Gas-particle Partitioning Research Articles

Research Progress of SOA Formation from Anthropogenic VOCs Under Complex Pollution Condition

Although the air quality in China has been greatly improved in recent years, the air pollution remains severe. The annual mean PM2.5 concentrations have not met the second grade of the National Ambient Air Quality Standards in China and are still much higher than the guideline value of the World Health Organization. Thus, the PM2.5 concentration needs to be further reduced. Secondary organic aerosol (SOA) is an important component of PM2.5 and has an important impact on air quality, global climate change, and human health. Therefore, understanding the formation mechanism of SOA is an important basis to control SOA and further reduce PM2.5. As an important precursor of SOA, volatile organic compounds (VOCs) can be oxidized by oxidants such as ·OH, NO3[KG-*2/3]·, Cl·, and O3 to generate low volatile organic compounds and further to form SOA through gas-particle partitioning, homogeneous nucleation, aqueous phase reaction, and heterogeneous reaction processes. The formation of SOA can be affected by many factors, such as the types and initial concentrations of VOCs, VOCs/NOx ratios, relative humidity (RH), temperature (T), seed aerosols, oxidants, aqueous phase process, and photochemical process. The observed SOA concentration is always underestimated by air quality models because a comprehensive understanding of the complexity of SOA chemical composition and formation mechanisms is still lacking, especially that under the highly complex air pollution conditions in China. Therefore, the formation mechanism and influencing factors of SOA under highly complex air pollution conditions have become an important concern in the field of atmospheric sciences. Recently, much laboratory work has focused on the formation of SOA under complex conditions. The research progress of SOA formation from different anthropogenic VOCs are reviewed here, and the methods used and the impact of different influencing factors on SOA formation are introduced. Finally, the key scientific issues that exist in the research of the SOA mechanism at present are put forward, and the future research direction is projected.

Volatility distribution of primary organic aerosol emissions from household crop waste combustion in China

Biomass-burning emissions are a significant source of primary organic aerosol (POA). Volatility is one of the most important physical properties of organic aerosol (OA). Dilution and thermodenuder (TD) measurements were used to investigate the volatility of POA from household crop waste combustion in China. Between 10% and 30% of the POA desorbed when diluted from 20:1 to 120:1, while 10%–40% of POA evaporated in the TD when heated to 150 °C. Thus, a considerable proportion of the POA emissions were volatile. A dynamic mass transfer model was applied to derived volatility distributions of POA based on TD data. A best fit volatility distributions for POA and associated mass accommodation coefficients (α), and the enthalpy of vaporization (ΔHvap) were presented. The emissions factors and volatility distribution of POA emission from household crop waste combustion in this study can be used to improve emission inventories and simulate gas-particle partitioning of organic aerosol in chemical transport models.

Gas-Particle Partitioning of Semivolatile Organic Compounds in a Residence: Influence of Particles from Candles, Cooking, and Outdoors.

Semivolatile organic compounds (SVOCs) represent an important class of indoor pollutants. The partitioning of SVOCs between airborne particles and the adjacent air influences human exposure and uptake. Presently, little direct experimental evidence exists about the influence of indoor particle pollution on the gas-particle phase partitioning of indoor SVOCs. In this study, we present time-resolved gas- and particle-phase distribution data for indoor SVOCs in a normally occupied residence using semivolatile thermal desorption aerosol gas chromatography. Although SVOCs in indoor air are found mostly in the gas phase, we show that indoor particles from cooking, candle use, and outdoor particle infiltration strongly affect the gas-particle phase distribution of specific indoor SVOCs. From gas- and particle-phase measurements of SVOCs spanning a range of chemical functionalities (alkanes, alcohols, alkanoic acids, and phthalates) and volatilities (vapor pressures from 10-13 to 10-4 atm), we find that the chemical composition of the airborne particles influences the partitioning of individual SVOC species. During candle burning, the enhanced partitioning of gas-phase SVOCs to indoor particles not only affects the particle composition but also enhances surface off-gassing, thereby increasing the total airborne concentration of specific SVOCs, including diethylhexyl phthalate.

