Hygroscopicity Tandem Differential Mobility Analyzer Research Articles

Additive Water Uptake of the Mixtures of Urban Atmospheric HULIS and Ammonium Sulfate

AbstractThe hygroscopicity of atmospheric aerosols affect the global climate and human health. However, the hygroscopic behavior of mixtures of inorganic salts and organics in atmospheric aerosols have not been well characterized for ambient complex organic mixtures. Here, the hygroscopic growth of humic‐like substances (HULIS), which represent the complexity of organic aerosol compounds, from urban aerosols and their mixtures with ammonium sulfate were investigated with measurements from a hygroscopicity tandem differential mobility analyzer and model analyses. The Zdanovskii–Stokes–Robinson (ZSR) relationship, which assumes that the water uptake of each component is additive, was examined for the mixtures. The dependence of the hygroscopicity parameters (κ) of the mixtures on the volume fraction of HULIS is generally represented by the ZSR relationship with the deviations of κ on average of 16% (4%–27% in different mixing ratios), and 0.03 (0.02–0.04) on absolute basis. An assumption of asphericity for the dry particles reduced the deviations (14%). Approximations for the surface tension depression by surfactants and surface‐bulk partitioning were predicted to account for the deviations to a small extent. Furthermore, a thermodynamic model for simplified compound systems showed that the non‐ideality of the solutions potentially explained the deviations from the ZSR relationship. The results of this study support the use of the ZSR relationship for organic‒inorganic mixtures as a practical approximation in atmospheric models, provide a guide for the uncertainty associated with this approximation, and suggest directions for future studies.

62°S Witnesses the Transition of Boundary Layer Marine Aerosol Pattern Over the Southern Ocean (50°S–68°S, 63°E–150°E) During the Spring and Summer: Results From MARCUS (I)

AbstractThe Atmospheric Radiation Measurement Mobile Facility‐2 was installed onboard the research vessel Aurora Australis to measure aerosol properties during the 2017–2018 Measurement of Aerosols, Radiation, and CloUds over the pristine Southern ocean (MARCUS) Experiment, providing unique data on aerosols latitudinal and seasonal variation, including south of 60°S where previous observations are scarce. Data from a Cloud Condensation Nuclei (CCN) counter and Ultra‐High‐Sensitivity Aerosol Spectrometer show that both the number concentration (NCCN) and size distribution of CCN‐active aerosols, with diameters (D) between 60 nm < D < 1,000 nm are different over the North Southern Ocean (NSO) (50°S–60°S) and the South Southern Ocean (SSO) (62°S–68°S). The average NSO NCCN at 0.2% and 0.5% supersaturation were 28% and 49% less than that over the SSO. This increase of CCN over the SSO is caused by the increase of aerosols with 60 nm < D < 200 nm, consistent with calculations of Aerosol Scattering Angstrom Exponents derived from a nephelometer. Aerosol hygroscopicity growth factor measured by the Hygroscopic Tandem Differential Mobility Analyzer stayed close to 1.41 for aerosols with 50 nm < D < 250 nm over the SSO, but increased from 1.30 to 1.67 over the NSO, indicating different chemical compositions. Both CCN and Ice Nucleating Particles (INPs) showed a stronger variation with season than with latitude. The variation of heat‐labile and presumably proteinacous INPs suggests an increase of ice nucleating‐active microbes in summer.

Measurement report: Hygroscopicity of size-selected aerosol particles in the heavily polluted urban atmosphere of Delhi: impacts of chloride aerosol

