Components Of Atmospheric Aerosols Research Articles

Multiyear high-temporal-resolution measurements of submicron aerosols at 13 French urban sites: data processing and chemical composition

Abstract. This paper presents a first comprehensive analysis of long-term measurements of atmospheric aerosol components from aerosol chemical speciation monitor (ACSM) and multiwavelength Aethalometer (AE33) instruments collected between 2015 and 2021 at 13 (sub)urban sites as part of the French CARA (Chemical Characterization of Particles) program. The datasets contain the mass concentrations of major chemical species within submicron aerosols (PM1), namely organic aerosols (OAs), nitrate (NO3-), ammonium (NH4+), sulfate (SO42-), non-sea-salt chloride (Cl−), and equivalent black carbon (eBC). Rigorous quality control, technical validation, and environmental evaluation processes were applied, adhering to both guidance from the French Reference Laboratory for Air Quality Monitoring (LCSQA) and the Aerosol, Clouds, and Trace Gases Research Infrastructure (ACTRIS) standard operating procedures. Key findings include geographical differences in the aerosol chemical composition, seasonal variations, and diel patterns, which are influenced by meteorological conditions, anthropogenic activities, and proximity to emission sources. Overall, OA dominates PM1 at each site (43 %–60 % of total mass), showing distinct seasonality with higher concentrations (i) in winter, due to enhanced residential heating emissions, and (ii) in summer, due to increased photochemistry favoring secondary aerosol formation. NO3 is the second most important contributor to PM1 (15 %–30 %), peaking in late winter and early spring, especially in northern France, and playing a significant role during pollution episodes. SO4 (8 %–14 %) and eBC (5 %–11 %) complement the major fine-aerosol species, with their relative contributions strongly influenced by the origin of air masses and the stability of meteorological conditions, respectively. A comparison with the 3D chemical transport model (CTM) CHIMERE shows high correlations between simulations and measurements, albeit with an OA concentration underestimation of 46 %–76 %. Regional discrepancies in NO3 concentration levels emphasize the importance of these datasets with respect to validating air quality models and tailoring air pollution mitigation strategies. The datasets can be found at https://doi.org/10.5281/zenodo.13318298 (Chebaicheb et al., 2024).

CHARACTERIZATION OF FINE CARBONACEOUS AEROSOLS FROM THE EASTERN MEDITERRANEAN: CONTRIBUTIONS OF FOSSIL AND NON-FOSSIL CARBON SOURCES

ABSTRACT In order to better characterise carbonaceous components in atmospheric aerosols and to assess the contributions of fossil carbon (FC) and non-fossil carbon (NFC) sources and their seasonality in the Eastern Mediterranean, we collected fine (PM1.3) aerosols at a remote marine background site, the Finokalia Research Station, Crete, Greece, over a period of one-year. PM1.3 samples were analysed for elemental carbon (EC), organic carbon (OC), water-soluble OC (WSOC), and stable carbon isotope ratio (δ13CTC) and radiocarbon content (14CTC) (pMC) of total carbon (TC). All the parameters, i.e., PM1.3, δ13CTC and 14CTC showed a clear temporal pattern with higher values in summer and lower values in autumn. The 14CTC ranged from 54.7 to 99.1 pMC with an average of 74.5 pMC during the entire year. The FC content in TC (FCTC) was found to be slightly lower in winter and almost stable in other seasons, whereas the NFC contents (NFCTC) showed a clear seasonality with the highest level in summer followed by spring and the lowest level in winter. Based on these results together with the seasonal distributions of organic tracers, we found that biomass burning (BB) and soil dust are two major sources of the fine aerosols in winter. Although biogenic emissions of VOCs followed by subsequent secondary oxidation processes are significant in summer followed by spring and autumn, pollen is a significant contributor to TC in spring. This study showed that emissions from fossil fuel combustion are significant (25.5%) but minor compared to NFC sources in the eastern Mediterranean.

