Fraction Of Aerosol Mass Research Articles

Enhanced Aerosol Mass in the Tropical Tropopause Layer Linked to Ozone Abundance

AbstractAerosol particles play a critical role in the tropical tropopause layer (TTL) through cloud formation and heterogeneous chemistry, influencing the radiative and chemical balance of the stratosphere. However, aerosol measurements in the TTL are sparse, resulting in poor knowledge of aerosol abundance and distribution in this important region. Here, we present in situ aircraft measurements over the western tropical Pacific, revealing a persistent and altitude‐dependent enhancement of aerosol mass in the TTL compared to the convectively influenced troposphere below. Notably, our data demonstrate a striking positive correlation between aerosol mass and ozone. Model simulations suggest that organic materials constitute a substantial fraction of the total aerosol mass within the TTL. We further derived an empirical parameterization of TTL aerosol mass as a function of ozone based on their linear relationship. This framework holds potential for estimating the TTL aerosol abundance but requires further validation and refinement through future measurements.

Impact of acidity and surface-modulated acid dissociation on cloud response to organic aerosol

Abstract. Acid dissociation of the organic aerosol fraction has the potential to impact cloud-activating properties by altering aqueous-phase H+ concentrations and water activity but is currently overlooked in most atmospheric aerosol models. We implemented a simple representation of organic acid dissociation in the aerosol–chemistry–climate box model ECHAM6.3–HAM2.3 and investigated the impact on aerosol-forming aqueous sulfur chemistry, cloud droplet number concentrations, and the shortwave radiative effect. Many atmospheric organic acids are also surface-active and may be strongly adsorbed at the surface of small aqueous droplets. The degree of dissociation has recently been observed for several atmospheric surface-active organics with Brönsted acid character to be significantly shifted in the surface, compared to the bulk aqueous solution. In addition to the well-known bulk acidity, we therefore introduced an empirical account of this surface-modulated dissociation to further explore the potential impact on aerosol climate effects. Malonic acid and decanoic acid were used as proxies for atmospheric organic aerosols of different surface-active and acid strengths. Both acids were found to yield sufficient hydrogen ion concentrations from dissociation in an aqueous droplet population to strongly influence aqueous aerosol sulfur chemistry, leading to enhanced cloud droplet number concentrations and a cooling shortwave radiative effect. Further considering the surface modulation of organic acid dissociation, the impact on cloud microphysics was smaller than according to the well-known bulk solution acidity but still significant. Our results show that organic aerosol acid dissociation can significantly influence predictions of aerosol and cloud droplet formation and aerosol–cloud–climate effects and that, even for a well-known bulk solution phenomenon such as acidity, it may be important to also consider the specific influence of surface effects when surface-active acids comprise a significant fraction of the total organic aerosol mass.

ЗМІНА АЕРОЗОЛЬНИХ ПАРАМЕТРІВ В АТМОСФЕРІ ВНАСЛІДОК НАДХОДЖЕННЯ ПИЛУ З ОСУШЕНИХ ДІЛЯНОК КАХОВСЬКОГО ВОДОСХОВИЩА

The article presents main changes in atmospheric aerosol parameters due to the dust emission from the drained areas of the Kakhovka Reservoir and confirms the formation of a new source of aerosol pollution. The research was conducted using data on aerosol optical depth (AOD), Angstrom exponent, and aerosol mass fraction from the Moderate Resolution Imaging Spectroradiometer (MODIS) satellite instrument with support from LandSat satellite underlay surface images. An increase in AOD over the reservoir was established, resulting in a less pronounced change (-15%) during the fall compared to the regional background decrease of 50%. An increase in the aerosol mass fraction over the drained areas of the Kakhovka Reservoir was identified to be at least twice as much. Changes in the Angstrom exponent were identified, indicating a redistribution of the predominant size of aerosol particles in the atmospheric air. The frequency of cases with a predominance of the coarse fraction increased, while that of the fine fraction decreased. However, due to similar trends across the entire left bank of the Kherson region, it is currently impossible to be certain about the defining role of drying. At the same time, two indicators of changes in the Angstrom exponent suggest a shift in the size distribution of aerosol particles after the dam breach: an increased frequency of cases with an Angstrom exponent within 0.5-1.0, approaching the values over the Oleshky Sands; and a decrease in the frequency of cases with a predominance of the fine particles in October, unlike other territories. We emphasized the need for further monitoring of dust emissions into the atmosphere and modifications to emission inventories from natural sources for numerical atmospheric modeling purposes.