The Atmospheric Pollution Characteristics and Health Risk Assessment of Perfluorohexane Sulfonic Acid in Beijing

Perfluorohexane sulfonic acid (PFHxS), one of the substitutes for perfluorooctane sulfonic acid (PFOS), has been widely discussed around the world. In this study, the atmospheric concentrations of PFHxS in Beijing in the summer and autumn of 2021 were monitored, and the gas–particle partitioning and wet and dry deposition characteristics were analyzed. The results show that the average total concentrations of PFHxS in Beijing in the summer and autumn were 1.61 pg/m3 and 1.41 pg/m3, respectively. The particulate fraction φ of PFHxS was about 48% during the research period, and there was a significant positive correlation between φ and air temperatures. The linear fitting relationship between logKp(gas–particle partition coefficient) and logPL (compound vapor pressure) showed that the absorption between the PFHxS molecule and particulate matter dominated the process of gas–particle partitioning. The total deposition flux of PFHxS was the largest in July and the smallest in October, with values of 55.2 and 23.7 ng/m2, respectively. During the study period, PFHxS in the atmosphere had no obvious health impacts on humans. However, with their extensive use, the possible harmful effects on children should be continuously investigated.

Gas-particle partitioning and air-water exchange of polycyclic aromatic hydrocarbons in the Three Gorges Reservoir, southwest China

A 30 m vertical drawdown water level fluctuation zone (WLFZ) was formed annually due to seasonal water impoundment in the Three Gorges Reservoir (TGR) in Southwest China. In this study, a super site in downstream of WLFZ, ∼200 km off the Three Gorges Dam, was used to investigate the seasonally gas-particle partitioning and air-water exchange of USEPA 16 polycyclic aromatic hydrocarbons (16 PAHs). The average concentrations of 16 PAHs in the particle phase were 66.63 ± 9.15 ng/m3 in winter and 8.43 ± 2.95 ng/m3 in summer. In the gas phase, they were 28.47 ± 4.79 ng/m3 in winter and 10.57 ± 1.51 ng/m3 in summer. In the dissolved phase of surface water, they were 38.65 ± 6.37 ng/L in winter and 56.53 ± 8.86 ng/L in summer. The logarithmic gas-particle partitioning coefficient (lgKp) was negatively correlated with the logarithmic subcooled liquid vapor pressure (lgPL0). While the lgKp was positively correlated with logarithmic octanol-air distribution coefficient (lgKOA). These two regressions both indicated un-equilibrium of gas-particle partitioning of PAHs in the atmosphere. Applying “Whitman two-film resistance model” to our datasets shows that 3-ring PAHs had a net volatilization from water to air (2.74–6.43 ng/m2/d), and 4 ∼ 5-ring PAHs favored deposition from air to water (−0.614 to −0.413 ng/m2/d). The water as a potential ‘source’ for 3-ring and a ‘sink’ for 4 ∼ 5-ring PAHs was thereby revealed. The results of this study are crucial for understanding atmospheric gas-particle partitioning of PAHs and for revealing the factors and mechanisms governing their geochemical cycling at air and water interfaces.

Molecular Understanding of the Enhancement in Organic Aerosol Mass at High Relative Humidity.

The mechanistic pathway by which high relative humidity (RH) affects gas-particle partitioning remains poorly understood, although many studies report increased secondary organic aerosol (SOA) yields at high RH. Here, we use real-time, molecular measurements of both the gas and particle phase to provide a mechanistic understanding of the effect of RH on the partitioning of biogenic oxidized organic molecules (from α-pinene and isoprene) at low temperatures (243 and 263 K) at the CLOUD chamber at CERN. We observe increases in SOA mass of 45 and 85% with increasing RH from 10-20 to 60-80% at 243 and 263 K, respectively, and attribute it to the increased partitioning of semi-volatile compounds. At 263 K, we measure an increase of a factor 2-4 in the concentration of C10H16O2-3, while the particle-phase concentrations of low-volatility species, such as C10H16O6-8, remain almost constant. This results in a substantial shift in the chemical composition and volatility distribution toward less oxygenated and more volatile species at higher RH (e.g., at 263 K, O/C ratio = 0.55 and 0.40, at RH = 10 and 80%, respectively). By modeling particle growth using an aerosol growth model, which accounts for kinetic limitations, we can explain the enhancement in the semi-volatile fraction through the complementary effect of decreased compound activity and increased bulk-phase diffusivity. Our results highlight the importance of particle water content as a diluting agent and a plasticizer for organic aerosol growth.