Abstract. Recent research has revealed the crucial role of wintertime, episodic high chloride (H-Cl) emissions in the Delhi region, which significantly impact aerosol hygroscopicity and aerosol-bound liquid water, thus contributing to the initiation of Delhi fog episodes. However, these findings have primarily relied on modeled aerosol hygroscopicity, necessitating validation through direct hygroscopicity measurements. This study presents the measurements of non-refractory bulk aerosol composition of PM1 from an Aerodyne aerosol chemical speciation monitor and for first-time size-resolved hygroscopic growth factors (nucleation, Aitken, and accumulated mode particles) along with their associated hygroscopicity parameters at 90 % relative humidity using a hygroscopic tandem differential mobility analyzer at the Delhi Aerosol Supersite. Our observations demonstrate that the hygroscopicity parameter for aerosol particles varies from 0.00 to 0.11 (with an average of 0.03 ± 0.02) for 20 nm particles, 0.05 to 0.22 (0.11 ± 0.03) for 50 nm particles, 0.05 to 0.30 (0.14 ± 0.04) for 100 nm particles, 0.05 to 0.41 (0.18 ± 0.06) for 150 nm particles, and 0.05 to 0.56 (0.22 ± 0.07) for 200 nm particles. Surprisingly, our findings demonstrate that the period with H-Cl emissions displays notably greater hygroscopicity (0.35 ± 0.06) in comparison to spans marked by high biomass burning (0.18 ± 0.04) and high hydrocarbon-like organic aerosol (0.17 ± 0.05) and relatively cleaner periods (0.27 ± 0.07). This research presents initial observational proof that ammonium chloride is the main factor behind aerosol hygroscopic growth and aerosol-bound liquid water content in Delhi. The finding emphasizes ammonium chloride's role in aerosol–water interaction and related haze/fog development. Moreover, the high chloride levels in aerosols seem to prevent the adverse impact of high organic aerosol concentrations on cloud condensation nuclei activity.

Measurement report: High Arctic aerosol hygroscopicity at sub- and supersaturated conditions during spring and summer

Abstract. Aerosol hygroscopic growth and cloud droplet formation influence the radiation transfer budget of the atmosphere and thereby the climate. In the Arctic, these aerosol properties may have a more pronounced effect on the climate compared to the midlatitudes. Hygroscopic growth and cloud condensation nuclei (CCN) concentrations of high Arctic aerosols were measured during two field studies in the spring and summer of 2016. The study site was the Villum Research Station (Villum) at Station Nord in the northeastern region of Greenland. Aerosol hygroscopic growth was measured with a hygroscopic tandem differential mobility analyzer (HTDMA) over a total of 23 d, and CCN concentrations were measured over a period of 95 d. Continuous particle number size distributions were recorded, facilitating calculations of aerosol CCN activation diameters and aerosol κ values. In spring, average CCN concentrations, at supersaturations (SSs) of 0.1 % to 0.3 %, ranged from 53.7 to 85.3 cm−3, with critical activation diameters ranging from 130.2 to 80.2 nm and κCCN ranging from 0.28–0.35. In summer, average CCN concentrations were 20.8 to 47.6 cm−3, while critical activation diameters and κCCN were from 137.1 to 76.7 nm and 0.23–0.35, respectively. Mean particle hygroscopic growth factors ranged from 1.60 to 1.75 at 90 % relative humidity in spring, while values between 1.47 and 1.67 were observed in summer depending on the initial dry size. Although the summer aerosol number size distributions were characterized by frequent new particle formation events, the CCN population at cloud-relevant supersaturations was determined by accumulation-mode aerosols.

Seasonal variation of particle hygroscopicity and its impact on cloud-condensation nucleus activation in the Beijing urban area

Hygroscopicity is a key parameter for characterizing the ability of particles to be activated as cloud-condensation nuclei (CCN). In this study, we present a 10-month size-resolved measurement of the hygroscopicity of particles with diameters of 50, 100 and 200 nm in the Beijing urban area using a Hygroscopicity-Tandem Differential Mobility Analyzer (H-TDMA). Compared with that in other studies conducted in China, the hygroscopicity parameter (κ) in this study was relatively higher than that in the Pearl River Delta region but lower than that in the Yangtze River Delta region. As the mass fraction of inorganic matter (especially nitrate) increased, the particles became more hygroscopic during spring and summer, as influenced by the chemical composition. Polluted southerly air masses also enhanced particle hygroscopicity. The CCN concentration was calculated based on κ-Köhler theory, with a moderate supersaturation of 0.4%. The critical diameter of particles as potential CCNs was smaller in spring than that in the other seasons. The critical diameters of aerosols in autumn, winter and spring were 142, 123 and 114 nm, respectively, with calculated CCN concentrations of 1683, 1909 and 1765 cm−3, respectively. Activation ratios, calculated as CCN divided by condensation nuclei (CN), were 0.13, 0.15 and 0.18 in autumn, spring and summer, respectively. During episodes of heavy pollution, the CCN concentration highly depended on the particle mass loading, as the accumulation mode dominated the particle number size distribution and the chemical composition was quasi-homogeneous. However, under other conditions, both particle size and chemical composition were important. This study revealed the relationship between particle hygroscopicity, CCN and air pollution level, and it will be useful for evaluating the environmental and climatic effects of aerosols.