Global organic and inorganic aerosol hygroscopicity and its effect on radiative forcing

The climate effects of atmospheric aerosol particles serving as cloud condensation nuclei (CCN) depend on chemical composition and hygroscopicity, which are highly variable on spatial and temporal scales. Here we present global CCN measurements, covering diverse environments from pristine to highly polluted conditions. We show that the effective aerosol hygroscopicity, κ, can be derived accurately from the fine aerosol mass fractions of organic particulate matter (ϵorg) and inorganic ions (ϵinorg) through a linear combination, κ = ϵorg ⋅ κorg + ϵinorg ⋅ κinorg. In spite of the chemical complexity of organic matter, its hygroscopicity is well captured and represented by a global average value of κorg = 0.12 ± 0.02 with κinorg = 0.63 ± 0.01 as the corresponding value for inorganic ions. By showing that the sensitivity of global climate forcing to changes in κorg and κinorg is small, we constrain a critically important aspect of global climate modelling.

Modeling dust mineralogical composition: sensitivity to soil mineralogy atlases and their expected climate impacts

Abstract. Soil dust aerosols are a key component of the climate system, as they interact with short- and long-wave radiation, alter cloud formation processes, affect atmospheric chemistry and play a role in biogeochemical cycles by providing nutrient inputs such as iron and phosphorus. The influence of dust on these processes depends on its physicochemical properties, which, far from being homogeneous, are shaped by its regionally varying mineral composition. The relative amount of minerals in dust depends on the source region and shows a large geographical variability. However, many state-of-the-art Earth system models (ESMs), upon which climate analyses and projections rely, still consider dust mineralogy to be invariant. The explicit representation of minerals in ESMs is more hindered by our limited knowledge of the global soil composition along with the resulting size-resolved airborne mineralogy than by computational constraints. In this work we introduce an explicit mineralogy representation within the state-of-the-art Multiscale Online Nonhydrostatic AtmospheRe CHemistry (MONARCH) model. We review and compare two existing soil mineralogy datasets, which remain a source of uncertainty for dust mineralogy modeling and provide an evaluation of multiannual simulations against available mineralogy observations. Soil mineralogy datasets are based on measurements performed after wet sieving, which breaks the aggregates found in the parent soil. Our model predicts the emitted particle size distribution (PSD) in terms of its constituent minerals based on brittle fragmentation theory (BFT), which reconstructs the emitted mineral aggregates destroyed by wet sieving. Our simulations broadly reproduce the most abundant mineral fractions independently of the soil composition data used. Feldspars and calcite are highly sensitive to the soil mineralogy map, mainly due to the different assumptions made in each soil dataset to extrapolate a handful of soil measurements to arid and semi-arid regions worldwide. For the least abundant or more difficult-to-determine minerals, such as iron oxides, uncertainties in soil mineralogy yield differences in annual mean aerosol mass fractions of up to ∼ 100 %. Although BFT restores coarse aggregates including phyllosilicates that usually break during soil analysis, we still identify an overestimation of coarse quartz mass fractions (above 2 µm in diameter). In a dedicated experiment, we estimate the fraction of dust with undetermined composition as given by a soil map, which makes up ∼ 10 % of the emitted dust mass at the global scale and can be regionally larger. Changes in the underlying soil mineralogy impact our estimates of climate-relevant variables, particularly affecting the regional variability of the single-scattering albedo at solar wavelengths or the total iron deposited over oceans. All in all, this assessment represents a baseline for future model experiments including new mineralogical maps constrained by high-quality spaceborne hyperspectral measurements, such as those arising from the NASA Earth Surface Mineral Dust Source Investigation (EMIT) mission.