Modeling the influence of chain length on secondary organic aerosol (SOA) formation via multiphase reactions of alkanes

Abstract. Secondary organic aerosol (SOA) from diesel fuel is known to be significantly sourced from the atmospheric oxidation of aliphatic hydrocarbons. In this study, the formation of linear alkane SOA was predicted using the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model that simulated multiphase reactions of hydrocarbons. In the model, the formation of oxygenated products from the photooxidation of linear alkanes was simulated using a nearly explicit gas kinetic mechanism. Autoxidation paths integrated with alkyl peroxy radicals were added to the Master Chemical Mechanism v3.3.1 to improve the prediction of low-volatility products in the gas phase and SOA mass. The resulting gas products were then lumped into volatility- and reactivity-based groups that are linked to mass-based stoichiometric coefficients. The SOA mass in the UNIPAR model is produced via three major pathways: partitioning of gaseous oxidized products onto both the organic and wet inorganic phases, oligomerization in the organic phase, and reactions in the wet inorganic phase (acid-catalyzed oligomerization and organosulfate formation). The model performance was demonstrated for SOA data that were produced through the photooxidation of a homologous series of linear alkanes ranging from C9–C15 under varying environments (NOx levels and inorganic seed conditions) in a large outdoor photochemical smog chamber. The product distributions of linear alkanes were mathematically predicted as a function of carbon number using an incremental volatility coefficient (IVC) to cover a wide range of alkane lengths. The prediction of alkane SOA using the incremental volatility-based product distributions, which were obtained with C9–C12 alkanes, was evaluated for C13 and C15 chamber data and further extrapolated to predict the SOA from longer-chain alkanes (≥ C15) that can be found in diesel. The model simulation of linear alkanes in diesel fuel suggests that SOA mass is mainly produced by alkanes C15 and higher. Alkane SOA is insignificantly impacted by the reactions of organic species in the wet inorganic phase due to the hydrophobicity of products but significantly influenced by gas–particle partitioning.

Modeling daytime and nighttime secondary organic aerosol formation via multiphase reactions of biogenic hydrocarbons

Abstract. The daytime oxidation of biogenic hydrocarbons is attributed to both OH radicals and O3, while nighttime chemistry is dominated by the reaction with O3 and NO3 radicals. Here, daytime and nighttime patterns of secondary organic aerosol (SOA) originating from biogenic hydrocarbons were predicted under varying environmental conditions (temperature, humidity, sunlight intensity, NOx levels, and seed conditions) by using the UNIfied Partitioning Aerosol phase Reaction (UNIPAR) model, which comprises multiphase gas–particle partitioning and in-particle chemistry. The products originating from the atmospheric oxidation of three different hydrocarbons (isoprene, α-pinene, and β-caryophyllene) were predicted by using extended semi-explicit mechanisms for four major oxidants (OH, O3, NO3, and O(3P)) during day and night. The resulting oxygenated products were then classified into volatility–reactivity-based lumping species. The stoichiometric coefficients associated with lumping species were dynamically constructed under varying NOx levels, and they were applied to the UNIPAR SOA model. The predictability of the model was demonstrated by simulating chamber-generated SOA data under varying environments. For daytime SOA formation, both isoprene and α-pinene were dominated by the OH-radical-initiated oxidation showing a gradual increase in SOA yields with decreasing NOx levels. The nighttime isoprene SOA formation was processed mainly by the NO3-driven oxidation, yielding higher SOA mass than daytime at higher NOx level (isoprene / NOx < 5 ppb C ppb−1). At a given amount of ozone, the oxidation to produce the nighttime α-pinene SOA gradually transited from the NO3-initiated reaction to ozonolysis as NOx levels decreased. Nighttime α-pinene SOA yields were also significantly higher than daytime SOA yields, although the nighttime α-pinene SOA yields gradually decreased with decreasing NOx levels. β-Caryophyllene, which rapidly produced SOA with high yields, showed a relatively small variation in SOA yields from changes in environmental conditions (i.e., NOx levels, seed conditions, and sunlight intensity), and its SOA formation was mainly attributed to ozonolysis day and night. The daytime SOA formation was generally more sensitive to the aqueous reactions than the nighttime SOA because the daytime chemistry produced more highly oxidized multifunctional products. The simulation of α-pinene SOA in the presence of gasoline fuel, which can compete with α-pinene for the reaction with OH radicals in typical urban air, suggested more growth of α-pinene SOA by the enhanced ozonolysis path. We concluded that the oxidation of the biogenic hydrocarbon with O3 or NO3 radicals is a source of the production of a sizable amount of nocturnal SOA, despite the low emission at night.

