospheric nanoparticles.

Future vegetation–climate interactions in Eastern Siberia: an assessment of the competing effects of CO<sub>2</sub> and secondary organic aerosols

Abstract. Disproportional warming in the northern high latitudes and large carbon stocks in boreal and (sub)arctic ecosystems have raised concerns as to whether substantial positive climate feedbacks from biogeochemical process responses should be expected. Such feedbacks occur when increasing temperatures lead, for example, to a net release of CO2 or CH4. However, temperature-enhanced emissions of biogenic volatile organic compounds (BVOCs) have been shown to contribute to the growth of secondary organic aerosol (SOA), which is known to have a negative radiative climate effect. Combining measurements in Eastern Siberia with model-based estimates of vegetation and permafrost dynamics, BVOC emissions, and aerosol growth, we assess here possible future changes in ecosystem CO2 balance and BVOC–SOA interactions and discuss these changes in terms of possible climate effects. Globally, the effects of changes in Siberian ecosystem CO2 balance and SOA formation are small, but when concentrating on Siberia and the Northern Hemisphere the negative forcing from changed aerosol direct and indirect effects become notable – even though the associated temperature response would not necessarily follow a similar spatial pattern. While our analysis does not include other important processes that are of relevance for the climate system, the CO2 and BVOC–SOA interplay serves as an example for the complexity of the interactions between emissions and vegetation dynamics that underlie individual terrestrial processes and highlights the importance of addressing ecosystem–climate feedbacks in consistent, process-based model frameworks.

Phase, composition, and growth mechanism for secondary organic aerosol from the ozonolysis of <i>α</i>-cedrene

Abstract. Sesquiterpenes are an important class of biogenic volatile organic compounds (BVOCs) and have a high secondary organic aerosol (SOA) forming potential. However, SOA formation from sesquiterpene oxidation has received less attention compared to other BVOCs such as monoterpenes, and the underlying mechanisms remain poorly understood. In this work, we present a comprehensive experimental investigation of the ozonolysis of α-cedrene both in a glass flow reactor (27–44 s reaction times) and in static Teflon chambers (30–60 min reaction times). The SOA was collected by impaction or filters, followed by analysis using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and electrospray ionization mass spectrometry (ESI-MS), or measured online using direct analysis in real-time mass spectrometry (DART-MS) and aerosol mass spectrometry (AMS). The slow evaporation of 2-ethylhexyl nitrate that was incorporated into the SOA during its formation and growth gives an estimated diffusion coefficient of 3 × 10−15 cm2 s−1 and shows that SOA is a highly viscous semisolid. Possible structures of four newly observed low molecular weight (MW ≤ 300 Da) reaction products with higher oxygen content than those previously reported were identified. High molecular weight (HMW) products formed in the early stages of the oxidation have structures consistent with aldol condensation products, peroxyhemiacetals, and esters. The size-dependent distributions of HMW products in the SOA, as well as the effects of stabilized Criegee intermediate (SCI) scavengers on HMW products and particle formation, confirm that HMW products and reactions of SCI play a crucial role in early stages of particle formation. Our studies provide new insights into mechanisms of SOA formation and growth in α-cedrene ozonolysis and the important role of sesquiterpenes in new particle formation as suggested by field measurements.

"APEC Blue": Secondary Aerosol Reductions from Emission Controls in Beijing.

China implemented strict emission control measures in Beijing and surrounding regions to ensure good air quality during the 2014 Asia-Pacific Economic Cooperation (APEC) summit. We conducted synchronous aerosol particle measurements with two aerosol mass spectrometers at different heights on a meteorological tower in urban Beijing to investigate the variations in particulate composition, sources and size distributions in response to emission controls. Our results show consistently large reductions in secondary inorganic aerosol (SIA) of 61–67% and 51–57%, and in secondary organic aerosol (SOA) of 55% and 37%, at 260 m and ground level, respectively, during the APEC summit. These changes were mainly caused by large reductions in accumulation mode particles and by suppression of the growth of SIA and SOA by a factor of 2–3, which led to blue sky days during APEC commonly referred to as “APEC Blue”. We propose a conceptual framework for the evolution of primary and secondary species and highlight the importance of regional atmospheric transport in the formation of severe pollution episodes in Beijing. Our results indicate that reducing the precursors of secondary aerosol over regional scales is crucial and effective in suppressing the formation of secondary particulates and mitigating PM pollution.

