Secondary Organic Aerosol Particles Research Articles

Kinetics of oligomer-forming reactions involving the major functional groups present in atmospheric secondary organic aerosol particles.

Atmospheric organic aerosol particles impact climate as well as human and environmental health. Secondary organic aerosol (SOA), which is formed by the gas-to-particle partitioning of products of the oxidation of volatile organic compounds (VOCs) emitted from biogenic or anthropogenic sources, contributes a large fraction of this material. In the particle phase, these products can undergo accretion reactions to form oligomers that impact the formation, composition, and chemical-physical properties of aerosols. While these reactions are known to occur in the atmosphere, data and models describing their kinetics and equilibria are sparse. Here, reactions of compounds containing potentially reactive hydroperoxide, hydroxyl, carboxyl, aldehyde, and ketone groups were investigated in single and phase-separated organic/aqueous mixtures in the absence and presence of a sulfuric acid catalyst. Compounds containing these groups and a nonreactive UV-absorbing nitrate group were synthesized and their reactions and products were monitored and characterized using high-performance liquid chromatography with UV detection (HPLC-UV), electrospray ionization-mass spectrometry (ESI-MS), and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. Reactions were observed between hydroperoxides and aldehydes to form peroxyhemiacetals, and between carboxylic acids and alcohols to form esters, and their rate and equilibrium constants were determined. No reactions were observed in other mixtures, indicating that under the conditions of these experiments only a few reaction pathways form oligomers. Reactions were also conducted with probe compounds and SOA formed in an environmental chamber reaction of α-pinene with O3. Whereas in a previous study we observed a rapid hydroperoxide reaction in this SOA, among the other compounds studied here only alcohols reacted. These results provide insight into the types of accretion reactions that are likely to occur in atmospheric aerosols, and the rate and equilibrium constants can be used to better model SOA chemistry.

Effects of NO2 and SO2 on the secondary organic aerosol formation from [formula omitted]-pinene photooxidation

Elucidating the effects of anthropogenic pollutants on the photooxidation of biogenic volatile organic compounds is crucial to understanding the fundamental mechanisms of secondary organic aerosol (SOA) formation. Here, the impacts of NO2 and SO2 on SOA formation from the photooxidation of a representative monoterpene, β-pinene, were investigated by a number of laboratory studies. The results indicated NO2 enhanced the SOA mass concentrations and particle number concentrations under both low and high β-pinene conditions. This could be rationalized that the increased O3 concentrations upon the NOx photolysis was helpful for the generation of more amounts of O3-oxidized products, which accelerated the SOA nucleation and growth. Combing with NO2, the promotion of the SOA yield by SO2 was mainly reflected in the increase of mass concentration, which might be due to the elimination of the newly formed particles by the initially formed particles. The observed low oxidation degree of SOA might be attributed to the fast growth of SOA, resulting in the uptake of less oxygenated gas-phase species onto the particle phase. The present findings have important implications for SOA formation affected by anthropogenic–biogenic interactions in the ambient atmosphere.

Sunlight can convert atmospheric aerosols into a glassy solid state and modify their environmental impacts

Secondary organic aerosol (SOA) plays a critical, yet uncertain, role in air quality and climate. Once formed, SOA is transported throughout the atmosphere and is exposed to solar UV light. Information on the viscosity of SOA, and how it may change with solar UV exposure, is needed to accurately predict air quality and climate. However, the effect of solar UV radiation on the viscosity of SOA and the associated implications for air quality and climate predictions is largely unknown. Here, we report the viscosity of SOA after exposure to UV radiation, equivalent to a UV exposure of 6 to 14 d at midlatitudes in summer. Surprisingly, UV-aging led to as much as five orders of magnitude increase in viscosity compared to unirradiated SOA. This increase in viscosity can be rationalized in part by an increase in molecular mass and oxidation of organic molecules constituting the SOA material, as determined by high-resolution mass spectrometry. We demonstrate that UV-aging can lead to an increased abundance of aerosols in the atmosphere in a glassy solid state. Therefore, UV-aging could represent an unrecognized source of nuclei for ice clouds in the atmosphere, with important implications for Earth's energy budget. We also show that UV-aging increases the mixing times within SOA particles by up to five orders of magnitude throughout the troposphere with important implications for predicting the growth, evaporation, and size distribution of SOA, and hence, air pollution and climate.