Size-resolved gas-particle partitioning characteristics of typical semi-volatile organic compounds in urban atmosphere

Understanding particle size distribution and size-resolved gas-particle partitioning of semi-volatile organic compounds (SVOCs) is important for characterizing their fate in atmosphere. However, the size-resolved gas-particle partitioning characteristics of SVOCs has not been adequately considered. To address this issue, the present study collected gaseous and size-fractioned particulate samples both in and outside of schools, offices, and residences in three districts of different urbanization levels in a megacity, Guangzhou, South China during two seasons. Typical SVOCs, including 15 polycyclic aromatic hydrocarbons (PAHs), six organophosphate esters and seven phthalic acid esters were measured. Emission sources, physicochemical properties, and environmental conditions at the sampling sites considerably impacted the spatiotemporal distribution patterns and particle size distribution of target SVOCs. Not all observed gas-particle partition coefficients (Kp) of target SVOCs were negatively correlated with subcooled liquid-vapor pressures (PL0), probably because certain factors, such as the non-exchangeable part of the particle-bound SVOCs, were not considered in traditional gas-particle partition theories. Particle size was an important factor affecting gas-particle partitioning. Adsorption was the dominant mechanism for PAHs with high molecular weight in different particle modes. A new model was established to predict size-resolved Kp of PAHs with high molecular weight based on PL0 and particle size.

Gas Particle Partitioning of PAHs Emissions from Typical Solid Fuel Combustions as Well as Their Health Risk Assessment in Rural Guanzhong Plain, China.

Air pollutants from the incomplete combustion of rural solid fuels are seriously harmful to both air quality and human health. To quantify the health effects of different fuel-stove combinations, gas and particle partitioning of twenty-nine species of polycyclic aromatic hydrocarbons (PAHs) emitted from seven fuel-stove combinations were examined in this study, and the benzo (a) pyrene toxicity equivalent (BaPeq) and cancer risks were estimated accordingly. The results showed that the gas phase PAHs (accounting for 68-78% of the total PAHs) had higher emission factors (EFs) than particulate ones. For all combustion combinations, pPAHs accounted for the highest proportion (84.5% to 99.3%) in both the gas and particulate phases, followed by aPAHs (0.63-14.7%), while the proportions of nPAHs and oPAHs were much lower (2-4 orders of magnitude) than pPAHs. For BaPeq, particulate phase PAHs dominated the BaPeq rather than gas ones, which may be due to the greater abundance of 5-ring particle PAHs. Gas and particle pPAHs were both predominant in the BaPeq, with proportions of 95.2-98.6% for all combustion combinations. Cancer risk results showed a descending order of bituminous coal combustion (0.003-0.05), biomass burning (0.002-0.01), and clean briquette coal combustion (10-5-0.001), indicating that local residents caused a severe health threat by solid fuel combustion (the threshold: 10-4). The results also highlighted that clean briquette coal could reduce cancer risks by 1-2 orders of magnitude compared to bulk coal and biomass. For oPAH, BcdPQ (6H-benzo(c,d)pyrene-6-one) had the highest cancer risk, ranging from 4.83 × 10-5 to 2.45 × 10-4, which were even higher than the total of aPAHs and nPAHs. The dramatically high toxicity and cancer risk of PAHs from solid fuel combustion strengthened the necessity and urgency of clean heating innovation in Guanzhong Plain and in similar places.