Measurement report: Long-range transport and the fate of dimethyl sulfide oxidation products in the free troposphere derived from observations at the high-altitude research station Chacaltaya (5240 m a.s.l.) in the Bolivian Andes

Abstract. Dimethyl sulfide (DMS) is the primary natural contributor to the atmospheric sulfur burden. Observations concerning the fate of DMS oxidation products after long-range transport in the remote free troposphere are, however, sparse. Here we present quantitative chemical ionization mass spectrometric measurements of DMS and its oxidation products sulfuric acid (H2SO4), methanesulfonic acid (MSA), dimethylsulfoxide (DMSO), dimethylsulfone (DMSO2), methanesulfinic acid (MSIA), methyl thioformate (MTF), methanesulfenic acid (MSEA, CH3SOH), and a compound of the likely structure CH3S(O)2OOH in the gas phase, as well as measurements of the sulfate and methanesulfonate aerosol mass fractions. The measurements were performed at the Global Atmosphere Watch (GAW) station Chacaltaya in the Bolivian Andes located at 5240 m above sea level (a.s.l.). DMS and DMS oxidation products are brought to the Andean high-altitude station by Pacific air masses during the dry season after convective lifting over the remote Pacific ocean to 6000–8000 m a.s.l. and subsequent long-range transport in the free troposphere (FT). Most of the DMS reaching the station is already converted to the rather unreactive sulfur reservoirs DMSO2 in the gas phase and methanesulfonate (MS−) in the particle phase, which carried nearly equal amounts of sulfur to the station. The particulate sulfate at Chacaltaya is however dominated by regional volcanic emissions during the time of the measurement and not significantly affected by the marine air masses. In one of the FT events, even some DMS was observed next to reactive intermediates such as methyl thioformate, dimethylsulfoxide, and methanesulfinic acid. Also for this event, back trajectory calculations show that the air masses came from above the ocean (distance >330 km) with no local surface contacts. This study demonstrates the potential impact of marine DMS emissions on the availability of sulfur-containing vapors in the remote free troposphere far away from the ocean.

Characterization of Propane Fueled Flames: A Significant Source of Brown Carbon

In this study, we developed a framework for interpreting the in situ morphological properties of black carbon (BC, also referred to as “soot” due to combustion relevance) mixed with primary organic aerosol. Integration of the experiment considering primary organic aerosol (POA) evaporation from the soot particles was examined using a Differential mass–mobility analyzer (DMA) and showed the untold story of the mixing of BC and POA. We also hypothesize that morphological transformation of soots and determined such as (i) the evaporation of externally and internally mixed POA led to a decline in the particle number and size of monodisperse aerosol; (ii) presence of externally mixed BC was interpreted from the occurrence of two peaks of soot upon heating; (iii) heat-induced collapse of the BC core possibly resulted from the evaporation of material from the voids and effect of heat; (iv) volume equivalent to changes in the mobility diameter represented evaporation of POA from the surface and collapse upon heating. POA constituted a high fraction (20–40% by mass) of aerosol mass from these flames and was predominantly (i.e., 92–97% by mass) internally mixed with BC. POA was found to be highly light absorptive, i.e., an Ångström absorption exponent (AAE) value of (in general) >1.5 was estimated for BC + POA at 405/781 nm wavelengths. Interestingly, a much more highly absorptive POA [mass absorption cross-section (MAC)-5 m2 g−1] at 405 nm was discovered under a specific flame setting, which was comparable to MACs of BC particles (8–9 m2 g−1).