Chemistry of Secondary Organic Aerosol Formation from Reactions of Monoterpenes with OH Radicals in the Presence of NOx

The oxidation of volatile organic compounds (VOCs), which are emitted to the atmosphere from natural and anthropogenic sources, leads to the formation of ozone and secondary organic aerosol (SOA) particles that impact air quality and climate. In the study reported here, we investigated the products of the reactions of five biogenic monoterpenes with OH radicals (an important daytime oxidant) under conditions that mimic the chemistry that occurs in polluted air, and developed mechanisms to explain their formation. Experiments were conducted in an environmental chamber, and information on the identity of gas-phase molecular products was obtained using online mass spectrometry, while liquid chromatography and two methods of functional group analysis were used to characterize the SOA composition. The gas-phase products of the reactions were similar to those formed in our previous studies of the reactions of these monoterpenes with NO3 radicals (an important nighttime oxidant), in that they all contained various combinations of nitrate, carbonyl, hydroxyl, ester, and ether groups. But in spite of this, less SOA was formed in OH/NOx reactions and it was composed of monomers, while SOA formed in NO3 radical reactions consisted of acetal and hemiacetal oligomers formed by particle-phase accretion reactions. In addition, it appeared that some monomers underwent particle-phase hydrolysis, whereas oligomers did not. These differences are due primarily to the arrangement of hydroxyl, carbonyl, nitrate, and ether groups in the monomers, which can in turn be explained by differences in OH and NO3 radical reaction mechanisms. The results provide insight into the impact of VOC structure on the amount and composition of SOA formed by atmospheric oxidation, which influence important aerosol properties such as volatility and hygroscopicity.

Identification of highly oxygenated organic molecules and their role in aerosol formation in the reaction of limonene with nitrate radical

Abstract. Nighttime NO3-initiated oxidation of biogenic volatile organic compounds (BVOCs) such as monoterpenes is important for the atmospheric formation and growth of secondary organic aerosol (SOA), which has significant impact on climate, air quality, and human health. In such SOA formation and growth, highly oxygenated organic molecules (HOM) may be crucial, but their formation pathways and role in aerosol formation have yet to be clarified. Among monoterpenes, limonene is of particular interest for its high emission globally and high SOA yield. In this work, HOM formation in the reaction of limonene with nitrate radical (NO3) was investigated in the SAPHIR chamber (Simulation of Atmospheric PHotochemistry In a large Reaction chamber). About 280 HOM products were identified, grouped into 19 monomer families, 11 dimer families, and 3 trimer families. Both closed-shell products and open-shell peroxy radicals (RO2⚫) were observed, and many of them have not been reported previously. Monomers and dimers accounted for 47 % and 47 % of HOM concentrations, respectively, with trimers making up the remaining 6 %. In the most abundant monomer families, C10H15−17NO6−14, carbonyl products outnumbered hydroxyl products, indicating the importance of RO2⚫ termination by unimolecular dissociation. Both RO2⚫ autoxidation and alkoxy–peroxy pathways were found to be important processes leading to HOM. Time-dependent concentration profiles of monomer products containing nitrogen showed mainly second-generation formation patterns. Dimers were likely formed via the accretion reaction of two monomer RO2⚫, and HOM-trimers via the accretion reaction between monomer RO2⚫ and dimer RO2⚫. Trimers are suggested to play an important role in new particle formation (NPF) observed in our experiment. A HOM yield of 1.5%-0.7%+1.7% was estimated considering only first-generation products. SOA mass growth could be reasonably explained by HOM condensation on particles assuming irreversible uptake of ultra-low volatility organic compounds (ULVOCs), extremely low volatility organic compounds (ELVOCs), and low volatility organic compounds (LVOCs). This work provides evidence for the important role of HOM formed via the limonene +NO3 reaction in NPF and growth of SOA particles.

Characterization and Quantification of Particle-Bound Criegee Intermediates in Secondary Organic Aerosol.