Organic Peroxides in Aerosol: Key Reactive Intermediates for Multiphase Processes in the Atmosphere.

Organic peroxides (POs) are organic molecules with one or more peroxide (-O-O-) functional groups. POs are commonly regarded as chemically labile termination products from gas-phase radical chemistry and therefore serve as temporary reservoirs for oxidative radicals (HOx and ROx) in the atmosphere. Owing to their ubiquity, active gas-particle partitioning behavior, and reactivity, POs are key reactive intermediates in atmospheric multiphase processes determining the life cycle (formation, growth, and aging), climate, and health impacts of aerosol. However, there remain substantial gaps in the origin, molecular diversity, and fate of POs due to their complex nature and dynamic behavior. Here, we summarize the current understanding on atmospheric POs, with a focus on their identification and quantification, state-of-the-art analytical developments, molecular-level formation mechanisms, multiphase chemical transformation pathways, as well as environmental and health impacts. We find that interactions with SO2 and transition metal ions are generally the fast PO transformation pathways in atmospheric liquid water, with lifetimes estimated to be minutes to hours, while hydrolysis is particularly important for α-substituted hydroperoxides. Meanwhile, photolysis and thermolysis are likely minor sinks for POs. These multiphase PO transformation pathways are distinctly different from their gas-phase fates, such as photolysis and reaction with OH radicals, which highlights the need to understand the multiphase partitioning of POs. By summarizing the current advances and remaining challenges for the investigation of POs, we propose future research priorities regarding their origin, fate, and impacts in the atmosphere.

Impact of phase state and non-ideal mixing on equilibration timescales of secondary organic aerosol partitioning

Abstract. Evidence has accumulated that secondary organic aerosols (SOAs) exhibit complex morphologies with multiple phases that can adopt amorphous semisolid or glassy phase states. However, experimental analysis and numerical modeling on the formation and evolution of SOA still often employ equilibrium partitioning with an ideal mixing assumption in the particle phase. Here we apply the kinetic multilayer model of gas–particle partitioning (KM-GAP) to simulate condensation of semi-volatile species into a core–shell phase-separated particle to evaluate equilibration timescales of SOA partitioning. By varying bulk diffusivity and the activity coefficient of the condensing species in the shell, we probe the complex interplay of mass transfer kinetics and the thermodynamics of partitioning. We found that the interplay of non-ideality and phase state can impact SOA partitioning kinetics significantly. The effect of non-ideality on SOA partitioning is slight for liquid particles but becomes prominent in semisolid or solid particles. If the condensing species is miscible with a low activity coefficient in the viscous shell phase, the particle can reach equilibrium with the gas phase long before the dissolution of concentration gradients in the particle bulk. For the condensation of immiscible species with a high activity coefficient in the semisolid shell, the mass concentration in the shell may become higher or overshoot its equilibrium concentration due to slow bulk diffusion through the viscous shell for excess mass to be transferred to the core phase. Equilibration timescales are shorter for the condensation of lower-volatility species into semisolid shell; as the volatility increases, re-evaporation becomes significant as desorption is faster for volatile species than bulk diffusion in a semisolid matrix, leading to an increase in equilibration timescale. We also show that the equilibration timescale is longer in an open system relative to a closed system especially for partitioning of miscible species; hence, caution should be exercised when interpreting and extrapolating closed-system chamber experimental results to atmosphere conditions. Our results provide a possible explanation for discrepancies between experimental observations of fast particle–particle mixing and predictions of long mixing timescales in viscous particles and provide useful insights into description and treatment of SOA in aerosol models.