Long-term spatiotemporal distribution characterization of atmospheric black carbon MERRA-2 concentration over China

Black carbon (BC), a component of atmospheric aerosols, strongly adsorbs solar radiation, thereby influencing atmospheric stability and air quality. In this study, the spatiotemporal distribution, historical trends, and influencing factors of BC concentration in China from 1980 to 2020 have been investigated using MERRA-2 (Modern-era Retrospective Analysis for Research and Applications, Vision2) reanalysis dataset, population distribution, and industrial statistics data. The annual total MERRA-2 BC concentration in China (averaging 1.08 μg/m3 over the study period) exhibited three distinct phases: slow growth (1980–1999, 0.02 μg/m3/year), rapid growth (2000–2007, 0.61 μg/m3/year), and gradual decline (2008–2020, -0.014 μg/m3/year). The BC concentration was consistently higher in autumn and winter than in spring and summer, being lowest in July (9.6 μg/m3) and highest in December (14 μg/m3). Spatially, the annual average BC concentration from 1980 to 2020 followed the order: central Yangtze River region (3.14 μg/m3) > eastern coastal region (2.72 μg/m3) > northeastern region (1.40 μg/m3) > western riverine region (0.69 μg/m3) > northwestern frontier region (0.31 μg/m3). High BC-concentration areas, mainly in the central and eastern regions, correlate with regions of vigorous human activities and high industrialization levels, confirming that human activity markedly influences BC pollution. Since 2013, the implementation of emission control strategies and adjustments in the energy structure in China had led to a significant decline in BC concentration. By revealing the spatiotemporal distribution and trends of BC concentration in China, this study provides valuable scientific insights for atmospheric science, environmental protection, and air pollution.

Saltation‐Induced Dust Emission of Dust Devils in the Convective Boundary Layer—An LES Study on the Meter Scale

AbstractDust devils are vertically oriented, columnar vortices that form within the atmospheric convective boundary layer (CBL) of dry regions. They are able to lift a sufficient amount of soil particles including dust to become visible and are considered as a potentially important dust source for the atmosphere. Mineral dust, a key component of atmospheric aerosols, influences the climate by affecting the radiation budget and cloud formation. Current estimates of the contribution of dust devils to the global, regional, and local dust release vary considerably from less than 1% to more than 50%. To address this uncertainty, we perform the highest resolved large‐eddy simulation (LES) study on dust emission in the CBL to date, using the PALM model system and the saltation‐based Air Force Weather Agency (AFWA) dust emission scheme. Our results show that under desert‐like conditions, dust devils are responsible for an average of 5% of regional dust emissions, with temporary maxima of up to 15%. This contrasts with previous measurement‐based (>35%) and LES‐based estimates (∼0.1%). Local emissions of dust devils (up to 10 mg m−2 s−1) are 1–3 orders of magnitude higher than the emission in the surroundings. This makes dust devils important for air quality and visibility. Additionally, our study reveals previously unknown large‐scale convective dust emission patterns. These patterns are tied to the CBL's cellular flow structure and are the main cause of dust release. Contrary to other studies, our findings clarify the important role of saltation‐induced dust emission.

Morphological and optical properties of carbonaceous aerosol particles from ship emissions and biomass burning during a summer cruise measurement in the South China Sea