The ozonolysis of alkenes contributes substantially to the formation of secondary organic aerosol (SOA), which are important modulators of air quality and the Earth’s climate. Criegee intermediates (CIs) are abundantly formed through this reaction. However, their contributions to aerosol particle chemistry remain highly uncertain. In this work, we present the first application of a novel methodology, using spin traps, which simultaneously quantifies CIs produced from the ozonolysis of volatile organic compounds in the gas and particle phases. Only the smallest CI with one carbon atom was detected in the gas phase of a β-caryophyllene ozonolysis reaction system. However, multiple particle-bound CIs were observed in β-caryophyllene SOA. The concentration of the most abundant CI isomer in the particle phase was estimated to constitute ∼0.013% of the SOA mass under atmospherically relevant conditions. We also demonstrate that the lifetime of CIs in highly viscous SOA particles is at least on the order of minutes, substantially greater than their gas-phase lifetime. The confirmation of substantial concentrations of large CIs with elongated lifetimes in SOA raises new questions regarding their influence on the chemical evolution of viscous SOA particles, where CIs may be a previously underestimated source of reactive species.

Experimental study on the imidazoles of aqueous secondary organic aerosol formed from reaction of methylglyoxal and ammonium sulphate

Imidazole and its derivatives are the main heterocyclic nitrogen-containing brown carbon constituents in aerosol particles. Imidazoles of aqueous secondary organic aerosol (aqSOA) particles formed from the reaction of methylglyoxal and ammonium sulphate ((NH4)2SO4) are detected by vacuum ultraviolet photoionization aerosol mass spectrometer (VUV-PIMS) in real-time and verified off-line with optical spectrometry in current study. The experimental results showed that the single photon ionization mass spectrum of aqSOA particles measured by VUV-PIMS emerged the molecular ion peaks at m/z = 68, 82 and 110. While, the extraction solution of aqSOA particles detected by off-line techniques demonstrated that the characteristic peaks at 217 and 282 nm appeared in the UV–Vis spectrum; the strong emission in 405–480 nm with maximum emission wavelength at 435 nm contained in the 3D fluorescence spectra; and the chemical shift peaks of hydrogen atoms on N–H, CC and CN bond on imidazole ring and methyl group arised in the 1H-NMR spectrum. In view of these spectral information, 4-methyl-imidazole and 4-methyl-imidazole-2-carbaldehyde are determined as the principal products of the aqueous reaction between methylglyoxal and (NH4)2SO4. The possible reaction mechanism leading to the generation of imidazole compounds are also discussed. These will help to understand the formation process of imidazole compounds in atmospheric aerosol particles, and provide experimental basis for the model mechanism study of aqSOA particles.

Chemical composition of secondary organic aerosol particles formed from mixtures of anthropogenic and biogenic precursors

Abstract. A series of experiments was designed and conducted in the Manchester Aerosol Chamber (MAC) to study the photo-oxidation of single and mixed biogenic (isoprene and α-pinene) and anthropogenic (o-cresol) precursors in the presence of NOx and ammonium sulfate seed particles. Several online techniques (HR-ToF-AMS, semi-continuous GC-MS, NOx and O3 analyser) were coupled to the MAC to monitor the gas and particle mass concentrations. Secondary organic aerosol (SOA) particles were collected onto a quartz-fibre filter at the end of each experiment and analysed using liquid chromatography–ultrahigh-resolution mass spectrometry (LC-Orbitrap MS). The SOA particle chemical composition in single and mixed precursor systems was investigated using non-targeted accurate mass analysis of measurements in both negative and positive ionization modes, significantly reducing data complexity and analysis time, thereby providing a more complete assessment of the chemical composition. This non-targeted analysis is not widely used in environmental science and has never been previously used in atmospheric simulation chamber studies. Products from α-pinene were found to dominate the binary mixed α-pinene–isoprene system in terms of signal contributed and the number of particle components detected. Isoprene photo-oxidation was found to generate negligible SOA particle mass under the investigated experimental conditions, and isoprene-derived products made a negligible contribution to particle composition in the α-pinene–isoprene system. No compounds uniquely found in this system sufficiently contributed to be reliably considered a tracer compound for the mixture. Methyl-nitrocatechol isomers (C7H7NO4) and methyl-nitrophenol (C7H7NO3) from o-cresol oxidation made dominant contributions to the SOA particle composition in both the o-cresol–isoprene and o-cresol–α-pinene binary systems in negative ionization mode. In contrast, interactions in the oxidation mechanisms led to the formation of compounds uniquely found in the mixed o-cresol-containing binary systems in positive ionization mode. C9H11NO and C8H8O10 made large signal contributions in the o-cresol–isoprene binary system. The SOA molecular composition in the o-cresol–α-pinene system in positive ionization mode is mainly driven by the high-molecular-weight compounds (e.g. C20H31NO4 and C20H30O3) uniquely found in the mixture. The SOA particle chemical composition formed in the ternary system is more complex. The molecular composition and signal abundance are both markedly similar to those in the single α-pinene system in positive ionization mode, with major contributions from o-cresol products in negative ionization mode.