Real-time measurement of phase partitioning of organic compounds using a proton-transfer-reaction time-of-flight mass spectrometer coupled to a CHARON inlet

Abstract. Understanding the gas–particle partitioning of semivolatile organic compounds (SVOCs) is of crucial importance in the accurate representation of the global budget of atmospheric organic aerosols. In this study, we quantified the gas- vs. particle-phase fractions of a large number of SVOCs in real time in an urban area of East China with the use of a CHemical Analysis of aeRosols ONline (CHARON) inlet coupled to a high-resolution proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS). We demonstrated the use of the CHARON inlet for highly efficient collection of particulate SVOCs while maintaining the intact molecular structures of these compounds. The collected month-long dataset with hourly resolution allows us to examine the gas–particle partitioning of a variety of SVOCs under ambient conditions. By comparing the measurements with model predictions using instantaneous equilibrium partitioning theory, we found that the dissociation of large parent molecules during the PTR ionization process likely introduces large uncertainties to the measured gas- vs. particle-phase fractions of less oxidized SVOCs, and therefore, caution should be taken when linking the molecular composition to the particle volatility when interpreting the PTR-ToF-MS data. Our analysis suggests that understanding the fragmentation mechanism of SVOCs and accounting for the neutral losses of small moieties during the molecular feature extraction from the raw PTR mass spectra could reduce, to a large extent, the uncertainties associated with the gas–particle partitioning measurement of SVOCs in the ambient atmosphere.

Exploring controls on perfluorocarboxylic acid (PFCA) gas-particle partitioning using a model with observational constraints.

The atmospheric fate of perfluorocarboxylic acids (PFCAs) has attracted much attention in recent decades due to the role of the atmosphere in global transport of these persistent chemicals. There is a gap in our understanding of gas-particle partitioning, limited by availability of reliable atmospheric measurements, partitioning properties, and models of gas-particle interactions. The gas-particle equilibrium phase partitioning of C2-C16 PFCAs in the atmosphere were modeled here by taking account of both deprotonation and phase partitioning equilibria among air, aerosol liquid water, and particulate water-insoluble organic matter using a range of available PFCA partitioning properties. We systematically varied water and organic matter content to simulate the full range of atmospheric conditions. Except in severe organic matter pollution episodes, shorter-chain PFCAs are predicted to mainly partition between air and aqueous phase, while for PFCAs with carbon chains longer than 12, organic matter is more likely to be the dominant particle phase reservoir. The model framework underestimated the particle fraction of C2-C8 PFCAs compared with several ambient observations, with larger discrepancies observed for longer-chain PFCAs. The discrepancy could result from externally mixed dust components, non-ideality of aerosol liquid water, surfactant descriptions at phase boundaries, and missed interactions between organic matter and charged PFCA molecules. Reliable measurements of ambient PFCAs with high time resolution and the measurement of uptake parameters by particle-relevant components will be beneficial to more reliable environmental fate modeling of ambient PFCAs.

PFAS on atmospheric aerosol particles: a review.

Per- and polyfluoroalkyl substances (PFAS) are persistent organic pollutants of concern to human health. These synthetic chemicals are in widespread use for consumer products, firefighting foams, and industrial applications. They have been detected all over the globe, including at remote locations distant from any possible point sources. One mechanism for long-range transport of PFAS is through sorption to aerosol particles in the atmosphere. PFAS can be transferred from the sea surface to sea spray aerosol particles through wave breaking and bubble bursting, and PFAS emitted to the atmosphere in the gas phase can sorb to particulate matter through gas-particle partitioning. Here we present a comprehensive review of global measurements of PFAS on ambient particulate matter dating back to the first reports from the early 2000s. We summarize findings for the historically important C8 species, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), including detection of isomers and size-segregated measurements, as well as studies of newer and emerging PFAS. We conclude that long-term monitoring of PFAS on particulate matter should be expanded to include more measurement sites in under-sampled regions of the world and that further non-targeted work to identify novel PFAS structures is needed as PFAS manufacturing and regulations continue to evolve.