Quantifying particle-to-particle heterogeneity in aerosol hygroscopicity

Abstract. The particle-to-particle heterogeneity in aerosol hygroscopicity is crucial for understanding aerosol climatic and environmental effects. The hygroscopic parameter κ, widely applied to describe the hygroscopicity for aerosols both in models and observations, is a probability distribution highly related to aerosol heterogeneity due to the complex sources and aging processes. However, the heterogeneity in aerosol hygroscopicity is not adequately represented in observations and model simulations, leading to challenges in accurately estimating aerosol climatic and environmental effects. Here, we propose an algorithm for quantifying the particle-to-particle heterogeneity in aerosol hygroscopicity, based on information-theoretic entropy measures, by using the data that come only from the in situ measurement of the hygroscopicity tandem differential mobility analyzer (H-TDMA). Aerosols in this algorithm are assumed to be simple binary systems consisting of the less hygroscopic and more hygroscopic components, which are commonly used in H-TDMA measurement. Three indices, including the average per-particle species diversity Dα, the bulk population species diversity Dγ, and their affine ratio χ are calculated from the probability distribution of κ to describe aerosol heterogeneity. This algorithm can efficiently characterize the evolution of aerosol heterogeneity with time in the real atmosphere. Our results show that the heterogeneity varies much with aerosol particle size, and large discrepancies exist in the width and peak value of particle number size distribution (PNSD) with varied heterogeneity after hygroscopic growth, especially for conditions with high relative humidity. This reveals a vital role of the heterogeneity in ambient PNSD and significant uncertainties in calculating the climate-relevant properties if the population-averaged hygroscopicity is applied by neglecting its heterogeneity. This work points the way toward a better understanding of the role of hygroscopicity in evaluating aerosol climatic and environmental impacts.

Atmospheric nanoparticles hygroscopic growth measurement by a combined surface plasmon resonance microscope and hygroscopic tandem differential mobility analyzer

Abstract. The hygroscopic growth of atmospheric aerosols plays an important role in regional radiation, cloud formation, and hence climate. Aerosol hygroscopic growth is often characterized by hygroscopic tandem differential mobility analyzers (HTDMAs), and Xie et al. (2020) recently demonstrated that hygroscopic growth measurements of a single particle are possible using a surface plasmon resonance microscope-azimuthal rotation illumination (SPRM-ARI). The hygroscopic properties of ambient aerosols are not uniform and often exhibit large relative humidity (RH) and size variabilities due to different chemical compositions and mixing states. To better understand the contribution of different aerosol components and establish a link between the apparent hygroscopic properties of single particles and bulk aerosols, we conduct combined hygroscopic growth measurements using a SPRM-ARI and an HTDMA as a case study to prove the concept (experimental information: 100–200 nm, during noontime on 28 September 2021 and 22 March 2022 in Hefei, China). According to the distinct hygroscopic growth behavior from single-particle probing using a SPRM-ARI, the individual particles can be classified into three categories defined as non-hygroscopic (NH), less hygroscopic (LH), and more hygroscopic (MH). The mean growth factor (GF) of the three categories can be utilized to reproduce the GF distribution obtained from the HTDMA measurement. The chemical compositions of individual particles from the three categories are identified to be organic carbon (OC), soot (mainly elemental carbon), fly ash, and secondary aerosols (mainly OC and sulfate), using scanning electron microscopy (SEM) with an energy-dispersive spectrometer (EDS). The coupled SPRM–HTDMA measurement suggests a size-dependent variation of aerosol chemical components, i.e., an increase of OC fraction with increasing particle sizes, which agrees reasonably well with the chemical compositions from collected aerosol samples. This likely links the hygroscopic properties of individual particles to their bulk hygroscopic growth and chemical composition.

Missed Evaporation from Atmospherically Relevant Inorganic Mixtures Confounds Experimental Aerosol Studies.