Effects of the VACES particle concentrator on secondary organic aerosol and ambient particle composition

Effects of the VACES particle concentrator on secondary organic aerosol and ambient particle composition

Bridged-ozonolysis of mixed aromatic hydrocarbons and organic amines: Inter-inhibited decay rate, altered product yield and synergistic-effect-enhanced secondary organic aerosol formation

Ozonolysis of aromatic hydrocarbons (AHs) or organic amines (OAs) occurs via different transformation processes, with varying rate constants and contributions to secondary organic aerosol (SOA) formation. However, to date no data is available on the ozonolysis of mixtures of AHs and OAs. This study investigated the kinetics, products and SOA yield from ozonolysis of mixture of trimethylamine with styrene, toluene or m-xylene. In the mixed system, the decay rates of styrene and trimethylamine were (1.32 ± 0.26) × 10−4 s−1 and (0.80 ± 0.02) × 10−4 s−1, decreasing up to 36.5 % and 54.4 % compared with their respective individual systems. This inter-inhibition of decay rates increased the yield of main products from styrene (i.e. benzaldehyde) by 23.5 % and trimethylamine (i.e. nitromethane) by 346.4 %. Ozonolysis of styrene or trimethylamine produced formaldehyde, which acted as a bridged product connecting the ozonolysis pathways of these two substrates, altering the yields of all products. Ozonolysis of styrene to benzaldehyde determined the increase of SOA particle number concentration (from 9.5 × 105 to 1.9 × 106 particles cm−3), while trimethylamine ozonolysis to N, N-dimethylformamide contributed to synergistic-effect-enhanced SOA yield (from (64.3 ± 3.5)% to (68.1 ± 4.8)%). The findings provide a novel insight into the kinetics and mechanism of ozonolysis, as well as the resulting SOA formation from mixtures of AHs and OAs, helping to comprehensively understand the transformation and fate of organics in real atmospheric environments.

Partitioning of Organonitrates in the Production of Secondary Organic Aerosols from α-Pinene Photo-Oxidation.

The chemical pathways for the production of secondary organic aerosols (SOA) are influenced by the concentration of nitrogen oxides (NOx), including the production of organonitrates (ON). Herein, a series of experiments conducted in an environmental chamber investigated the production and partitioning of total organonitrates from α-pinene photo-oxidation from <1 to 24 ppb NOx. Gas-phase and particle-phase organonitrates (gON and pON, respectively) were measured by laser-induced fluorescence (LIF). The composition of the particle phase and the particle mass concentration were simultaneously characterized by online aerosol mass spectrometry. The LIF and MS measurements of pON concentrations had a Pearson correlation coefficient of 0.91 from 0.3 to 1.1 μg m–3. For 1–6 ppb NOx, the yield of SOA particle mass concentration increased from 0.02 to 0.044 with NOx concentration. For >6 ppb NOx, the yield steadily dropped, reaching 0.034 at 24 ppb NOx. By comparison, the yield of pON steadily increased from 0.002 to 0.022 across the range of investigated NOx concentrations. The yield of gON likewise increased from 0.005 to 0.148. The gas-to-particle partitioning ratio (pON/(pON + gON)) depended strongly on the NOx concentration, changing from 0.27 to 0.13 as the NOx increased from <1 to 24 ppb. In the atmosphere, there is typically a cross-over point between clean and polluted conditions that strongly affects SOA production, and the results herein quantitatively identify 6 ppb NOx as that point for α-pinene photo-oxidation under these study conditions, including the production and partitioning of organonitrates. The trends in SOA yield and partitioning ratio as a function of NOx occur because of the changes in pON volatility.