Using aerosols to make an integrated rapid assessment of the ecological state of territories

Introduction. Indicators of aerosol suspensions, used to make an integrated rapid assessment of the ecological state of territories, allow quickly assessing the ecological status of residential areas of settlements without installing mobile or stationary ecological posts. Aerosol particles are the subject of this study. The purpose of the study is an integrated rapid assessment of the ecological state of the residential area of the Srednyaya Akhtuba settlement (the Volgograd region) located in close proximity to operating enterprises, engaged in the production of expanded clay. The following aerosol indicators are employed to achieve this goal: acidity (pH); specific electrical conductivity (EC, µS/cm); toxicity (development of tested objects (Lr, cm)); the number of particles and their mass fraction from the perspective of convolution of normalized basic factors. The research objectives include sampling of aerosol particles; preparation of aerosol suspensions; study of indicators of aerosol suspensions; identification of the ecological status of the territory of the residential area of the Srednyaya Akhtuba settlement.
 Materials and methods. The studied material is the aerosol particles taken from the surface of the leaves of apricot trees (Prúnus armeníaca L.) in the residential area of Srednyaya Akhtuba, Sredneakhtubinskiy district, Volgograd region, October 2018. The sampling of aerosol particles and the preparation of aerosol suspensions were carried out using international methods. The study of the acidity index (pH) and specific electrical conductivity (EC, μS/cm) was carried out using the electrochemical equipment of the MULTEST series (Russia): an ion meter (IPL-101-1) and a conductometer (KSL-111), respectively. The study of the toxicity of aerosol suspensions was based on measuring the development of tested objects (Lr, cm); the study of the dispersed composition of aerosol particles, their quantity and mass fraction were carried out according to GOST R (All-Russian State Standard) 56929-2016.
 Results. The studies allowed assigning the ecological status of “an environmental crisis” to the territory of the residential area in Srednyaya Akhtuba as of the spring and summer of 2018.
 Conclusions. Sources of pollution must be identified and environmental actions must be developed to protect the residential area of the settlement from aerosol particles with a diameter of less than 10 microns (PM10).

Enhanced secondary aerosol formation driven by excess ammonia during fog episodes in Delhi, India

The Indo-Gangetic Plain (IGP) has high wintertime fine aerosol loadings that significantly modulate the widespread fog formation and sustenance. Here, we investigate the potential formation of secondary inorganic aerosol driven by excess ammonia during winter fog. Physicochemical properties of fine aerosols (PM1 and PM2.5) and trace gases (HCl, HONO, HNO3, SO2, and NH3) were simultaneously monitored at hourly resolution using Monitor for AeRosols and Gases in Ambient air (MARGA-2S) for the first time in India. Results showed that four major ions, i.e., Cl−, NO3−, SO42−, and NH4+ contributed approximately 97% of the total measured inorganic ionic mass. The atmosphere was ammonia-rich in winter and ammonium was the dominant neutralizer with aerosol neutralization ratio (ANR) close to unity. The correlation between ammonium and chloride was ≥0.8, implying the significant formation of ammonium chloride during fog in Delhi. Thermodynamical model ISORROPIA-II showed the predicted PM1 and PM2.5 pH to be 4.49 ± 0.53, and 4.58 ± 0.48 respectively which were in good agreement with measurements. The ALWC increased from non-foggy to foggy periods and a considerable fraction of fine aerosol mass existed in the supermicron size range of 1–2.5 μm. The sulfur oxidation ratio (SOR) of PM1, PM2.5 reached up to 0.60, 0.75 in dense fog and 0.74, 0.87 when ambient RH crossed a threshold of 95%, much higher than non-foggy periods (with confidence level of ≥95%) pointing to enhanced formation of secondary aerosol in fog.

Rapid mass growth and enhanced light extinction of atmospheric aerosols during the heating season haze episodes in Beijing revealed by aerosol–chemistry–radiation–boundary layer interaction

