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The particle phase state is crucial for reactive gas uptake, heterogeneous, and multiphase chemical reactions, thereby impacting secondary aerosol formation. This study provides valuable insights into the significance of particle-phase transition and aerosol liquid water (ALW) in particle mass growth during winter. Our findings reveal that particles predominantly exist in a semi-solid or solid state during clean winter days with ambient relative humidity (RH) below 30 %. However, a non-liquid to liquid phase transition occurs when the ALW mass fraction exceeds 15 % (dry mass) at transition RH thresholds of 40 %–60 %. During haze episodes, the transformation rates of sulfate and nitrate aerosols rapidly increase through phase transition and increased ALW by 48 % and 11 %, respectively, resulting in noticeable increases in secondary inorganic aerosols (SIA). The presence of abundant ALW, favored by elevated RH and higher proportion of SIA, facilitates the partitioning of water-soluble compounds from the gas to the particle phase, as well as heterogeneous and aqueous processes in liquid particles. This leads to a substantial increase in the formation of secondary organic aerosols and elevated aerosol oxidation. Consequently, the overall hygroscopicity parameters exhibit a substantial enhancement, with a mean value of 23 %. These results highlight phase transition as a key factor initiating the positive feedback loops between ALW and secondary aerosol formation during haze episodes over the North China Plain. Accurate predictions of secondary aerosol formation necessitate explicit consideration of the particle phase state in chemical transport models. [ABSTRACT FROM AUTHOR]

Simple Summary: This study examined the levels of certain pollutants, primarily ammonia and particulate matter (PM), emitted by a commercial pig farm in Korea. Understanding these levels is vital for reducing the environmental impact of pig farming and ensuring a sustainable future for this industry. Interestingly, the study found that previous guidelines in Korea might have overestimated these pollution levels, although the current findings are consistent with global research. Seasonal variations also impacted pollution levels: more ammonia was released in spring and autumn, while other pollutants increased in summer. Factors such as the number and age of the pigs significantly influenced these emission levels, as did airflow and ventilation. In essence, continued research in this area will help to improve pig farming practices in Korea, ensuring a balance between successful farming and environmental preservation. Quantifying emission factors of ammonia and particulate matter (PM) in livestock production systems is crucial for assessing and mitigating the environmental impact of animal production and for ensuring industry sustainability. This study aimed to determine emission factors of ammonia, total suspended particles (TSPs), PM10, and PM2.5 for piglets and growing–finishing pigs at a commercial pig farm in Korea. It also sought to identify factors influencing these emission factors. The research found that the emission factors measured were generally lower than those currently used in Korea, but were consistent with findings from individual research studies in the literature. Seasonal variations were observed, with ammonia emissions peaking in spring and autumn, and PM emissions rising in summer. Correlation analyses indicated that the number of animals and their average age correlated positively with both ammonia and PM emission factors. Ventilation rate was also positively correlated with PM emissions. Future extended field measurements across diverse pig farms will offer deeper insights into the emission factors of pig farms in Korea, guiding the development of sustainable livestock management practices. [ABSTRACT FROM AUTHOR]

The particle-phase state is crucial for reactive gas uptake, heterogeneous, and multiphase chemical reactions, thereby impacting secondary aerosol formation. This study provides valuable insights into the significance of particle-phase transition and aerosol liquid water (ALW) in winter particulate growth. Our findings reveal that particles predominantly exist as semi-solid or solid during clean winter days with ambient relative humidity (RH) below 30 %. However, non-liquid to liquid phase transition occurs when the ALW mass fraction exceeds 15 % (dry mass) at transition RH thresholds of 40–60 %. During haze episodes, the transformation rates of sulfate and nitrate aerosols rapidly increase through phase transition and increased ALW by 48 % and 11 %, respectively, resulting in noticeable increases in secondary inorganic aerosols (SIA). The presence of abundant ALW, favored by elevated RH and higher proportion of SIA, facilitates heterogeneous and aqueous processes in liquid particles, leading to a substantial increase in the formation of secondary organic aerosols and elevated aerosol oxidation. Consequently, the overall hygroscopicity parameters exhibit a substantial enhancement with a mean value of 23 %. These results highlight phase transition as a key factor initiating the positive feedback loops between ALW and secondary aerosol formation during haze episodes over the North China Plain. Accurate predictions of secondary aerosol formation necessitate explicit consideration of the particle-phase state in chemical transport models. [ABSTRACT FROM AUTHOR]