Cytotoxicity and oxidative stress induced by atmospheric mono-nitrophenols in human lung cells

Nitrophenols (NPs) are hazardous pollutants found in various environmental matrices, including ambient fine particulate matter (PM2.5), agricultural residues, rainwater, wildfires, and industrial wastes. This study showed for the first time the effect of three pure nitrophenols and their mixture on human lung cells to provide basic understanding of the NP influence on cell elements and processes. We identified NPs in ambient PM2.5 and secondary organic aerosol (SOA) particles generated from the photooxidation of monocyclic aromatic hydrocarbons in the U.S. EPA smog chamber. We assessed the toxicity of identified NPs and their equimolar mixture in normal bronchial epithelial (BEAS-2B) and alveolar epithelial cancer (A549) lung cell lines. The inhibitory concentration-50 (IC50) values were highest and lowest in BEAS-2B cells treated with 2-nitrophenol (2NP) and 4-nitrophenol (4NP), respectively, at 24 h of exposure. The lactate dehydrogenase (LDH) assay showed that 4NP, the most abundant NP we identified in PM2.5, was the most cytotoxic NP examined in both cell lines. The annexin-V/fluorescein isothiocyanate (FITC) analysis showed that the populations of late apoptotic/necrotic BEAS-2B and A549 cells exposed to 3NP, 4NP, and NP equimolar mixture increased between 24 and 48 h. Cellular reactive oxygen species (ROS) buildup led to cellular death post exposure to 3NP, 4NP and the NP mixtures, while 2NP induced the lowest ROS buildup. An increased mitochondrial ROS signal following NP exposure occurred only in BEAS-2B cells. The tetramethylrhodamine, methyl ester, perchlorate (TMRM) assay showed that exposed cells exhibited collapse of the mitochondrial membrane potential. TMRM signals decreased significantly only in BEAS-2B cells, and most strongly with 4NP exposures. Our results suggest that acute atmospheric exposures to NPs may be toxic at high concentrations, but not at ambient PM2.5 concentrations. Further chronic studies with NP and NP-containing PM2.5 are warranted to assess their contribution to lung pathologies.

Description and evaluation of a secondary organic aerosol and new particle formation scheme within TM5-MP v1.2

Abstract. We have implemented and evaluated a secondary organic aerosol scheme within the chemistry transport model TM5-MP in this work. In earlier versions of TM5-MP the secondary organic aerosol (SOA) was emitted as Aitken-sized particle mass emulating the condensation. In the current scheme we simulate the formation of secondary organic aerosol from oxidation of isoprene and monoterpenes by ozone and hydroxyl radicals, which produce semi-volatile organic compounds (SVOCs) and extremely low-volatility compounds (EVOCs). Subsequently, SVOCs and ELVOCs can condense on particles. Furthermore, we have introduced a new particle formation mechanism depending on the concentration of ELVOCs. For evaluation purposes, we have simulated the year 2010 with the old and new scheme; we see an increase in simulated production of SOA from 39.9 Tg yr−1 with the old scheme to 52.5 Tg yr−1 with the new scheme. For more detailed analysis, the particle mass and number concentrations and their influence on the simulated aerosol optical depth are compared to observations. Phenomenologically, the new particle formation scheme implemented here is able to reproduce the occurrence of observed particle formation events. However, the modelled concentrations of formed particles are clearly lower than in observations, as is the subsequent growth to larger sizes. Compared to the old scheme, the new scheme increases the number concentrations across the observation stations while still underestimating the observations. The organic aerosol mass concentrations in the US show a much better seasonal cycle and no clear overestimation of mass concentrations anymore. In Europe the mass concentrations are lowered, leading to a larger underestimation of observations. Aerosol optical depth (AOD) is generally slightly increased except in the northern high latitudes. This brings the simulated annual global mean AOD closer to the observational estimate. However, as the increase is rather uniform, biases tend to be reduced only in regions where the model underestimates the AOD. Furthermore, the correlations with satellite retrievals and ground-based sun-photometer observations of AOD are improved. Although the process-based approach to SOA formation causes a reduction in model performance in some areas, overall the new scheme improves the simulated aerosol fields.