Abstract. Despite the numerous studies investigating haze formation mechanism in China, it is still puzzling that intensive haze episodes could form within hours directly following relatively clean periods. Haze has been suggested to be initiated by the variation of meteorological parameters and then to be substantially enhanced by aerosol–radiation–boundary layer feedback. However, knowledge on the detailed chemical processes and the driving factors for extensive aerosol mass accumulation during the feedback is still scarce. Here, the dependency of the aerosol number size distribution, mass concentration and chemical composition on the daytime mixing layer height (MLH) in urban Beijing is investigated. The size distribution and chemical composition-resolved dry aerosol light extinction is also explored. The results indicate that the aerosol mass concentration and fraction of nitrate increased dramatically when the MLH decreased from high to low conditions, corresponding to relatively clean and polluted conditions, respectively. Particles having their dry diameters in the size of ∼400–700 nm, and especially particle-phase ammonium nitrate and liquid water, contributed greatly to visibility degradation during the winter haze periods. The dependency of aerosol composition on the MLH revealed that ammonium nitrate and aerosol water content increased the most during low MLH conditions, which may have further triggered enhanced formation of sulfate and organic aerosol via heterogeneous reactions. As a result, more sulfate, nitrate and water-soluble organics were formed, leading to an enhanced water uptake ability and increased light extinction by the aerosols. The results of this study contribute towards a more detailed understanding of the aerosol–chemistry–radiation–boundary layer feedback that is likely to be responsible for explosive aerosol mass growth events in urban Beijing.

Spatio-Temporal Variability of Aerosol Components, Their Optical and Microphysical Properties over North China during Winter Haze in 2012, as Derived from POLDER/PARASOL Satellite Observations

Pollution haze is a frequent phenomenon in the North China Plain (NCP) appearing during winter when the aerosol is affected by various pollutant sources and has complex distribution of the aerosol properties, while different aerosol components may have various critical effects on air quality, human health and radiative balance. Therefore, large-scale and accurate aerosol components characterization is urgently and highly desirable but hardly achievable at the regional scale. In this respect, directional and polarimetric remote sensing observations have great potential for providing information about the aerosol components. In this study, a state-of-the-art GRASP/Component approach was employed for attempting to characterize aerosol components in the NCP using POLDER/PARASOL satellite observations. The analysis was done for January 2012 in Beijing (BJ) and Shanxi (SX). The results indicate a peak of the BC mass concentration in an atmospheric column of 82.8 mg/m2 in the SX region, with a mean of 29.2 mg/m2 that is about four times higher than one in BJ (8.9 mg/m2). The mean BrC mass concentrations are, however, higher in BJ (up to ca. 271 mg/m2) than that in SX, which can be attributed to a higher anthropogenic emission. The mean amount of fine ammonium sulfate-like particles observed in the BJ region was three times lower than in SX (131 mg/m2). The study also analyzes meteorological and air quality data for characterizing the pollution event in BJ. During the haze episode, the results suggest a rapid increase in the fine mode aerosol volume concentration associated with a decrease of a scale height of aerosol down to 1500 m. As expected, the values of aerosol optical depth (AOD), absorbing aerosol optical depth (AAOD) and fine mode aerosol optical depth (AODf) are much higher on hazy days. The mass fraction of ammonium sulfate-like aerosol increases from about 13% to 29% and mass concentration increases from 300 mg/m2 to 500 mg/m2. The daily mean PM2.5 concentration and RH independently measured during these reported pollution episodes reach up to 425 g/m3 and 80% correspondingly. The monthly mean mass concentrations of other aerosol components in the BJ are found to be in agreement with the results of previous research works. Finally, a preliminary comparison of these remote sensing derived results with literature and in situ PM2.5 measurements is also presented.

Enrichment of calcium in sea spray aerosol in the Arctic summer atmosphere

Significant calcium enrichment relative to seawater was observed in bulk and size-segregated aerosols in the marine atmospheric boundary layer over the Arctic Ocean in summer. The calcium enrichment factor generally increased with decreasing particle size (aerodynamic diameter) in the fine mode (particle size <1.8 μm), especially within the particle size ranges of 1.8 μm to 0.56 μm and 0.18 μm to 0.1 μm. Potassium was slightly enriched and showed a similar trend of enrichment in fine mode particles. No positive enrichment was observed for magnesium. Calcium bound to certain organic compounds and possibly calcareous debris from marine organisms may have contributed to the calcium enrichment in aerosols. Model results predict that observed calcium enrichments would increase hygroscopic growth in both coarse (10 μm and 5.6 μm) and fine (0.56 μm and 1 μm) aerosol particles. Possible alteration of this model result due to interactions with anions notwithstanding, increases in hygroscopic growth would be particularly important in the Arctic summer when sea-salts constitute the major fraction of aerosol dry mass. This study provides unique insights into ocean-atmosphere chemical interactions in the high-latitude Arctic Ocean.