PM2.5-bound trace elements were chosen for health risk assessment because they have been linked to an increased risk of respiratory and cardiovascular illness. Since the Korean national air quality standard for ambient particulate matter is based on PM2.5 mass concentration, there have only been a few measurements of PM2.5 particles together with trace elements that can be utilized to evaluate their effects on air quality and human health. Thus, this study describes the trace elements bound to PM2.5 in Seoul (urban area) and Seosan (rural area) using online nondestructive energy-dispersive X-ray fluorescence analysis from December 2020 to January 2021. At both the Seoul and Seosan sites, S, K, Si, Ca, and Fe constituted most of the PM2.5-bound trace elements (~95%); major components such as S, K, and soil (estimatedcalculatedcalculated based on oxides of Si, Fe, Ca, and Ti) were presumably from anthropogenic and crustal sources, as well as favorable meteorological conditions. During winter, synoptic meteorology favored the transport of particles from severely contaminated regions, such as the East Asian outflow and local emissions. The total dry deposition flux for crustal elements was 894.5 ± 320.8 µg m−2 d−1 in Seoul and 1088.8 ± 302.4 µg m−2 d−1 in Seosan. Moreover, potential health risks from the trace elements were estimated. Cancer risk values for carcinogenic trace elements (Cr, As, Ni, and Pb) were within the tolerable limit (1 × 10−6), suggesting that adults and children were not at risk of cancer throughout the study period in Seoul and Seosan. Furthermore, a potential risk assessment of human exposure to remaining carcinogens (Cr, As, Ni, and Pb) and non-carcinogens (Cu, Fe, Zn, V, Mn, and Se) indicated that these trace elements posed no health risks. Nevertheless, trace element monitoring, risk assessment, and mitigation must be strengthened throughout the study area to confirm that trace-element-related health effects remain harmless. Researchers and policymakers can use the database from this study on spatial and temporal variation to establish actions and plans in the future. [ABSTRACT FROM AUTHOR]

Although knowledge of the physical state of aerosol particles is essential to understand atmospheric chemistry model and measurements, information on the viscosity and physical state of aerosol particles consisting of organic and inorganic salts is still rare. Herein, we quantified viscosities at 293 ± 1 K upon dehydration for the binary systems, sucrose– H2O and ammonium sulfate (AS)– H2O , and the ternary systems, sucrose– AS – H2O for organic-to-inorganic dry mass ratios (OIRs) = 4:1 , 1:1 , and 1:4 using bead-mobility and poke-and-flow techniques. Based on the viscosity value of the aerosol particles, we defined the physical states of the total aerosol particles studied in this work. For binary systems, the viscosity of sucrose– H2O particles gradually increased from ∼ 4 × 10 -1 to > ∼ 1 × 10 8 Pas when the relative humidity (RH) decreased from ∼ 81 % to ∼ 24 %, ranging from liquid to semisolid or solid state, which agrees with previous studies. The viscosity of AS – H2O particles remained in the liquid state (< 10 2 Pas) for RH > ∼ 50 %, while for RH ≤∼ 50 %, the particles showed a viscosity of > ∼ 1 × 10 12 Pas , corresponding to a solid state. In case of the ternary systems, the viscosity of organic-rich particles (OIR = 4:1) gradually increased from ∼ 1 × 10 -1 to ∼ 1 × 10 8 Pas for a RH decrease from ∼ 81 % to ∼ 18 %, similar to the binary sucrose– H2O particles. This indicates that the sucrose– AS – H2O particles range from liquid to semisolid or solid across the RH. In the ternary particles for OIR = 1:1 , the viscosities ranged from less than ∼ 1 × 10 2 for RH > 34 % to > ∼ 1 × 10 8 Pas at ∼ 27 %RH. The viscosities correspond to liquid for RH > ∼ 34 %, semisolid for ∼ 34 % < RH < ∼ 27 %, and semisolid or solid for RH < ∼ 27 %. Compared to the organic-rich particles, in the inorganic-rich particles (OIR = 1:4), drastic enhancement in viscosity was observed as RH decreased; the viscosity increased by approximately 8 orders of magnitude during a decrease in RH from 43 % to 25 %, resulting in liquid to semisolid or solid in the RH range. Overall, all particles studied in this work were observed to exist as a liquid, semisolid, or solid depending on the RH. Furthermore, we compared the measured viscosities of ternary systems with OIRs of 4:1 , 1:1 , and 1:4 to the predicted viscosities using the Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients Viscosity model (AIOMFAC-VISC) predictions with the Zdanovskii–Stokes–Robinson (ZSR) organic–inorganic mixing model, with excellent model–measurement agreement for all OIRs. [ABSTRACT FROM AUTHOR]