Sea salt aerosol particles are highly abundant in the atmosphere and play important roles in the global radiative balance. After influence from continental air, they are typically composed of Na+, Cl-, NH4+, and SO42- and organics. Analogous particle systems are often studied in laboratory settings by atomizing and drying particles from a solution. Here, we present evidence that such laboratory studies may be consistently biased in that they neglect losses of solutes to the gas phase. We present experimental evidence from a hygroscopic tandem differential mobility analyzer and an aerosol mass spectrometer, further supported by thermodynamic modeling. We show that, at normally prevailing laboratory aerosol mass concentrations, for mixtures of NaCl and (NH4)2SO4, a significant portion of the Cl- and NH4+ ions are lost to the gas phase, in some cases, leaving mainly Na2SO4 in the dry particles. Not considering losses of solutes to the gas phase during experimental studies will likely result in misinterpretation of the data. One example of such data is that from particle water uptake experiments. This may bias the explanatory models constructed from the data and introduce errors inte predictions made by air quality or climate models.

Annual cycle of hygroscopic properties and mixing state of the suburban aerosol in Athens, Greece

Abstract. The hygroscopic properties of atmospheric aerosol were investigated at a suburban environment in Athens, Greece, from August 2016 to July 2017. The growth factor distribution probability density function (GF-PDF) and mixing state were determined with a hygroscopicity tandem differential mobility analyser (HTDMA). Four dry particle sizes (D0) were selected to be analysed in terms of their hygroscopic properties at 90 % relative humidity. The annual mean GFs for D0 = 30, 50, 80 and 250 nm were found to be equal to 1.28, 1.11, 1.13 and 1.22, respectively. The hygroscopic growth spectra were divided into two distinct hygroscopic ranges: a non- and/or slightly hygroscopic mode (GF < 1.12) and a moderately hygroscopic mode (GF > 1.12), which are representative of a suburban environment influenced by local/urban emissions and background aerosol. The standard deviation σ of the GF-PDF was employed as a measure of the mixing state of ambient aerosol. The 30 nm particles were mostly internally mixed, whereas larger particles were found to be externally mixed, either with a distinct bimodal structure or with partly overlapping modes. Cluster analysis on the hourly dry number size distributions was performed to identify the link between aerosol hygroscopicity and aerosol emission sources and formation processes. The size distributions were classified into five groups, with the “mixed urban and regional background” aerosol (67 %) and the “fresh traffic-related particles” from the neighbourhood urban area (15 %) accounting for more than 80 % of the results. The hygroscopic properties for 50 and 80 nm were found to be similar in all cases, indicating particles of similar nature and origin across these sizes. This was also confirmed through the modal analysis of the average number size distributions for each cluster; the 50 and 80 nm particles were found to belong to the same Aitken mode in most cases. The 250 nm particles (i.e. accumulation mode) were generally more hygroscopic than Aitken particles but less hygroscopic than the 30 nm particles (nuclei mode).

Relationships of the Hygroscopicity of HULIS With Their Degrees of Oxygenation and Sources in the Urban Atmosphere

AbstractHumic‐like substances (HULIS) are unresolved compounds isolated from organic matter in atmospheric aerosols. Understanding the chemical structures and sources that control the hygroscopicity of HULIS is important for predicting its environmental impacts and possibly useful for parameterization of the hygroscopicity of organic aerosol (OA). Here, the hygroscopic growth of HULIS from total suspended particles samples in Beijing was analyzed using a hygroscopicity tandem differential mobility analyzer. The hygroscopicity parameter of HULIS (κHULIS) was determined to be 0.06 ± 0.03, and was found to correlate positively with O:C and f44 from offline aerosol mass spectrometry. Additionally, κHULIS was correlated positively with oxygenated organic aerosol (OOA) and correlated negatively with cooking OA and biomass burning OA, for which the source‐related OA types were from mass‐spectral‐based positive matrix factorization analyses. Further analysis resolved substantial κ values of 0.09 and 0.22, respectively, for less‐oxidized and more‐oxidized OOA, in contrast to the low κ values for cooking OA and biomass burning OA. Extensions of O:C‐ and source‐based parameterizations reasonably estimated the hygroscopicity of total OA with a moderate contribution from HULIS. This result and the fact that the obtained OOA contributions to κ of OA were similar to those from different environments suggest the applicability of parameterizing the hygroscopicity for a wide range of OA in particular based on source‐related structural characteristics.