Constraining condensed-phase formation kinetics of secondary organic aerosol components from isoprene epoxydiols

Abstract. Isomeric epoxydiols from isoprene photooxidation (IEPOX) have been shown to produce substantial amounts of secondary organic aerosol (SOA) mass and are therefore considered a major isoprene-derived SOA precursor. Heterogeneous reactions of IEPOX on atmospheric aerosols form various aerosol-phase components or "tracers" that contribute to the SOA mass burden. A limited number of the reaction rate constants for these acid-catalyzed aqueous-phase tracer formation reactions have been constrained through bulk laboratory measurements. We have designed a chemical box model with multiple experimental constraints to explicitly simulate gas- and aqueous-phase reactions during chamber experiments of SOA growth from IEPOX uptake onto acidic sulfate aerosol. The model is constrained by measurements of the IEPOX reactive uptake coefficient, IEPOX and aerosol chamber wall losses, chamber-measured aerosol mass and surface area concentrations, aerosol thermodynamic model calculations, and offline filter-based measurements of SOA tracers. By requiring the model output to match the SOA growth and offline filter measurements collected during the chamber experiments, we derive estimates of the tracer formation reaction rate constants that have not yet been measured or estimated for bulk solutions.

First Quantification of Imidazoles in Ambient Aerosol Particles: Potential Photosensitizers, Brown Carbon Constituents, and Hazardous Components.

Imidazoles are widely discussed in recent literature. They have been studied as a secondary product of the reaction of dicarbonyls with nitrogen containing compounds in a number of laboratory studies, potentially acting as photosensitizers triggering secondary organic aerosol growth and are forming constituents of light absorbing brown carbon. Despite the knowledge from laboratory studies, no quantitative information about imidazoles in ambient aerosol particles is available. Within the present study, five imidazoles (1-butylimidazole, 1-ethylimidazole, 2-ethylimidazole, imidazol-2-carboxaldehyde, and 4(5)-methylimidazole) were successfully identified and quantified for the first time in ambient aerosol samples from different environments in Europe and China. Their concentrations range between 0.2 and 14 ng/m(3). 4(5)-Methylimidazole was found to be the most abundant imidazole. The occurrence of imidazoles seems to be favored at sites with strong biomass burning influence or connected to more polluted air masses. No connection was found between aerosol particle pH and imidazole concentration. Our work corroborates the laboratory studies by showing that imidazoles are present in ambient aerosol samples in measurable amounts. Moreover, it further motivates to explore the potential photosensitizing properties of small alkyl-substituted imidazoles.

Insights into the Formation and Evolution of Individual Compounds in the Particulate Phase during Aromatic Photo-Oxidation.

Secondary organic aerosol (SOA) is well-known to have adverse effects on air quality and human health. However, the dynamic mechanisms occurring during SOA formation and evolution are poorly understood. The time-resolved SOA composition formed during the photo-oxidation of three aromatic compounds, methyl chavicol, toluene and 4-methyl catechol, were investigated at the European Photoreactor. SOA was collected using a particle into liquid sampler and analyzed offline using state-of-the-art mass spectrometry to produce temporal profiles of individual photo-oxidation products. In the photo-oxidation of methyl chavicol, 70 individual compounds were characterized and three distinctive temporal profile shapes were observed. The calculated mass fraction (Ci,aer/COA) of the individual SOA compounds showed either a linear trend (increasing/decreasing) or exponential decay with time. Substituted nitrophenols showed an exponential decay, with the nitro-group on the aromatic ring found to control the formation and loss of these species in the aerosol phase. Nitrophenols from both methyl chavicol and toluene photo-oxidation experiments showed a strong relationship with the NO2/NO (ppbv/ppbv) ratio and were observed during initial SOA growth. The location of the nitrophenol aromatic substitutions was found to be critically important, with the nitrophenol in the photo-oxidation of 4-methyl catechol not partitioning into the aerosol phase until irradiation had stopped; highlighting the importance of studying SOA formation and evolution at a molecular level.