Research on the viscosity and phase state of aerosol particles is essential because of their significant influence on the particle growth rate, equilibration times, and related evolution of mass concentration as well as heterogeneous reactions. So far, most studies of viscosity and phase state have been focused on organic aerosol particles, yet data on how viscosity can vary when the organic materials are mixed with inorganic salts remain scarce. Herein, using bead-mobility and poke-and-flow techniques, we quantified viscosities at 293 ± 1 K for binary mixtures of organic material / H2O and inorganic salts / H2O , as well as ternary mixtures of organic material / inorganic salts / H2O over the atmospheric relative humidity (RH) range. Sucrose as the organic species and calcium nitrate (Ca(NO3)2) or magnesium nitrate (Mg(NO3)2) as the inorganic salts were examined. For binary sucrose / H2O particles, the viscosities gradually increased from ∼ 3 × 10 -2 to ≳ 1 × 10 8 Pas as RH decreased from ∼ 75 % to ∼ 25 %. Compared with the results for the sucrose / H2O particles, binary Ca(NO3)2/H2O and Mg(NO3)2/H2O particles showed drastic enhancements to ≳ 1 × 10 8 Pas at low RH close to the efflorescence RH. For ternary mixtures of sucrose / Ca(NO3)2 / H2O or sucrose / Mg(NO3)2 / H2O , with organic-to-inorganic mass ratios of 1:1 , the viscosities of the particles gradually increased from ∼ 3 × 10 -2 to greater than ∼ 1 × 10 8 Pas for RH values from ∼ 75 % to ∼ 5 %. Compared to the viscosities of the Ca(NO3)2/H2O particles, higher viscosities were observed for the ternary sucrose / Ca(NO3)2 / H2O particles, with values increased by about 1 order of magnitude at 50 % RH and about 6 orders of magnitude at 35 % RH. Moreover, we applied a thermodynamics-based group-contribution model (AIOMFAC-VISC, Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients Viscosity) to predict aerosol viscosities for the studied systems. The model predictions and viscosity measurements show good agreement within ∼ 1 order of magnitude in viscosity. The viscosity measurements indicate that the studied mixed organic–inorganic particles range in phase state from liquid to semi-solid or even solid across the atmospheric RH range at a temperature of 293 K. These results support our understanding that organic / inorganic / H2O particles can exist in a liquid, semisolid, or even a solid state in the troposphere. [ABSTRACT FROM AUTHOR]

Organic compounds residing near the surface of atmospheric aerosol particles are exposed to chemical reactions initiated by gas-phase oxidants, such as hydroxyl (OH) radicals. Aqueous droplets composed of inorganic salts and organic compounds can undergo phase separation into two liquid phases, depending on aerosol composition and relative humidity (RH). Such phase behavior can govern the surface characteristics and morphology of the aerosols, which in turn affect the heterogeneous reactivity of organic compounds toward gas-phase oxidants. In this work, we used an aerosol flow tube reactor coupled with an atmospheric pressure ionization source (direct analysis in real time) and a high-resolution mass spectrometer to investigate how phase separation in model aqueous droplets containing an inorganic salt (ammonium sulfate, AS) and an organic acid (3-methylglutaric acid, 3-MGA) with an organic-to-inorganic dry mass ratio (OIR) of 1 alters the heterogeneous OH reactivity. At high RH, 3-MGA/AS aerosols were aqueous droplets with a single liquid phase. When the RH decreased, aqueous 3-MGA/AS droplets underwent phase separation at ∼75 % RH. Once the droplets were phase-separated, they exhibited either a core–shell, partially engulfed or a transition from core–shell to partially engulfed structure, with an organic-rich outer phase and an inorganic-rich inner phase. The kinetics, quantified by an effective heterogenous OH rate constant, was found to increase gradually from 1.01±0.02×10-12 to 1.73±0.02×10-12 cm 3 molec. -1 s -1 when the RH decreased from 88 % to 55 %. The heterogeneous reactivity of phase-separated droplets is slightly higher than that of aqueous droplets with a single liquid phase. This could be explained by the finding that when the RH decreases, higher concentrations of organic molecules (i.e., 3-MGA) are present at or near the droplet surface, which are more readily exposed to OH oxidation, as demonstrated by phase separation measurements and model simulations. This could increase the reactive collision probability between 3-MGA molecules and OH radicals dissolved near the droplet surface and secondary chain reactions. Even for phase-separated droplets with a fully established core–shell structure, the diffusion rate of organic molecules across the organic-rich outer shell is predicted to be fast in this system. Thus, the overall rate of reactions is likely governed by the surface concentration of 3-MGA rather than a diffusion limitation. Overall, understanding the aerosol phase state (single liquid phase versus two separate liquid phases) is essential to better probe the heterogenous reactivity under different aerosol chemical composition and environmental conditions (e.g., RH). [ABSTRACT FROM AUTHOR]