Abstract. Carbonaceous aerosols constitute a crucial component of atmospheric marine aerosols among which black carbon (BC) and brown carbon (BrC) are important contributors to light absorption and hence the positive climatic radiative forcing in the marine atmosphere. We conducted month-long (5 May–9 June 2021) onboard sample collections and online measurements of carbonaceous aerosols to characterize their morphological and optical properties during a ship cruise in the South China Sea (SCS), covering a marine region of 11.9–24.5° N, 111.1–118.2° E. Single particles were collected by a single-particle sampler, and offline analyses were performed using a transmission electron microscope (TEM) coupled with energy-dispersive X-ray spectroscopy (EDS). Online measurements of BC in PM2.5 were made by a seven-wavelength aethalometer, and organic carbon (OC) and elemental carbon (EC) mass concentrations were measured by a semi-online OC/EC analyzer. Feret diameters of the single particles during navigation and stop showed size distributions with the lognormal fitting peaks at 307 and 325 nm, respectively. The fresh (without coating) and aged BC particles (after removal of coating by the electron beams in the TEM) showed same median fractal dimensions (1.61), in contrast to their different median lacunarities (0.53 vs. 0.59). The aged BC particles showed narrower Feret diameters (229–2557 nm) during navigation than those (78–2926 nm) of freshly emitted BC from the ship's own exhaust during stop. Moreover, tar balls, as one important component of single particles from ship emissions and as the tracer of biomass burning, were identified with geometrical diameters of 160–420 nm in the TEM images. The EDS analyses showed those tar balls are mainly mixed with sea salt, organics, BC, and sulfate. We also found a significant fraction of aged BC in various mixing states (core–shell, embedded) with other components of the aerosol particles after long-range transport. The campaign was further divided into several periods (the before-monsoon period, BMP; transition monsoon period, TMP; after-monsoon period, AMP; and ship pollution period, SPP) according to the wind direction during monsoon and the ship's own pollution. The median absorption Ångström exponent (AAE) values derived from all wavelengths were 1.14, 1.02, 1.08, and 1.06 for BMP, TMP, AMP, and SPP, respectively. Particularly, a median AAE value of 1.93 was obtained during two significant biomass burning events. These results showed that biomass burning (BB) and fossil fuel (FF) combustion contributed to 18 %–22 % and 78 %–82 % of all the BC light absorption without the two intense biomass burning events, during which BB and FF accounted for 42 % and 58 %, respectively. The two BB events originated from the Philippines and Southeast Asia before and after the summer monsoon. Our results demonstrated that BC can serve as the core of aged particles, but the fractal dimensions of BC aggregates were subject to little variation; moreover, such BC particles become much more aggregated after aging in the marine atmosphere, which further affects the light absorption of the BC particles in the SCS.

Characteristics and Source Analysis of Carbonaceous Aerosols in PM2.5 in Huaxi District, Guiyang

Carbonaceous aerosol, as an important component of atmospheric aerosol, has a significant impact on atmospheric environmental quality, human health, and global climate change. To investigate the characteristics and sources of carbonaceous aerosol in atmospheric fine particulate matter (PM2.5) in Huaxi District of Guiyang, an in-situ observational study was conducted during different seasons in 2020, and the carbonaceous components of PM2.5 were measured using a thermal-optical carbon analyzer (DRI Model 2015). The results of the study showed that the average concentrations of PM2.5, total carbonaceous aerosol (TCA), organic carbon (OC), secondary organic carbon (SOC), and elemental carbon (EC) concentrations during the observation period were (39.7±22.3), (14.1±7.2), (7.6±3.9), (4.4±2.6), and (2.0±1.0) μg·m-3, respectively, and the mean value of OC/EC was (3.9±0.8). ρ(PM2.5), ρ(TCA), ρ(OC), ρ(SOC), and ρ(EC) showed a seasonal variation pattern with the highest in winter [(52.6±28.6), (17.0±9.6), (9.1±5.2), (6.1±3.9), and (2.4±1.2) μg·m-3, respectively] and the lowest in summer [(25.1±7.1), (11.6±3.6), (6.3±1.9), (3.7±1.2), and (1.6±0.6) μg·m-3, respectively]. The seasonal variation in OC/EC showed summer (4.2±0.8) > winter (3.8±0.9) > autumn (3.8±0.5) > spring (3.7±0.9), indicating the presence of SOC generation in all seasons in Huaxi District. SOC showed a significant correlation with OC (R2 =0.9), and the SOC concentration tended to increase with the increase in atmospheric oxidation. OC showed a good correlation with EC in all seasons, with the highest in autumn (R2 =0.9) and lower correlations in the other three seasons (R2 ranged from 0.74 to 0.75), indicating a common source. According to OC/EC ratio range, it was preliminarily determined that carbonaceous aerosol came from vehicle exhaust emissions, coal burning emissions, and biomass combustion emissions. In order to further quantify the contribution of major emission sources to carbonaceous aerosol, the results of this study using PMF to analyze the sources of carbonaceous aerosol showed that the main sources of carbonaceous aerosol in Huaxi District of Guiyang were coal combustion sources (29.3%), motor vehicle emission sources (21.5%), and biomass combustion sources (49.2%).