The influences of mass loading and rapid dilution of secondary organic aerosol on particle volatility

Abstract. The thermally induced evaporation of secondary organic aerosol (SOA) has been characterized for SOA formed from the dark ozonolysis of α-pinene at initial mass concentrations ranging from 1 to 800 μg m−3. Temperature-dependent particle size distributions were measured using a thermodenuder and the resulting mass thermograms were compared between the SOA formed at the various SOA mass concentrations. Negligible differences were observed between the mass thermograms for SOA concentrations < 300 μg m−3. At higher SOA concentrations, the observed mass thermograms indicated the SOA was actually slightly less volatile than the SOA at lower concentrations; this is likely an artifact due to either saturation of the gas phase or to recondensation during cooling. The thermograms observed when the SOA was formed at high concentrations (> 380 μg m−3) and then rapidly isothermally diluted to low concentrations (1–20 μg m−3) were identical to those for the SOA that was initially formed at low concentrations. The experimental results were compared to a kinetic model that simulates particle evaporation upon heating in a thermodenuder for a given input volatility distribution and particle composition. Three cases were considered: (1) the SOA was composed of semi-volatile monomer species with a volatility distribution based on that derived previously from consideration of SOA growth experiments; (2) the initial SOA was composed almost entirely of non-volatile dimers that decompose upon heating into their semi-volatile monomer units, which can then evaporate; and (3) where a volatility distribution was derived by fitting the model to the observed mass thermograms. It was found that good agreement is obtained between model predictions and the observations when the particle composition is dominated by either compounds of low volatility or by dimers. These same models were used to simulate isothermal evaporation of the SOA and were found to be broadly consistent with literature observations that indicate that SOA evaporation occurs with multiple timescales. The use of the semi-volatile monomer volatility distribution fails to reproduce the observed evaporation. The presence of dimers and larger oligomers in secondary organic aerosol formed from products of the reaction of α-pinene and O3 has been well established in laboratory studies. However, the timescale and relative importance of the formation of oligomers or low-volatility compounds in the growth and evaporation of SOA has been debated. This study provides further support that low-volatility compounds and oligomers are formed in α-pinene + O3 in high abundances and suggests that their formation occurs rapidly upon particle formation.

Instantaneous nitric oxide effect on secondary organic aerosol formation from m-xylene photooxidation

Secondary organic aerosol (SOA) formation from aromatic hydrocarbon photooxidation is highly sensitive to NO concentration. The instantaneous effect of NO on SOA formation from m-xylene photooxidation is investigated in this work by data mining 10 years of aromatic hydrocarbon chamber experiments conducted in the UC Riverside/CE-CERT chamber. First, the effect of sub-ppb NO concentrations on SOA formation is explored. The relationship of SOA growth rate to 1) NO2/NO ratio; 2) instantaneous HC/NO; 3) absolute NO concentration; 4) peroxy radical reaction branching ratio and 5) hydroxyl radical concentration are illustrated. Second, continuous and stepwise NO, NO2 and HONO injection are applied to m-xylene photooxidation experiments to simulate continuous NO sources in an urban area. The influence of these reaction scenarios on radical concentrations and SOA formation is explored. [HO2]/[RO2] shows a strong correlation with SOA yields in addition to [OH]/[HO2], [OH], [HO2] and [RO2]. Enhanced SOA formation is observed when low NO levels (<1 ppb) are artificially maintained by continuous or step-wise injection; consistent with earlier research, SOA formation is observed to be suppressed by large initial NO injections. It is proposed that NO at sub-ppb level enhances OH formation increasing HO2 and RO2 and therefore promoting SOA formation. Further, two NO pathways (one promoting and one suppressing SOA formation) and one extremely low NO phase (NO “free”) are used to demonstrate the evolution of NO impact on SOA formation during photooxidation. This study implies that SOA yields from aromatic hydrocarbon and low NOx photooxidation is previously underestimated due to differences between traditional environmental chamber experiments and atmospheric reactivity.