Liquid–liquid phase separation (LLPS) in organic aerosol particles can impact several properties of atmospheric particulate matter, such as cloud condensation nuclei (CCN) properties, optical properties, and gas-to-particle partitioning. Yet, our understanding of LLPS in organic aerosols is far from complete. Here, we report on the LLPS of one-component and two-component organic particles consisting of α -pinene- and β -caryophyllene-derived ozonolysis products and commercially available organic compounds of relevance to atmospheric organic particles. In the experiments involving single-component organic particles, LLPS was observed in 8 out of 11 particle types studied. LLPS almost always occurred when the oxygen-to-carbon elemental ratio (O:C) was ≤0.44 but did not occur when O:C was >0.44. The phase separation occurred by spinodal decomposition as well as the nucleation and growth mechanism, and when LLPS occurred, two liquid phases coexisted up to ∼100 % relative humidity (RH). In the experiments involving two-component organic particles, LLPS was observed in 23 out of 25 particles types studied. LLPS almost always occurred when the average was O:C ≤0.67 but never occurred when the average O:C was >0.67. The phase separation occurred by spinodal decomposition as well as the nucleation and growth mechanism. When LLPS occurred, two liquid phases coexisted up to ∼100 % RH. These results provide further evidence that LLPS is likely a frequent occurrence in organic aerosol particles in the troposphere, even in the absence of inorganic salts. [ABSTRACT FROM AUTHOR]

Organic compounds residing near the surface of atmospheric aerosol particles are exposed to chemical reactions initiated by gas-phase oxidants, such as hydroxyl (OH) radicals. Aqueous droplets composed of inorganic salts and organic compounds can undergo phase separation into two liquid phases, depending on aerosol composition and relative humidity (RH). Such phase behavior can govern the surface characteristics and morphology of the aerosols, which in turn affect the heterogeneous reactivity of organic compounds toward gas-phase oxidants. In this work, we used an aerosol flow tube reactor coupled with an atmospheric pressure ionization source (Direct Analysis in Real Time) and a high-resolution mass spectrometer to investigate how phase separation in model aqueous droplets containing an inorganic salt (ammonium sulfate, AS) and an organic acid (3-methyglutaric acid, 3-MGA) with an organicto- inorganic dry mass ratio (OIR) of 1 alters the heterogeneous OH reactivity. At high RH, 3- MGA/AS aerosols were aqueous droplets with a single liquid phase. When the RH decreased, aqueous 3-MGA/AS droplets underwent phase separation at ~75% RH. Once the droplets were phase-separated, they exhibited either a core-shell, partially engulfed, 35 or a transition from core-shell to partially engulfed structure, with an organic-rich outer phase and an inorganicrich inner phase. The kinetics, quantified by an effective heterogenous OH rate constant, was found to increase gradually from 1.01 ± 0.02 × 10-12 to 1.73 ± 0.02 × 10-12 cm3 molecule-1 s-1 when the RH decreased from 88% to 55%. The heterogeneous reactivity of phase-separated droplets is slightly higher than that of aqueous droplets with a single liquid phase. This could be explained by the finding that when the RH decreases, higher concentrations of organic molecules (i.e. 3-MGA) are present at or near the droplet surface, which are more readily exposed to OH oxidation, as demonstrated by phase separation measurements and model simulations. This could increase the reactive collision probability between 3-MGA molecules and OH radicals dissolved near the droplet surface and secondary chain reactions. Even for phase-separated droplets with a fully established core-shell structure, the diffusion rate of organic molecules across the organic-rich outer shell is predicted to be fast in this system. Thus, the overall rate of reactions is likely governed by the surface concentration of 3-MGA rather than a diffusion limitation. Overall, understanding the aerosol phase state (single liquid phase versus two separate liquid phases) is essential to better probe the heterogenous reactivity under different aerosol chemical composition and environmental conditions (e.g. RH). [ABSTRACT FROM AUTHOR]

The 2-methyltetrols have been widely chosen as chemical tracers for isoprene-derived secondary organic aerosols. While they are often assumed to be relatively unreactive, a laboratory study reported that pure erythritol particles (an analog of 2-methyltetrols) can be heterogeneously oxidized by gas-phase OH radicals at a significant rate. This might question the efficacy of these compounds as tracers in aerosol source-apportionment studies. Additional uncertainty could arise as organic compounds and inorganic salts often coexist in atmospheric particles. To gain more insights into the chemical stability of 2-methyltetrols in atmospheric particles, this study investigates the heterogeneous OH oxidation of pure erythritol particles and particles containing erythritol and ammonium sulfate (AS) at different dry inorganic-to-organic mass ratios (IOR) in an aerosol flow tube reactor at a high relative humidity of 85 %. The same reaction products are formed upon heterogenous OH oxidation of erythritol and erythritol–AS particles, suggesting that the reaction pathways are not strongly affected by the presence and amount of AS. On the other hand, the effective OH uptake coefficient, γeff , is found to decrease by about a factor of ∼20 from 0.45±0.025 to 0.02±0.001 when the relative abundance of AS increases and the IOR increases from 0.0 to 5.0. One likely explanation is the presence of dissolved ions slows down the reaction rates by decreasing the surface concentration of erythritol and reducing the frequency of collision between erythritol and gas-phase OH radicals at the particle surface. Hence, the heterogeneous OH reactivity of erythritol and likely 2-methyltetrols in atmospheric particles would be slower than previously thought when the salts are present. Given 2-methyltetrols often coexist with a significant amount of AS in many environments, where ambient IOR can vary from ∼1.89 to ∼250 , our kinetic data would suggest that 2-methyltetrols in atmospheric particles are likely chemically stable against heterogeneous OH oxidation under humid conditions. [ABSTRACT FROM AUTHOR]