Numerical Simulation and Validation of Aerosol Particle Removal by Water Spray Droplets With OpenFOAM During the Fukushima Daiichi Fuel Debris Retrieval

In the decommissioning of damaged Fukushima Daiichi reactors, the melted and re-solidified fuel debris in the bottom of the reactor pressure vessel and primary containment vessel need to be cut into small pieces before removing them from reactor buildings. During the cutting operations, submicron radioactive aerosol particles are expected to be generated and dispersed into the atmosphere of the primary containment vessel. Those suspended particles must be removed from the air atmosphere inside the containment before escaping to the environment. The water spray system in the upper part of the primary containment vessel is an effective and applicable method to remove airborne radioactive aerosol particles. Computational Fluid Dynamics simulation of aerosol scavenging by spray droplets is complicated but necessary to investigate the aerosol removal process inside the vessel. In this paper, a numerical model was developed and implemented into an open-source computational fluid dynamic code OpenFOAM to simulate the aerosol removal by water spray droplets with considering the collection mechanisms of inertial impaction, interception, and Brownian diffusion. In this model, the dispersed spray droplets were described using the Lagrangian particle tracking method, the continuous particle-laden gas was described using the Eulerian method, and a two-way interaction between dispersed and continuous phases was considered. The polydisperse aerosol particles at different diameters from 0.2 – 1 μm were treated as different gas species of the continuous phase. Continuity equations of each gas specie were solved using a passive scalar transport equation. The numerical model was validated by comparing the simulation results with the experimental data obtained from UTARTS facility. Simulation results agreed well with the experimental results. The simulation results provided more insights to better understand the aerosol removal process, including the time evolution of aerosol mass fraction and flow field of the gas phase.

Wintertime hygroscopic growth factors (HGFs) of accumulation mode particles and their linkage to chemical composition in a heavily polluted urban atmosphere of Kanpur at the Centre of IGP, India: Impact of ambient relative humidity

This study reported results of the wintertime simultaneous measurements of hygroscopic growth factors (HGFs) and particle-phase chemical composition of accumulation mode particles using a self-assembled Hygroscopic Tandem Differential Mobility Analyzer (H-TDMA) and an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS), respectively at a heavily polluted urban atmosphere of Kanpur, situated in the center of IGP in India. HGFs at 85% relative humidity (RH) and the size-resolved composition of ambient aerosol particles (dry electrical mobility diameters of 100 and 150 nm) were investigated. HGF_85% was found to increase with particle size. The relative mass fraction of organic aerosol (OA) and NH4NO3 are probably the major contributors to the fluctuation of the HGF_85% for both particle sizes. The HGF_85% of accumulation mode particles were observed to increase from the minimum value observed during the morning until its maximum afternoon value. This study reported two maximum (early morning and afternoon time) and two minimum values (morning and evening time) of HGF_85%s. As a consequence, the main reasons for this incremental behavior were, increase in the ratio of inorganic to OA and oxidation level, f44 (m/z44/OA) of the OA within the particle phase. In context to the effect of ambient RH, this study reported two distinct variations of mean HGF_85% as the function of ambient RH. The positive linear relationship at low RH (LRH, RH ≤ 50%) was clearly associated with low OA loading, relatively higher substantial temperature, and wind speed. We also observed increment in f44, and effective density indicating aging of aerosol. However, HGF_85% was found to inversely decline as a function of RH at higher RH (HRH, RH > 50%) conditions, which clearly reflect the more significant contribution of primary OA and lower oxidation level of OA. Our results show the declining trend in size-resolved effective density at HRH conditions, confirming the above conclusions.