Development of Volatility Distributions for Organic Matter in Biomass Burning Emissions.

The volatility distribution of organic emissions from biomass burning and other combustion sources can determine their atmospheric evolution due to partitioning/aging. The gap between measurements and models predicting secondary organic aerosol has been partially attributed to the absence of semi- and intermediate volatility organic compounds (S/I-VOC) in models and measurements. However, S/I-VOCs emitted from these sources and typically quantified using the volatility basis framework (VBS) are not well understood. For example, the amount and composition of S/I-VOCs and their variability across different biomass burning sources such as residential woodstoves, open field burns, and laboratory simulated open burning are uncertain. To address this, a novel filter-in-tube sorbent tube sampling method collected S/I-VOC samples from biomass burning experiments for a range of fuels and combustion conditions. Filter-in-tube samples were analyzed using thermal desorption-gas chromatography-mass spectrometry (TD/GC/MS) for compounds across a wide range of volatilities (saturation concentrations; -2 ≤ logC* ≤ 6). The S/I-VOC measurements were used to calculate volatility distributions for each emissions source. The distributions were broadly consistent across the sources with IVOCs accounting for 75% - 90% of the total captured organic matter, while SVOCs and LVOCs were responsible for 6% - 13% and 1% - 12%, respectively. The distributions and predicted partitioning were generally consistent with literature. Particulate matter emission factors spanned two orders of magnitude across the sources. This work highlights the potential of inferring gas-particle partitioning behavior of biomass burning emissions using filter-in-tube sorbent samples analyzed offline. This simplifies both sampling and analysis of S/I-VOCs for studies focused on capturing the full range of organics emitted.

Effective mass accommodation for partitioning of organic compounds into surface films with different viscosities.

Indoor surfaces can act as reservoirs and reaction media influencing the concentrations and type of species that people are exposed to indoors. Mass accommodation and partitioning are impacted by the phase state and viscosity of indoor surface films. We developed the kinetic multi-layer model KM-FILM to simulate organic film formation and growth, but it is computationally expensive to couple such comprehensive models with indoor air box models. Recently, a novel effective mass accommodation coefficient (αeff) was introduced for efficient and effective treatments of gas-particle partitioning. In this study, we extended this approach to a film geometry with αeff as a function of penetration depth into the film, partitioning coefficient, bulk diffusivity, and condensed-phase reaction rate constant. Comparisons between KM-FILM and the αeff method show excellent agreement under most conditions, but with deviations before the establishment of quasi-equilibrium within the penetration depth. We found that the deposition velocity of species and overall film growth are impacted by bulk diffusivity in highly viscous films (Db ∼<10-15 cm2 s-1). Reactions that lead to non-volatile products can increase film thicknesses significantly, with the extent of film growth being dependent on the gas-phase concentration, rate coefficient, partitioning coefficient and diffusivity. Amorphous semisolid films with Db > ∼10-17-10-19 cm2 s-1 can be efficient SVOC reservoirs for compounds with higher partitioning coefficients as they can be released back to the gas phase over extended periods of time, while glassy solid films would not be able to act as reservoirs as gas-film partitioning is impeded.

Long-range transport of atmospheric speciated mercury from the eastern waters of Taiwan Island to northern South China Sea