Information on liquid–liquid phase separation (LLPS) and viscosity (or diffusion) within secondary organic aerosol (SOA) is needed to improve predictions of particle size, mass, reactivity, and cloud nucleating properties in the atmosphere. Here we report on LLPS and viscosities within SOA generated by the photooxidation of diesel fuel vapors. Diesel fuel contains a wide range of volatile organic compounds, and SOA generated by the photooxidation of diesel fuel vapors may be a good proxy for SOA from anthropogenic emissions. In our experiments, LLPS occurred over the relative humidity (RH) range of ∼70 % to ∼100 %, resulting in an organic-rich outer phase and a water-rich inner phase. These results may have implications for predicting the cloud nucleating properties of anthropogenic SOA since the presence of an organic-rich outer phase at high-RH values can lower the supersaturation with respect to water required for cloud droplet formation. At ≤10 % RH, the viscosity was ≥1×108 Pa s, which corresponds to roughly the viscosity of tar pitch. At 38 %–50 % RH, the viscosity was in the range of 1×108 to 3×105 Pa s. These measured viscosities are consistent with predictions based on oxygen to carbon elemental ratio (O:C) and molar mass as well as predictions based on the number of carbon, hydrogen, and oxygen atoms. Based on the measured viscosities and the Stokes–Einstein relation, at ≤10 % RH diffusion coefficients of organics within diesel fuel SOA is ≤5.4×10-17 cm 2 s -1 and the mixing time of organics within 200 nm diesel fuel SOA particles (τmixing) is 50 h. These small diffusion coefficients and large mixing times may be important in laboratory experiments, where SOA is often generated and studied using low-RH conditions and on timescales of minutes to hours. At 38 %–50 % RH, the calculated organic diffusion coefficients are in the range of 5.4×10-17 to 1.8×10-13 cm 2 s -1 and calculated τmixing values are in the range of ∼0.01 h to ∼50 h. These values provide important constraints for the physicochemical properties of anthropogenic SOA. [ABSTRACT FROM AUTHOR]

Atmospheric particles, consisting of inorganic salts, organic compounds and a varying amount of water, can continuously undergo heterogeneous oxidation initiated by gas-phase oxidants at the particle surface, changing the composition and properties of particles over time. To date, most studies focus on the chemical evolution of pure organic particles upon oxidation. To gain more fundamental insights into the effects of inorganic salts on the heterogeneous kinetics and chemistry of organic compounds, we investigate the heterogeneous OH oxidation of 3-methylglutaric acid (3-MGA) particles and particles containing both 3-MGA and ammonium sulfate (AS) in an organic-to-inorganic mass ratio of 2 in an aerosol flow tube reactor at a high relative humidity of 85.0 %. The molecular information of the particles before and after OH oxidation is obtained using the direct analysis in real time (DART), a soft atmospheric pressure ionization source coupled to a high-resolution mass spectrometer. Optical microscopy measurements reveal that 3-MGA–AS particles are in a single liquid phase prior to oxidation at high relative humidity. Particle mass spectra show that C6 hydroxyl and C6 ketone functionalization products are the major products formed upon OH oxidation in the absence and presence of AS, suggesting that the dissolved salt does not significantly affect reaction pathways. The dominance of C6 hydroxyl products over C6 ketone products could be explained by the intermolecular hydrogen abstraction by tertiary alkoxy radicals formed at the methyl-substituted tertiary carbon site. On the other hand, kinetic measurements show that the effective OH uptake coefficient, γeff , for 3-MGA–AS particles (0.99±0.05) is smaller than that for 3-MGA particles (2.41±0.13) by about a factor of ∼2.4. A smaller reactivity observed in 3-MGA–AS particles might be attributed to a higher surface concentration of water molecules and the presence of ammonium and sulfate ions, which are chemically inert to OH radicals, at the particle surface. This could lower the collision probability between the 3-MGA and OH radicals, resulting in a smaller overall reaction rate. Our results suggest that inorganic salts likely alter the overall heterogeneous reactivity of organic compounds with gas-phase OH radicals rather than reaction mechanisms in well-mixed aqueous organic–inorganic droplets at a high humidity, i.e., 85 % relative humidity (RH). It also acknowledges that the effects of inorganic salts on the heterogeneous reactivity could vary greatly, depending on the particle composition and environmental conditions (e.g., RH and temperature). For instance, at lower relative humidities, aqueous 3-MGA–AS droplets likely become more concentrated and more viscous before efflorescence, possibly giving rise to diffusion limitation during oxidation under relatively dry or cold conditions. Further studies on the effects of inorganic salts on the diffusivity of the species under different relative humidities within the organic–inorganic particles are also desirable to better understand the role of inorganic salts in the heterogeneous reactivity of organic compounds. [ABSTRACT FROM AUTHOR]