Development of the low-temperature hygroscopicity tandem differential mobility analyzer (Low-T HTDMA) and its application to (NH4)2SO4 and NaCl particles

Influence of water vapor on aerosol particles depends on both relative humidity (RH) and temperature (T). Both temperature and RH should simultaneously be regulated to investigate physical properties of aerosol particles. We developed a low-temperature hygroscopicity tandem differential mobility analyzer (low-T HTDMA), which can be operated in the range of −20 °C ≤ T ≤ 22.5 °C (room temperature), and 0% < RH ≤ 90% (T > 0 °C) or slightly lower than ice saturation RH (T ≤ −10 °C). Temperature was controlled using a chest freezer, refrigerated liquid circulators, fans, and heat exchangers. The employment of heat exchangers allowed the operation of the instrument without immersing the whole setup into liquid coolant. Aerosol particles were humidified using a Shirasu porous glass (SPG) humidifier to facilitate efficient humidification. The performance of the low-T HTDMA was tested using (NH4)2SO4 and NaCl particles. The hygroscopic growth factors of these particles agreed well with previous studies. Deliquescence RH (DRH) of both (NH4)2SO4 and NaCl particles also agreed well with the literature. Compared with the exiting data, efflorescence RH (ERH) measured by the low-T HTDMA exhibited minimal temperature dependence. For instance, the ERH values were 42% (T = −20 °C), 42% (T = −10 °C), and 43% (T = 22.5 °C) for NaCl particles. We suggest that further independent laboratory studies will need to be conducted for experimentally constraining thermodynamic properties of atmospherically important chemical species for T < 0 °C.

Roles of Relative Humidity and Particle Size on Chemical Aging of Tropical Peatland Burning Particles: Potential Influence of Phase State and Implications for Hygroscopic Property

AbstractPeatland fires in Southeast Asia are an important source of primary organic aerosol (POA). Chemical aging of POA in the atmosphere produces oxygenated POA (OPOA). The OPOA production influences optical and hygroscopic properties, modulating the regional climate. However, the roles of environmental parameters such as relative humidity (RH) on chemical aging of peatland burning particles have rarely been investigated. Utilizing the potential aerosol mass (PAM) reactor, we conducted laboratory experiments for POA aging of particles generated from smoldering combustions of surface peat, fern, and Acacia leaves. The corresponding experiments for secondary organic aerosol formation were also separately conducted. Properties and chemical compositions of the resulting particle were quantified by both the hygroscopic tandem differential mobility analyzer and time‐of‐flight aerosol chemical speciation monitor (ToF‐ACSM). Conversion of peat combustion from POA to OPOA was pronounced when RH in the PAM reactor was higher. Considering that previous electromicroscopic observations demonstrated that peat combustion POA is likely (semi)solid, we postulate that oxidation of fresh peatland burning particles is faster at an elevated RH due to reduced viscosity following hygroscopic growth. Hygroscopicity parameter (κ) of aged POA particles linearly correlated with the mass fraction of OPOA that was quantified by the ToF‐ACSM. The above results highlight the importance of simultaneously measuring the chemical aging and particle phase state of peatland burning POA for quantifying their climatic impacts.

Measurement report: Hygroscopic growth of ambient fine particles measured at five sites in China