Hygroscopic growth and CCN activity of secondary organic aerosol produced from dark ozonolysis of γ-terpinene

The hygroscopic growth factor (GF) and cloud condensation nuclei (CCN) activity of secondary organic aerosol (SOA) particles produced during dark ozonolysis of γ-terpinene under different reaction conditions were investigated. The SOA particles were produced in the presence or absence of cyclohexane, an OH scavenger; 1,3,5-trimethylbenzene, an anthropogenic volatile organic compound; and (NH4)2SO4 seed particles. A hygroscopicity tandem differential mobility analyzer was used to determine the GFs of the SOA particles at RHs ≤ 93%. For some experiments, a CCN counter was used for size-resolved measurement of CCN activation at supersaturation (S) in the range of 0.1 to 1%. The single hygroscopicity parameter κ was derived from both the GF and CCN measurements. Under subsaturated conditions, all the SOA (except those in the presence of the (NH4)2SO4 seeds) showed small GF values. These GFs demonstrated that SOA mass loading affected the GF. A decrease in the SOA mass loading led to increased GF and corresponding κGFvalues. However, in a supersaturation regime, the SOA mass loading and the size of the particles did not significantly alter the CCN activity of the SOA. Our CCN measurements showed higher κCCN values (κCCN = 0.20–0.24) than those observed in most monoterpene ozonolysis studies (κCCN = 0.1–0.14). This difference may have been due to the presence of the two endocyclic double bonds in the γ-terpinene structure, which may have affected the SOA chemical composition, in contrast to monoterpenes that contain an exocyclic double bond. Our comparisons of sub- and supersaturated conditions showed a larger range of κ values than other experiments. Average κCCN/κGF ratios of ~7 and 14 were obtained in the unseeded SOA experiments at low and high SOA mass loadings, respectively. The average κCCN of 0.23 indicated that the SOA produced during ozonolysis of γ-terpinene exhibited fairly high CCN activity.

Equilibration times in viscous and viscoelastic aerosol particles

Secondary organic aerosol (SOA) particles in Earth's atmosphere can exist in phase states where mass transport and chemical transformations are greatly impeded.

Hygroscopicity of internally mixed ammonium sulfate and secondary organic aerosol particles formed at low and high relative humidity

Aged atmospheric volatile organic matter create secondary organic aerosols (SOA), influencing the indirect effect of aerosols. A difference in viscosity and hydrophobicity of SOA may be the primary cause of changes in hygroscopicity.

Four- and Five-Carbon Dicarboxylic Acids Present in Secondary Organic Aerosol Produced from Anthropogenic and Biogenic Volatile Organic Compounds

To better understand precursors of dicarboxylic acids in ambient secondary organic aerosol (SOA), we studied C4–C9 dicarboxylic acids present in SOA formed from the oxidation of toluene, naphthalene, α-pinene, and isoprene. C4–C9 dicarboxylic acids present in SOA were analyzed by offline derivatization gas chromatography–mass spectrometry. We revealed that C4 dicarboxylic acids including succinic acid, maleic acid, fumaric acid, malic acid, DL-tartaric acid, and meso-tartaric acid are produced by the photooxidation of toluene. Since meso-tartaric acid barely occurs in nature, it is a potential aerosol tracer of photochemical reaction products. In SOA particles from toluene, we also detected a compound and its isomer with similar mass spectra to methyltartaric acid standard; the compound and the isomer are tentatively identified as 2,3-dihydroxypentanedioic acid isomers. The ratio of detected C4–C5 dicarboxylic acids to total toluene SOA mass had no significant dependence on the initial VOC/NOx condition. Trace levels of maleic acid and fumaric acid were detected during the photooxidation of naphthalene. Malic acid was produced from the oxidation of α-pinene and isoprene. A trace amount of succinic acid was detected in the SOA produced from the oxidation of isoprene.