Recently, liquid–liquid phase separation (LLPS) of secondary organic aerosol (SOA) particles free of inorganic salts has been intensively studied due to the importance of cloud condensation nuclei (CCN) properties. In this study, we investigated LLPS in four different types of SOA particles generated from α -pinene ozonolysis and α -pinene photooxidation in the absence and presence of ammonia (NH3). LLPS was observed in SOA particles produced from α -pinene ozonolysis at ∼95.8 % relative humidity (RH) and α -pinene ozonolysis with NH3 at ∼95.4 % RH. However, LLPS was not observed in SOA particles produced from α -pinene photooxidation and α -pinene photooxidation with NH3. Based on datasets of the average oxygen to carbon elemental ratio (O:C) for different types of SOA particles from this study and from previous studies, there appears to be a relationship between the occurrence of LLPS and the O:C of the SOA particles. When LLPS was observed, the two liquid phases were present up to ∼100 % RH. This result can help more accurately predict the CCN properties of organic aerosol particles. [ABSTRACT FROM AUTHOR]

Information on liquid-liquid phase separation (LLPS) and viscosity (or diffusion) within secondary organic aerosol (SOA) is needed to improve predictions of particle size, mass, reactivity, and cloud nucleating properties in the atmosphere. Here we report on LLPS and viscosities within SOA generated by the photooxidation of diesel fuel vapors. Diesel fuel contains a wide range of volatile organic compounds, and SOA generated by the photooxidation of diesel fuel vapors may be a good proxy for SOA from anthropogenic emissions. In our experiments, LLPS occurred over the relative humidity (RH) range of ~70% to ~100%, resulting in an organic-rich outer phase and a water-rich inner phase. These results may have implications for predicting the cloud nucleating properties of anthropogenic SOA since the organic-rich outer phase can lower the kinetic barrier for activation to a cloud droplet. At ≤10% RH, the viscosity was in the range of ≥1×108Pas, which corresponds to roughly the viscosity of tar pitch. At 38-50% RH the viscosity was in the range of 1×108-3×105Pas. These measured viscosities are consistent with predictions based on oxygen to carbon elemental ratio (O:C) and molar mass as well as predictions based on the number of carbon, hydrogen, and oxygen atoms. Based on the measured viscosities and the Stokes-Einstein relation, at ≤10% RH diffusion coefficients of organics within diesel fuel SOA is ≤5.4×10-17cm²s-1 and the mixing time of organics within 200nm diesel fuel SOA particles (τmixing) is ⪆50h. These small diffusion coefficients and large mixing times may be important in laboratory experiments, where SOA is often generated and studied using low RH conditions and on time scales of minutes to hours. At 38-50% RH, the calculated organic diffusion coefficients are in the range of 5.4×10-17 to 1.8×10-13cm²s-1 and calculated τmixing values are in the range of ~0.01h to ~50h. These values provide important constraints for the physicochemical properties of anthropogenic SOA. [ABSTRACT FROM AUTHOR]

Recently, experimental studies have shown that liquid-liquid phase separation (LLPS) can occur in organic particles free of inorganic salts. Most of these studies used organic particles consisting of secondary organic materials generated in environmental chambers. To gain additional insight into LLPS in organic particles free of inorganic salts, we studied LLPS in organic particles consisting of one and two commercially available organic species. For particles containing one organic species, three out of the six particle types investigated underwent LLPS. In these cases, LLPS was observed when the O:C was ≤ 0:44 (but not always) and the relative humidity (RH) was between ~ 97% and ~ 100%. The mechanism of phase separation was likely nucleation and growth. For particles containing two organic species, 13 out of the 15 particle types investigated underwent LLPS. In these cases, LLPS was observed when the O:C was ≤ 0:58 (but not always) and mostly when the RH was between ~ 90% RH and ~ 100% RH. The mechanism of phase separation was likely spinodal decomposition. In almost all cases when LLPS was observed (for both onecomponent and two-component particles), the highest RH at which two liquids was observed was 100±2:0%, which has important implications for the cloud condensation nuclei (CCN) properties of these particles. These combined results provide additional evidence that LLPS needs to be considered when predicting the CCN properties of organic particles in the atmosphere. [ABSTRACT FROM AUTHOR]