Impact of Nitrate and Iron Ions on Uptake Coefficients and Condensed Phase Products From the Reaction of Gaseous NO2 With HULIS Proxies

AbstractHumic‐like substances (HULIS) are a ubiquitous reactive component of atmospheric aerosol. They participate in the formation of secondary organic aerosols via chemical reactions with atmospheric oxidants. Here, we assess the influence of transition metal ions (namely ferric iron, Fe(III)), and nitrate ions () on the heterogeneous reaction of gaseous NO2 with an aqueous film containing gallic acid (GA) or tannic acid (TA) as proxies for HULIS. Using a vertical wetted wall flow tube technique, the uptake coefficients of gaseous NO2 on GA and TA increased nonlinearly with increasing [Fe(III)], in dark and under light irradiation. However, the combined effect of both ions, Fe(III) and , led to a substantial decrease in NO2 uptake in the dark and under simulated near‐UV sunlight irradiation (300 < λ < 400 nm). The lifetime of GA in dilute aqueous phase, which corresponds to cloud water, due to reaction with NO2 would be 6 hr during both nighttime and daytime. However, the lifetime of GA in aerosol particles which contain both ions, that is, Fe(III) and , would increase to 27 hr during nighttime and 11 days and 6 hr due to light‐induced reaction with NO2. Also, we observed, using Fourier transform ion cyclotron resonance mass spectrometry, the formation of nitrocatechols compounds (e.g., methyl‐nitrocatechol), which contribute to brown carbon. Compounds with reduced functional groups such as amines were also observed in the presence of iron and nitrate ions in the dark and under irradiation, indicating that Fe(III) and , can influence the kinetics and product distribution in deliquescent aerosol particles.

High-altitude glacier archives lost due to climate change-related melting

Global warming has caused widespread surface lowering of mountain glaciers. By comparing two firn cores collected in 2018 and 2020 from Corbassière glacier in Switzerland, we demonstrate how vulnerable these precious archives of past environmental conditions have become. Within two years, the soluble impurity records were destroyed by melting. The glacier is now irrevocably lost as an archive for reconstructing major atmospheric aerosol components.

Uptake and reactivity of NO2 on the hydroxylated silica surface: A source of reactive oxygen species

We report state-of-the-art first-principles molecular dynamics results on the heterogeneous chemical uptake of NO2, a major anthropogenic pollutant, on the dry and wet hydroxylated surface of α-quartz, which is a significant component of silica-based catalysts and atmospheric dust aerosols. Our investigation spotlights an unexpected chemical pathway by which NO2 (i) can be adsorbed as HONO by deprotonation of interfacial silanols (i.e., –Si–OH group) on silica, (ii) can be barrierless converted to nitric acid, and (iii) can finally dissociated to surface bounded NO and hydroxyl gas phase radicals. This chemical pathway does not invoke any previously experimentally postulated NO2 dimerization, dimerization that is less likely to occur at low NO2 concentrations. Moreover, water significantly catalyzes the HONO formation and the dissociation of nitric acid into surface-bounded NO and OH radicals, while visible light adsorption can further promote these chemical transformations. This work highlights how water-restricted solvation regimes on common mineral substrates are likely to be a source of reactive oxygen species, and it offers a theoretical framework for further and desirable experimental efforts, aiming to better constrain trace gases/mineral interactions at different relative humidity conditions.

Evaluation of MERRA-2 and CAMS reanalysis for black carbon aerosol in China

Black carbon (BC) constitutes a pivotal component of atmospheric aerosols, significantly impacting regional and global radiation balance, climate, and human health. In this study, we evaluated BC data in two prominent atmospheric composition reanalysis datasets: the Modern-Era Retrospective analysis for Research and Applications, Version 2 (MERRA-2) and the Copernicus Atmosphere Monitoring Service (CAMS), and analyzed the causes of their deviations. This assessment is based on observational data collected from 34 monitoring stations across China from 2006 to 2022. Our research reveals a significant and consistent decline in BC concentrations within China, amounting to a reduction exceeding 67.33%. However, both MERRA-2 and CAMS reanalysis data fail to capture this declining trend. The average annual decrease of BC in MERRA-2 from 2006 to 2022 is only 0.06 μg/m3 per year, while the BC concentration in CAMS even increased with an average annual value of 0.014 μg/m3 per year. In 2022, MERRA-2 had overestimated BC concentration by 20% compared to observational data, while CAMS had overestimated it by approximately 66%. In the regional BC concentration analysis, the data quality of the reanalysis data is better in the South China (RM = 0.59, RC = 0.53), followed by the North China (RM = 0.50, RC = 0.42). Reanalysis BC data in Northwest China and the Tibetan Plateau are difficult to use for practical analysis due to their big difference with observation. In a comparison of the anthropogenic BC emissions inventory used in the two atmospheric composition reanalysis datasets with the Multi-resolution Emission Inventory model for Climate and air pollution research (MEIC) emissions inventory, we found that: Despite the significant decline in China's BC emissions, MERRA-2 still relies on the 2006 emissions inventory, while CAMS utilizes emission inventories that even show an increasing trend. These factors will undoubtedly lead to greater deviations between reanalysis and observational data.