Abstract. The aerosol hygroscopic growth describes the interaction between aerosols and water vapor, which varies largely, depending on the chemical composition, types, and emissions of gas precursors under diverse environments. In this study, we analyzed size-resolved hygroscopic growth measured at five field sites of China by a hygroscopic tandem differential mobility analyzer (H-TDMA). Results show that the probability density function of hygroscopic growth factor (GF-PDF) at the megacity sites of Guangzhou (GZ), Shanghai (SH), and Beijing (BG) was generally with bimodal hydrophobic and hydrophilic modes, while a unimodal hydrophilic mode was dominated at the suburb sites of Xinzhou (XZ) and Xingtai (XT) throughout the measured particle size of 40–200 nm. As a result, the more hygroscopic (MH) mode accounts for a number fraction of &gt;80 % at the suburb sites, compared to only 20 %–40 % for 40 nm particles at the megacity sites. Further analysis shows that the GF value increases with the aggravated PM2.5 pollution at the sites (BG, XZ, and XT) in northern China, but that is not the case for GZ and SH, which are located in the southern regions. The distinct dependence of GF on the variations in PM2.5 concentrations among the sites suggests the spatial variability in particle composition with the evolution of pollution events in different regions of China. Moreover, different particle hygroscopic behaviors during new particle formation (NPF) events were observed at the five sites, reflecting the distinct mechanisms of NPF in diverse atmospheric environments. By including results from more sites, we find that the aerosol particles observed at those suburb sites are basically more hygroscopic than those in megacities. However, a large variability in the hygroscopic parameter κ at a given particle size among different sites is also observed, suggesting a complex impact from local sources and atmospheric processes. The measured dataset is helpful for improving the understanding of the formation of fine particles and the regional environmental and climate change.

Offline analysis of the chemical composition and hygroscopicity of submicrometer aerosol at an Asian outflow receptor site and comparison with online measurements

Abstract. Filter-based offline analysis of atmospheric aerosol hygroscopicity coupled to composition analysis provides information complementary to that obtained from online analysis. However, its application itself and comparison to online analysis have remained limited to date. In this study, daily submicrometer aerosol particles (PM0.95, 50 % cutoff diameter 0.95 µm) were collected onto quartz fiber filters on Okinawa Island, a receptor of East Asian outflow, in the autumn of 2015. The chemical composition of water-soluble matter (WSM) in PM0.95, PM0.95 itself, and their respective hygroscopicities were characterized through the offline use of an aerosol mass spectrometer and a hygroscopicity tandem differential mobility analyzer. Thereafter, results were compared with those obtained from online analyses. Sulfate dominated the WSM mass (59 %), followed by water-soluble organic matter (WSOM, 20 %) and ammonium (13 %). WSOM accounted for most (91 %) of the mass of extracted organic matter (EOM) and the atomic O-to-C ratios (O:C) of WSOM and EOM were high (mean ± standard deviation were 0.84 ± 0.08 and 0.78 ± 0.08, respectively), both of which indicate highly aged characteristics of the observed aerosol. The hygroscopic growth curves showed clear hysteresis for most samples. At 85 % relative humidity (RH), the calculated hygroscopicity parameter κ values of the WSM (κWSM), WSOM, EOM, and PM0.95 (κPM0.95) were 0.50 ± 0.03, 0.22 ± 0.12, 0.20 ± 0.11, and 0.47 ± 0.03, respectively. An analysis using the thermodynamic Extended Aerosol Inorganics Model (E-AIM) shows, on average, that inorganic salts and WSOM contributed 88 % and 12 %, respectively, of the κWSM (or κPM0.95). High similarities were found between offline and online analysis for chemical compositions that are related to particle hygroscopicity (the mass fractions and O:C of organics and the degree of neutralization) and also for aerosol hygroscopicity. As possible factors governing the variation in κWSM, the influences of WSOM abundance and the neutralization of inorganic salts were assessed. At high RH (70 %–90 %), the hygroscopicity of WSM and PM0.95 was affected considerably by the presence of organic components; at low RH (20 %–50 %), the degree of neutralization could be important. This study not only characterized aerosol hygroscopicity at the receptor site of East Asian outflow but also shows that offline hygroscopicity analysis is an appropriate method, at least for aerosols of the studied type. The results encourage further applications to other environments and to more in-depth hygroscopicity analysis, in particular for organic fractions.

Experimental estimates of hygroscopic growth of particulate fission product species (mixed CsI–CsOH) with implications in reactor accident safety research