This work explores the effect of environmental conditions on the photodegradation rates of atmospherically relevant, photolabile, organic molecules embedded in a film of secondary organic material (SOM). Three types of SOM were studied: α-pinene/O3 SOM (PSOM), limonene/O3 SOM (LSOM), and aged limonene/O3 obtained by exposure of LSOM to ammonia (brown LSOM). PSOM and LSOM were impregnated with 2,4-dinitrophenol (2,4-DNP), an atmospherically relevant molecule that photodegrades faster than either PSOM or LSOM alone, to serve as a probe of SOM matrix effects on photochemistry. Brown LSOM contains an unidentified chromophore that absorbs strongly at 510 nm and photobleaches upon irradiation. This chromophore served as a probe molecule for the brown LSOM experiments. In all experiments, either the temperature or relative humidity (RH) surrounding the SOM films was varied. The extent of photochemical reaction in the samples was monitored using UV-vis absorption spectroscopy. For all three model systems examined, the observed photodegradation rates were slower at lower temperatures and lower RH, conditions that make SOM more viscous. Additionally, the activation energies for photodegradation of each system were positively correlated with the viscosity of the SOM matrix as measured in poke-flow experiments. These activation energies were calculated to be 50, 24, and 17 kJ mol−1 for 2,4-DNP in PSOM, 2,4-DNP in LSOM, and the chromophore in brown LSOM, respectively, and PSOM was found to be the most viscous of the three. These results suggest that the increased viscosity is hindering the motion of the molecules in SOM and is slowing down their respective photochemical reactions. [ABSTRACT FROM AUTHOR]

Laboratory studies of liquid–liquid phase separation in particles containing organic species and inorganic salts of atmospheric relevance are reviewed. The oxygen-to-carbon elemental ratio (O:C) of the organic component appears to be the most useful parameter for estimating, to a first approximation, the occurrence of liquid–liquid phase separation and the separation relative humidity (SRH) in these particles. A trend of decreasing SRH for increasing O:C was found for simple organic–inorganic mixtures (<11 species). Phase separation in particles composed of laboratory-produced secondary organic material and sulphate species and in ambient particles is generally consistent with this trend. A further constraint is that liquid–liquid phase separation was always observed for O:C < 0.5 and was never observed for O:C ≥ 0.8. For organic materials of intermediate O:C ranging from 0.5 to 0.8, phase separation in simple organic–inorganic mixtures was influenced by the organic functional groups represented. The organic-to-inorganic mass ratio (OIR) affected the occurrence of liquid–liquid phase separation in a small number of cases. A dependence on salt type was observed with 87% of the studied organics exhibiting the following trend in SRH values: (NH4)2SO4 ≥ NH4HSO4 ≥ NaCl ≥ NH4NO3, consistent with previous salting-out studies and the Hofmeister series. Liquid–liquid phase separation does not appear to be strongly influenced by the number of species making up the organic material. The morphology of phase separated particles appears to depend on composition, including O:C of the organic material, the inorganic salt and the OIR. [ABSTRACT FROM PUBLISHER]

Despite major progress in the understanding of properties of tropospheric aerosol particles, it remains challenging to understand their physical state and morphology. To obtain more detailed knowledge of the phases, phase transitions and morphologies of internally mixed organic/inorganic aerosol particles, we evaluated liquid–liquid phase separation (LLPS), deliquescence relative humidity (DRH) and efflorescence relative humidity (ERH) of 33 organic/ammonium sulfate (AS)/H2O systems from our own and literature data. The organic fraction consists of single compounds or mixtures with up to ten aliphatic and/or aromatic components with carboxylic acid, hydroxyl, carbonyl, ether, and ester functionalities, covering O : C ratios between 0.29 and 1.33. Thirteen out of these 33 systems did not show LLPS for any of the studied organic-to-inorganic mixing ratios, sixteen underwent LLPS showing core–shell morphology, and four showed both core–shell and partially engulfed configurations depending on the organic-to-inorganic ratio and RH. In all cases the organic fractions of the systems with partially engulfed configurations consisted of dicarboxylic acids. AS in mixed organic/AS/H2O particles deliquesced between 70 and 84% RH. AS effloresced below 58% RH or remained in a one-liquid-phase state. AS in droplets with LLPS always showed efflorescence with ERH between 30 and 50% RH, providing clear evidence that the presence of LLPS facilitates AS efflorescence. Spreading coefficients of the organic-rich phase on the AS-rich phase for systems containing polyethylene glycol 400 (PEG-400) and a mixture of dicarboxylic acids are in agreement with the optically observed morphologies of droplets deposited on the hydrophobic substrate. Analysis of high resolution elastic Mie resonance spectra allowed the detection of LLPS for single levitated droplets consisting of PEG-400/AS/H2O, whereas LLPS was difficult to detect in (2-methylglutaric acid + 3-methylglutaric acid + 2,2-dimethylsuccinic acid)/AS/H2O. Measured Mie spectra of PEG-400/AS/H2O at 93.5% and at 80.9% RH agreed with computed Mie spectra for a homogeneous and a core–shell configuration, respectively, confirming the results obtained from droplets deposited on a hydrophobic substrate. Based on the presented evidence, we therefore consider the core–shell morphology to be the prevalent configuration of liquid–liquid-phase-separated tropospheric organic/AS/H2O particles. [ABSTRACT FROM AUTHOR]