Aerosol Optical Tweezers Constrain the Morphology Evolution of Liquid-Liquid Phase-Separated Atmospheric Particles

Summary Chemical models of atmospheric particles are vital in understanding the role of aerosol particles in atmospheric chemistry, air pollution, human health, and climate change. Advancing these models requires new frameworks that can realistically predict how critical particle properties evolve. We present such a framework for predicting particle phase separation and which morphology will prevail; this controls how each particle interacts with and affects the atmosphere. We studied the mixing behavior of α-pinene secondary organic aerosol (SOA) with different organic phases, as relative humidity was varied to determine the interplay between polarity, miscibility, interfacial tension, and the resulting morphology. Using measurements from aerosol optical tweezers experiments and literature data, a general trend in morphology with increasing atmospheric oxidation was observed, from biphasic partially engulfed (where both phases are immediately accessible to the gas phase) to biphasic core shell (where the organic shell conceals the core) and finally to a single-phase, homogeneous morphology.

Photochemical Aging Alters Secondary Organic Aerosol Partitioning Behavior

Organic aerosol is the largest fraction of the atmospheric nonrefractory aerosol mass and has a significant impact on climate, visibility, and human health. A significant portion of organic aerosol is secondary organic aerosol (SOA), which forms when volatile organic compounds (VOCs) are oxidized and the reaction products partition to the particle phase. SOA formation and aging have been described using semivolatile partitioning theory, and a typical assumption invoked is that gas-particle partitioning rapidly reaches equilibrium. However, several studies have called into question whether traditional equilibrium assumptions are valid, either due to particle-phase diffusion limitations, particle-phase reactions, or liquid/liquid phase separation and immiscibility of organic phases. Here, we investigate the ability of equilibrium partitioning to describe laboratory SOA formation experiments using SOA mass and yield as the evaluation metric. We conduct two types of experiments: (1) co-condensation experiment...

Bouncier Particles at Night: Biogenic Secondary Organic Aerosol Chemistry and Sulfate Drive Diel Variations in the Aerosol Phase in a Mixed Forest.

Aerosol phase state is critical for quantifying aerosol effects on climate and air quality. However, significant challenges remain in our ability to predict and quantify phase state during its evolution in the atmosphere. Herein, we demonstrate that aerosol phase (liquid, semisolid, solid) exhibits a diel cycle in a mixed forest environment, oscillating between a viscous, semisolid phase state at night and liquid phase state with phase separation during the day. The viscous nighttime particles existed despite higher relative humidity and were independently confirmed by bounce factor measurements and atomic force microscopy. High-resolution mass spectrometry shows the more viscous phase state at night is impacted by the formation of terpene-derived and higher molecular weight secondary organic aerosol (SOA) and smaller inorganic sulfate mass fractions. Larger daytime particulate sulfate mass fractions, as well as a predominance of lower molecular weight isoprene-derived SOA, lead to the liquid state of the daytime particles and phase separation after greater uptake of liquid water, despite the lower daytime relative humidity. The observed diel cycle of aerosol phase should provoke rethinking of the SOA atmospheric lifecycle, as it suggests diurnal variability in gas-particle partitioning and mixing time scales, which influence aerosol multiphase chemistry, lifetime, and climate impacts.

Physical properties of secondary photochemical aerosol from OH oxidation of a cyclic siloxane.

Cyclic volatile methyl siloxanes (cVMS) are high-production chemicals present in many personal care products. They are volatile, hydrophobic, and relatively long-lived due to slow oxidation kinetics. Evidence from chamber and ambient studies indicates that oxidation products may be found in the condensed aerosol phase. In this work, we use an oxidation flow reactor to produce ~ 100 μgm-3 of organosilicon aerosol from OH oxidation of decamethyl-cyclopentasiloxane (D5) with aerosol mass fractions (i.e., yields) of 0.2-0.5. The aerosols were assessed for concentration, size distribution, morphology, sensitivity to seed aerosol, hygroscopicity, volatility and chemical composition through a combination of aerosol size distribution measurement, tandem differential mobility analysis, and electron microscopy. Similar aerosols were produced when vapor from solid antiperspirant was used as the reaction precursor. Aerosol yield was sensitive to chamber OH and to seed aerosol, suggesting sensitivity of lower-volatility species and recovered yields to oxidation conditions and chamber operation. The D5 oxidation aerosol products were relatively non-hygroscopic, with an average hygroscopicity kappa of ~ 0.01, and nearly non-volatile up to 190 °C temperature. Parameters for exploratory treatment as a semi-volatile organic aerosol in atmospheric models are provided.