Studies on severe nuclear reactor accidents consider CsI and CsOH as the two predominant forms of cesium expected to be released following a reactor accident; 137Cs, 134Cs and 131I being their dominant radioactive forms. Recent studies have measured the hygroscopic growth factors (HGF) and activation fractions for laboratory generated CsI and CsOH particles in sub-saturation and super-saturation relative humidity environments. This work measures and compares the HGF of mixed CsI–CsOH particles with those of individual components. The experiments have been performed with hygroscopic tandem differential mobility analyser for varying mass ratios (w/w) of CsI: CsOH and the results have been compared with the theoretical estimates made using Brechtel and Kredneweis (2000) theory in conjugation of ZSR (Zdanovskii–Stokes–Robinson) mixing rule. The study shows different behavioural pattern of hygroscopic growth of mixed particles in comparison to individual components. A clear transitional change in the growth factor patterns was observed for the ratio below 1:1. Additionally, the experiments to study the effect of different dry diameters (50, 100, 150 and 200 nm) for 1:1 ratio revealed that hygroscopic growth was independent of initial dry diameter. Effect of dehydration for 3 mixing ratios viz., 1:02, 1:1 and 1:10 showed continuous pattern indicating the dominance of CsOH. Terminal settling velocities for the mixed and individual particles are compared for highlighting the probable impact on surface deposition flux calculations. The aerosol hygroscopic growth of mixed CsI–CsOH particles has direct implications in improving source term estimates for a severe reactor accident safety analysis.

Measurement report: On the difference in aerosol hygroscopicity between high and low relative humidity conditions in the North China Plain

Abstract. Atmospheric processes, including both primary emissions and secondary formation, may exert complex effects on aerosol hygroscopicity, which is of significant importance in understanding and quantifying the effect of aerosols on climate and human health. In order to explore the influence of local emissions and secondary formation processes on aerosol hygroscopicity, we investigated the hygroscopic properties of submicron aerosol particles at a rural site in the North China Plain (NCP) in winter 2018. This was conducted by simultaneous measurements of aerosol hygroscopicity and chemical composition, using a custom-built hygroscopic tandem differential mobility analyzer (HTDMA) and a capture-vaporizer time-of-flight aerosol chemical speciation monitor (CV-ToF-ACSM). The hygroscopicity results showed that the particles during the entire campaign were mainly externally mixed, with a more hygroscopic (MH) mode and a less hygroscopic (LH) mode. The mean hygroscopicity parameter (κmean) values derived from hygroscopicity measurements for particles at 60, 100, 150, and 200 nm were 0.16, 0.18, 0.16, and 0.15, respectively. During this study, we classified two distinct episodes with different relative humidity (RH) and temperature (T) conditions, indicative of different primary emissions and secondary formation processes. It was observed that aerosols at all measured sizes were more hygroscopic under the high-RH (HRH) episode than those under the low-RH (LRH) episode. During the LRH, κ decreased with increasing particle size, which may be explained by the enhanced domestic heating at low temperature, causing large emissions of non-hygroscopic or less hygroscopic primary aerosols. This is particularly obvious for 200 nm particles, with a dominant number fraction (&gt;50 %) of LH mode particles. Using O:C-dependent hygroscopic parameters of secondary organic compounds (κSOA), closure analysis between the HTDMA-measured κ and the ACSM-derived κ was carried out. The results showed that κSOA under the LRH episode was less sensitive to the changes in organic oxidation level, while κSOA under HRH had a relatively stronger dependency on the organic O:C ratio. This feature suggests that the different sources and aerosol evolution processes, partly resulting from the variation in atmospheric RH and T conditions, may lead to significant changes in aerosol chemical composition, which will further influence their corresponding physical properties.

Hygroscopicity of organic compounds as a function of organic functionality, water solubility, molecular weight, and oxidation level

Abstract. Aerosol hygroscopicity strongly influences the number size distribution, phase state, optical properties, and multiphase chemistry of aerosol particles. Due to the large number of organic species in atmospheric aerosols, the determination of the hygroscopicity of ambient aerosols remains challenging. In this study, we measured the hygroscopic properties of 23 organics, including carboxylic acids, amino acids, sugars, and alcohols, using a hygroscopicity tandem differential mobility analyzer (HTDMA). Earlier studies have characterized the hygroscopicity either for a limited number of organic compounds using similar techniques or for particles at sizes beyond the microscale range or even bulk samples using other methodologies. Here, we validate these studies and extend the data by measuring the hygroscopicity of a broader suite of organics for particles with sizes under the submicrometer range that are more atmospherically relevant. Moreover, we systematically evaluate the roles of that related physicochemical properties play in organic hygroscopicity. We show that the hygroscopicity of organics varies widely with functional groups and organics with the same carbon number but that more functional groups show higher hygroscopicity. However, some isomers that are very similar in molecular structure show quite different hygroscopicity, demonstrating that other physicochemical properties, such as water solubility, may contribute to their hygroscopicity as well. If the organics are fully dissolved in water (solubility &gt;7×10-1 g mL−1), we found that their hygroscopicity is mainly controlled by their molecular weight. For the organics that are not fully dissolved in water (slightly soluble: 5×10-4 g mL−1 &lt; solubility &lt; 7×10-1 g mL−1), we observed that some of them show no obvious water uptake, which is probably due to the fact that they may not deliquesce under our studied conditions up to 90 % relative humidity (RH). The other type of slightly soluble organic material is moderately hygroscopic, and the larger its solubility is, the higher its hygroscopicity will be. Moreover, the hygroscopicity of organics generally increased with O:C ratios, although this relationship is not linear.