Atmospheric ammonia (NH3) plays a critical role in PM2.5 pollution. Data on atmospheric NH3 are scanty; thus, the role of NH3 in the formation of ammonium ions (NH4+) in various environments is understudied. Herein, we measured concentrations of NH3, PM2.5, and its water-soluble SO42−, NO3−, and NH4+ ions (SNA) at an urban site in Jeonju, South Korea from May 2019 to April 2020. During the measurement period, the average concentrations of NH3 and PM2.5 were 10.5 ± 4.8 ppb and 24.0 ± 12.8 μg/m3, respectively, and SNA amounted to 4.3 ± 3.1, 4.4 ± 4.9, and 1.6 ± 1.8 μg/m3, respectively. A three-dimensional photochemical model analysis revealed that a major portion of NH3, more than 88%, originated from Korea. The enhancement of the ammonium-to-total ratio of NH3, NHX (NHR = [NH4+]/[NH4+] + [NH3]) was observed up to ~0.61 during the increase of PM2.5 concentration (PM2.5 ≥ 25 μg/m3) under low temperature and high relative humidity conditions, particularly in winter. The PM2.5 and SNA concentrations increased exponentially as NHR increased, indicating that NH3 contributed significantly to SNA formation by gas-to-particle conversion. Our study provided experimental evidence that atmospheric NH3 in the urban area significantly contributed to SNA formation through gas-to-particle conversion during PM2.5 pollution episodes. [ABSTRACT FROM AUTHOR]

Ammonia (NH3) plays an important role in air quality and atmospheric chemistry, yet studies on the characteristics and impacts of NH3 are limited. Herein, we revealed the spatial distribution of atmospheric NH3, as measured by passive samplers, at three different sites (R1, R2, and R3) in the rural area (livestock environment) of Jeongeup, South Korea, from September 2019 to August 2020. At site R1, the boundary of a large-scale pig farm, dramatically high daily mean concentrations of NH3 were observed (118.7 ppb), whereas sites R2 and R3, located ~1 km from R1, exhibited lower concentrations of 18.2 and 30.4 ppb, respectively. In the rural environment, the monthly NH3 variations showed a peak in June (34.2 ppb), which was significantly higher than in the urban and remote areas. To examine the impact of NH3 from the rural area on a nearby urban area in June 2020, simultaneous measurements were performed using a real-time instrument in Jeonju. When high NH3 events occurred in the urban area in June, the results for the NH3 concentrations and observed meteorological conditions in the rural and urban areas showed that the rural area influenced the NH3 levels in the adjacent urban area. [ABSTRACT FROM AUTHOR]

Hygroscopic growth and cloud condensation nuclei activation are key processes for accurately modeling the climate impacts of organic particulate matter. Nevertheless, the microphysical mechanisms of these processes remain unresolved. Here we report complex thermodynamic behaviors, including humidity-dependent hygroscopicity, diameter-dependent cloud condensation nuclei activity, and liquid-liquid phase separation in the laboratory for biogenically derived secondary organic material representative of similar atmospheric organic particulate matter. These behaviors can be explained by the non-ideal mixing of water with hydrophobic and hydrophilic organic components. The non-ideality-driven liquid-liquid phase separation further enhances water uptake and induces lowered surface tension at high relative humidity, which result in a lower barrier to cloud condensation nuclei activation. By comparison, secondary organic material representing anthropogenic sources does not exhibit complex thermodynamic behavior. The combined results highlight the importance of detailed thermodynamic representations of the hygroscopicity and cloud condensation nuclei activity in models of the Earth’s climate system. The interactions between organic particulate matter and water vapour affect climate predictions, yet the mechanisms of these interactions remain unresolved. Here, the authors propose a phase separation mechanism that reconciles the observed hygroscopicity and cloud condensation nuclei activity. [ABSTRACT FROM AUTHOR]