This study explored the temporospatial distribution, gas-particle partition, and pollution sources of atmospheric speciated mercury (ASM) from the eastern offshore waters of the Taiwan Island (TI) to the northern South China Sea (SCS). Both gaseous and particulate mercury were simultaneously sampled at three remote sites in four seasons. The average concentrations of gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM), and particulate bound mercury (PBM) were 2.05 ± 0.45 ng/m3, 19.17 ± 5.39 pg/m3, and 0.11 ± 0.06 ng/m3, respectively. The concentrations of GEM and PBM in the cold seasons were higher than those in the warm seasons, but those of GOM had an opposite trend. In terms of gas-solid partition, ASM was apportioned as 91.3–97.3% of GEM and 2.7–8.7% of GOM and PBM. The average concentrations of GEM, GOM, and PBM at the Green Island (GI) were 2.21 ± 0.47 ng/m3, 22.31 ± 5.35 pg/m3, and 0.12 ± 0.06 ng/m3; those at the Kenting Peninsula (KT) were 2.11 ± 0.43 ng/m3, 20.57 ± 4.38 pg/m3, and 0.11 ± 0.06 ng/m3; and those at the Dongsha Islands (DS) were 1.84 ± 0.40 ng/m3, 15.19 ± 3.58 pg/m3, and 0.08 ± 0.05 ng/m3, respectively. Overall, the spatial distribution of ASM concentrations showed the order as: GI > KT > DS. Air masses blown mainly from the West Pacific Ocean (WPO) and SCS in summer showed the lowest ASM concentrations. Oppositely, high ASM concentrations were commonly observed in spring and winter when polluted air masses were blown by Asian Northeastern Monsoons (ANMs). The transport routes of polluted air masses were originated mainly from North China, Central China, Northeast China, Korea and Japan, and mostly passed through the urban and industrial regions in the northeastern Asian countries.

Molecular Tracer Characterization during COVID-19 Pandemic in Shanghai: Changes in the Aerosol Aqueous Environment and Implications for Secondary Organic Aerosol Formation

The COVID-19 lockdown has opened a unique window for investigating aerosol formation and evolution with controlled anthropogenic emissions in urban areas. Here, variations of PM2.5 chemical compositions, gaseous pollutants, meteorological conditions, and secondary organic aerosol (SOA) molecular tracers were monitored during three stages at an urban site (Pudong) and a suburban site (Qingpu) in Shanghai, which were defined as pre-COVID lockdown (PL), during COVID lockdown (DL), and after COVID lockdown (AL) in 2020. Abundances of pollutants during the same periods back in 2019 were also analyzed for a more comprehensive intercomparison and evaluation of the impact of the 2020 COVID-19 lockdown on regional air quality. With the sudden cessation of anthropogenic activities during the lockdown, significant reductions in PM2.5 were observed compared to both PL in 2020 (32% in Pudong and 36% in Qingpu) and the DL period back in 2019 (31% in Pudong and 35% in Qingpu), which was accompanied by the significantly reduced PM2.5 components (29–44% and 14–44% reductions in sulfate, nitrate, ammonium, organic carbon, and elemental carbon for Pudong and Qingpu, respectively). In particular, with the reduced secondary inorganic aerosol (SIA), the time series of SOA molecular tracers also underwent significant reduction that was characteristic to the lockdown. Amid the uncontrolled biogenic emissions and even slightly enhanced atmospheric oxidation capacity during the 2020 DL period, controlling anthropogenic emissions exhibits synergistic effects on the reduction of SIA and SOA, which could be further attributed to the changes in the aerosol aqueous-phase environment, such as aerosol liquid water content (ALWC), ionic strength, sulfate content, and particulate NH4+. Based on thermodynamic modeling, greatly reduced ALWC was observed during 2020 DL, which can prevent the partitioning of oxygenated organics into the condensed phase as well as the aqueous-phase formation of SOA. Higher ionic strength in 2020 DL may have a “salting-out” effect on gas–particle partitioning of oxygenated organics. The reduced SOA during 2020 DL at both sites can generally be reflected by the predicted heterogeneous reaction kinetics (γ) of the isoprene SOA formation pathway. Overall, our study showed a synergistic effect in suppressing SIA and SOA formation upon the reduction of anthropogenic emissions during the COVID-19 lockdown, which shed light on the importance of controlling anthropogenic emissions in regulating secondary aerosol formation in typical urban areas of East China.

Steady-state model for predicting size-resolved gas-particle partitioning of semi-volatile organic compounds (SVOCs) in indoor environments

Steady-state model for predicting size-resolved gas-particle partitioning of semi-volatile organic compounds (SVOCs) in indoor environments