Field measurements of biogenic volatile organic compounds in the atmosphere by dynamic solid-phase microextraction and portable gas chromatography-mass spectrometry

Biogenic volatile organic compounds (BVOCs) participate in many physicochemical processes in the atmosphere. Studies indicate that some of these volatile compounds can be photo-oxidized to non-volatile species that contribute to atmospheric formation and growth of secondary organic aerosols (SOA). In this study, the applicability of dynamic solid-phase microextraction (SPME) for the sampling of atmospheric BVOCs and their oxidation products was tested. These compounds were then analysed via portable gas chromatography-mass spectrometry (GC–MS). The measurements were performed in mid-summer 2013 at the Station for Measuring Ecosystem–Atmosphere Relations, SMEAR II in Hyytiälä, Finland. Numerous classes of compounds were efficiently sampled on PDMS/DVB coated SPME, thermally desorbed and analysed by GC–MS, including monoterpenes, their oxidation products, and amines. Results were analysed against meteorological conditions observed during the sampling campaign and the total amount of monoterpenes obtained by proton-transfer-reaction mass spectrometry (PTR-MS). The comparison of the referred data with obtained results demonstrated the capability of the dynamic SPME method for fast in-situ sampling and analysis of organic gaseous compounds in the atmosphere with minimal analytical steps.

A New Method to Measure Aerosol Particle Bounce Using a Cascade Electrical Low Pressure Impactor

The phase state of secondary organic aerosol (SOA) in the atmosphere is of scientific interest as it can impact SOA growth and reactivity. For this purpose, a simplified method is described herein to estimate SOA bounce factor to gain an improved understanding of the phase state of atmospheric aerosols. This new method involves the use of a multistage electrical low pressure cascade impactor operating with either smooth or sintered impaction plates. Measurement of the raw current on smooth and sintered plates allows one to calculate the bounce factor, eliminating the need for a scanning mobility particle sizer to independently measure the SOA aerodynamic size distribution. The proposed method provides the temporal resolution necessary to measure phase changes in a continuously evolving SOA parcel.We validate our method by measuring the bounce factor of solid and liquid aerosols, namely ammonium sulfate (AS), dioctyl sebacate (DOS), oleic acid (OA) and ozonized OA, and also present bounce factor evolution ...

Biogenic SOA formation through gas-phase oxidation and gas-to-particle partitioning – a comparison between process models of varying complexity

Abstract. Biogenic volatile organic compounds (BVOCs) emitted by vegetation play an important role for aerosol mass loadings since the oxidation products of these compounds can take part in the formation and growth of secondary organic aerosols (SOA). The concentrations and properties of BVOCs and their oxidation products in the atmosphere are poorly characterized, which leads to high uncertainties in modeled SOA mass and properties. In this study, the formation of SOA has been modeled along an air-mass trajectory over northern European boreal forest using two aerosol dynamics box models where the prediction of the condensable organics from the gas-phase oxidation of BVOC is handled with schemes of varying complexity. The use of box model simulations along an air-mass trajectory allows us to compare, under atmospheric relevant conditions, different model parameterizations and their effect on SOA formation. The result of the study shows that the modeled mass concentration of SOA is highly dependent on the organic oxidation scheme used to predict oxidation products. A near-explicit treatment of organic gas-phase oxidation (Master Chemical Mechanism version 3.2) was compared to oxidation schemes that use the volatility basis set (VBS) approach. The resulting SOA mass modeled with different VBS schemes varies by a factor of about 7 depending on how the first-generation oxidation products are parameterized and how they subsequently age (e.g., how fast the gas-phase oxidation products react with the OH radical, how they respond to temperature changes, and if they are allowed to fragment during the aging process). Since the VBS approach is frequently used in regional and global climate models due to its relatively simple treatment of the oxidation products compared to near-explicit oxidation schemes, a better understanding of the above-mentioned processes is needed. Based on the results of this study, fragmentation should be included in order to obtain a realistic SOA formation. Furthermore, compared to the most commonly used VBS schemes, the near-explicit method produces less – but more oxidized – SOA.