Evolution of volatility and composition in sesquiterpene-mixed and &amp;lt;i&amp;gt;α&amp;lt;/i&amp;gt;-pinene secondary organic aerosol particles during isothermal evaporation

Abstract. Efforts have been spent on investigating the isothermal evaporation of α-pinene secondary organic aerosol (SOA) particles at ranges of conditions and decoupling the impacts of viscosity and volatility on evaporation. However, little is known about the evaporation behavior of SOA particles from biogenic organic compounds other than α-pinene. In this study, we investigated the isothermal evaporation behavior of the α-pinene and sesquiterpene mixture (SQTmix) SOA particles under a series of relative humidity (RH) conditions. With a set of in situ instruments, we monitored the evolution of particle size, volatility, and composition during evaporation. Our finding demonstrates that the SQTmix SOA particles evaporated slower than the α-pinene ones at any set of RH (expressed with the volume fraction remaining, VFR), which is primarily due to their lower volatility and possibly aided by higher viscosity under dry conditions. We further applied positive matrix factorization (PMF) to the thermal desorption data containing volatility and composition information. Analyzing the net change ratios (NCRs) of each PMF-resolved factor, we can quantitatively compare how each sample factor evolves with increasing evaporation time or RH. When sufficient particulate water content was present in either SOA system, the most volatile sample factor was primarily lost via evaporation, and changes in the other sample factors were mainly governed by aqueous-phase processes. The evolution of each sample factor of the SQTmix SOA particles was controlled by a single type of process, whereas for the α-pinene SOA particles it was regulated by multiple processes. As indicated by the coevolution of VFR and NCR, the effect of aqueous-phase processes could vary from one to another according to particle type, sample factors, and evaporation timescale.

Global Distribution of the Phase State and Mixing Times within Secondary Organic Aerosol Particles in the Troposphere Based on Room-Temperature Viscosity Measurements

Information on the global distributions of secondary organic aerosol (SOA) phase state and mixing times within SOA is needed to predict the impact of SOA on air quality, climate, and atmospheric chemistry; nevertheless, such information is rare. In this study, we developed parameterizations for viscosity as a function of relative humidity (RH) and temperature based on room-temperature viscosity data for simulated pine tree SOA and toluene SOA. The viscosity parameterizations were then used together with tropospheric RH and temperature fields to predict the SOA phase state and mixing times of water and organic molecules within SOA in the troposphere for 200 nm particles. Based on our results, the glassy state can often occur, and the mixing times of water can often exceed 1 h within SOA at altitudes >6 km. Furthermore, the mixing times of organic molecules within SOA can often exceed 1 h throughout most of the free troposphere (i.e., ≳1 km in altitude). In most of the planetary boundary layer (i.e., ≲1 km in altitude), the glassy state is not important, and the mixing times of water and organic molecules are less than 1 h. Our results are qualitatively consistent with the results from Shiraiwa et al. (Nat. Commun., 2017), although there are quantitative differences. Additional studies are needed to better understand the reasons for these differences.

Effect of Humidity on the Reactive Uptake of Ammonia and Dimethylamine by Nitrogen-Containing Secondary Organic Aerosol

This study investigated the uptake of ammonia (NH3) by secondary organic aerosol (SOA) particles generated via limonene photooxidation or ozonolysis as well as the uptake of dimethylamine (DMA) by limonene ozonolysis, α-cedrene photooxidation, or toluene photooxidation SOA in an environmental chamber between 0–50% relative humidity. In addition to the acid-base equilibrium uptake, NH3 and DMA can react with SOA carbonyl compounds converting them into nitrogen-containing organic compounds (NOCs). The effective reactive uptake coefficients for the formation of NOCs from ammonia were measured on the order of 10−5. The observed DMA reactive uptake coefficients ranged from 10−5 to 10−4. Typically, the reactive uptake coefficient decreased with increasing relative humidity. This is consistent with NOC formation by a condensation reaction between NH3 or DMA with SOA, which produces water as a product. Ammonia is more abundant in the atmosphere than amines. However, the larger observed reactive uptake coefficient suggests that amine uptake may also be a potential source of organic nitrogen in particulate matter.