Atmospheric Particle Hygroscopicity and the Influence by Oxidation State of Organic Aerosols in Urban Beijing

A hygroscopic tandem differential mobility analyser (H-TDMA) was used to observe the size-resolved hygroscopic characteristics of submicron particles in January and April 2018 in urban Beijing. The probability distribution of the hygroscopic growth factor (HGF-PDF) in winter and spring usually showed a bimodal pattern, with more hygroscopic mode (MH) being more dominant. The seasonal variation in particle hygroscopicity was related to the origin of air mass, which received polluted southerly air masses in spring and clean northwesterly air masses in winter. Particles showed stronger hygroscopic behaviour during heavy pollution episodes (HPEs) with elevated concentrations of secondary aerosols, especially higher mass fraction of nitrate, which were indicated using the PM2.5 (particulate matter with diameter below 2.5 µm) mass concentration normalised by CO mass concentration. The hygroscopic parameter (κ) values were calculated using H-TDMA (κhtdma) and chemical composition (κchem). The closure study showed that κchem was overestimated in winter afternoon when compared with κhtdma, because the organic particle hygroscopic parameter (κorg) was overestimated in the calculations. It was influenced by the presence of a high concentration of hydrocarbon-like organic aerosol (HOA) with a weak water uptake ability. A positive relationship was observed between κorg and the ratio of oxygenated organic aerosol (OOA) and HOA, thereby indicating that the strong oxidation state enhanced the hygroscopicity of the particles. This study revealed the effect of local emission sources and secondary aerosol formation processes on particle hygroscopicity, which is of great significance for understanding the pollution formation mechanism in the North China Plain.

Evaluation of assumptions made by Hygroscopic Tandem Differential Mobility Analyzer inversion routines

The Hygroscopic Tandem Differential Mobility Analyzer (H-TDMA) measures the hygroscopicity of atmospheric particles, and many atmospheric processes that change this hygroscopicity also change the atmospheric size distribution. Two assumptions made during H-TDMA inversion create spurious hygroscopic trends as a function of the changing inlet size distribution. These two assumptions—that the particles exiting the first Differential Mobility Analyzer (DMA1) are singly charged and that the inlet size distribution has a slope of zero (flat)— generate Multi-Charge Dispersion (MCD) bias and Slope bias, respectively. First, we use a model, named TAO, to show that the inlet size distribution could theoretically change the measured ammonium sulfate hygroscopicity by 10%–20% as a function of diameter or experimental time with no change in relative humidity. Secondly, we show experimentally that aerosol emitted from the flaming combustion of grass creates MCD bias. In this experiment, we measure the CPC response of the first three charges and invert these responses using a new routine named Junior. Junior's inversion of each charge shows that one growth factor distribution describes all measured diameters (no growth dependence on diameter). As in the modeling study above, previous publications of this aerosol system, using traditional inversion assumptions, report a decrease in hygroscopicity as DMA1 diameter increases. Unlike traditional inversions, Junior's inversion does not assume the particles are singly charged nor does it make the flat inlet size distribution assumption. Instead, both the inlet size distribution and each charge's CPC response are measured quantities. Thus, the discrepancy between our inversion results and previous publications is likely due to the traditional inversion routine assumptions. This underscores the importance for accounting for Slope and MCD bias during inversions. Experimental results should be carefully analyzed when reporting hygroscopic trends with respect to diameter or experimental time when using the traditional inversion assumptions.

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

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