Characterization of aerosol chemical composition from urban pollution in Brazil and its possible impacts on the aerosol hygroscopicity and size distribution

We studied the effect of aerosols inorganic chemical composition on the aerosol hygroscopicity of urban pollution in Brazil, where biofuels have been used in large scale. We applied size segregated inorganic chemical composition analysis using ISORROPIA II model and κ-Köhler theory to determine the hygroscopicity parameter (κ) of submicrometer aerosols measured in São Paulo city. The size dependence of organic and black carbon (BC) mass were estimated by chemical mass balance and mean observed values.Results showed ultrafine mode particles with diameter smaller than 100 nm with a relatively K2SO4 and Na2SO4 large amount inducing further growth by diffusive condensation and coagulation of low-volatile organic compounds. The process could lead to modifications of aerosol size distribution and also to formation of more active Cloud Condensation Nuclei (CCN) due to the formation of aerosols with considerably increase of hygroscopicity (>40%). The contribution from BC can decreases up to 40% of the observed hygroscopicities values of particles around 100 nm in diameter.Moreover, we present a parameterization based on aerosol mass fraction to accurately predict κ derived from data of Aerosol Mass Spectrometer (AMS) collected in urban pollution in Brazil. Results are compared to hygroscopicity derived from observations of the pollution plume downwind Manaus, on the northern region of Brazil. Both cases were analogous indicating that, despite the fact of receiving influences of organic components from the forest, the pollution plume of Manaus shows the same characteristics of hygroscopicity, and can be modeled following the same parameterization.

Combined effects of boundary layer dynamics and atmospheric chemistry on aerosol composition during new particle formation periods

Abstract. Characterizing aerosol chemical composition in response to meteorological changes and atmospheric chemistry is important to gain insights into new particle formation mechanisms. A BAECC (Biogenic Aerosols – Effects on Clouds and Climate) campaign was conducted during the spring 2014 at the SMEAR II station (Station for Measuring Forest Ecosystem–Aerosol Relations) in Finland. The particles were characterized by a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). A PBL (planetary boundary layer) dilution model was developed to assist interpreting the measurement results. Right before nucleation events, the mass concentrations of organic and sulfate aerosol species were both decreased rapidly along with the growth of PBL heights. However, the mass fraction of sulfate aerosol of the total aerosol mass was increased, in contrast to a decrease for the organic mass fraction. Meanwhile, an increase in LVOOA (low-volatility oxygenated organic aerosol) mass fraction of the total organic mass was observed, in distinct comparison to a reduction of SVOOA (semi-volatile OOA) mass fraction. Our results demonstrate that, at the beginning of nucleation events, the observed sulfate aerosol mass was mainly driven by vertical turbulent mixing of sulfate-rich aerosols between the residual layer and the newly formed boundary layer, while the condensation of sulfuric acid (SA) played a minor role in interpreting the measured sulfate mass concentration. For the measured organic aerosols, their temporal profiles were mainly driven by dilution from PBL development, organic aerosol mixing in different boundary layers and/or partitioning of organic vapors, but accurate measurements of organic vapor concentrations and characterization on the spatial aerosol chemical composition are required. In general, the observed aerosol particles by AMS are subjected to joint effects of PBL dilution, atmospheric chemistry and aerosol mixing in different boundary layers. During aerosol growth periods in the nighttime, the mass concentrations of organic aerosols and organic nitrate aerosols were both increased. The increase in SVOOA mass correlated well with the calculated increase in condensed HOMs' (highly oxygenated organic molecules) mass. To our knowledge, our results are the first atmospheric observations showing a connection between increase in SVOOA and condensed HOMs during the nighttime.