Comparison of six approaches to predicting droplet activation of surface active aerosol – Part 2: Strong surfactants

Abstract. Surfactants have been a focus of investigation in atmospheric sciences for decades due to their ability to modify the water uptake and cloud formation potential of aerosols. Surfactants adsorb at the surface and can decrease the surface tension of aqueous solutions. In microscopic aqueous droplets with finite amounts of solute, surface adsorption may simultaneously deplete the droplet bulk of the surfactant. While this mechanism is now broadly accepted, the representation in atmospheric and cloud droplet models is still not well constrained. We compare the predictions of five bulk–surface partitioning models documented in the literature to represent aerosol surface activity in Köhler calculations of cloud droplet activation. The models are applied to common aerosol systems, consisting of strong atmospheric surfactants (sodium myristate or myristic acid) and sodium chloride in a wide range of relative mixing ratios. For the same particles, the partitioning models predict similar critical droplet properties at small surfactant mass fractions, but differences between the model predictions increase significantly with the surfactant mass fraction in the particles. Furthermore, significantly different surface tensions are predicted for growing droplets at given ambient conditions along the Köhler curves. The inter-model variation for these strong surfactant particles is different than previously observed for moderately surface active atmospheric aerosol components. Our results highlight the importance of establishing bulk–surface partitioning effects in Köhler calculations for a wide range of conditions and aerosol types relevant to the atmosphere. In particular, conclusions made for a single type of surface active aerosol and surface activity model may not be immediately generalized.

Observing Mineral Dust in Northern Africa, the Middle East, and Europe: Current Capabilities and Challenges ahead for the Development of Dust Services

Abstract Mineral dust produced by wind erosion of arid and semiarid surfaces is a major component of atmospheric aerosol that affects climate, weather, ecosystems, and socioeconomic sectors such as human health, transportation, solar energy, and air quality. Understanding these effects and ultimately improving the resilience of affected countries requires a reliable, dense, and diverse set of dust observations, fundamental for the development and the provision of skillful dust-forecast-tailored products. The last decade has seen a notable improvement of dust observational capabilities in terms of considered parameters, geographical coverage, and delivery times, as well as of tailored products of interest to both the scientific community and the various end-users. Given this progress, here we review the current state of observational capabilities, including in situ, ground-based, and satellite remote sensing observations in northern Africa, the Middle East, and Europe for the provision of dust information considering the needs of various users. We also critically discuss observational gaps and related unresolved questions while providing suggestions for overcoming the current limitations. Our review aims to be a milestone for discussing dust observational gaps at a global level to address the needs of users, from research communities to nonscientific stakeholders.

Mechanism-based structure-activity relationship investigation on hydrolysis kinetics of atmospheric organic nitrates

Organic nitrates are key components of atmospheric organic aerosols. Hydrolysis is one of their main transformation pathways, affecting atmospheric nitrogen cycle and the properties of organic aerosols. Studying hydrolysis using experiments is hindered by limited authentic chemical standards. To advance our understanding on the hydrolysis of organic nitrates, we apply quantum chemistry methods here to establish a structure-activity relationship of the mechanisms and kinetics by selecting eight organic nitrates as model compounds. The results indicate that an acid-catalyzed mechanism is dominant for the most considered organic nitrates at pH corresponding to ambient organic aerosol (pH < 5). More importantly, a hydrolysis pathway driven by the shift of hydrogen or methyl cation is unveiled. Based on the revealed mechanisms, quaternary C at the α-site, tertiary/quaternary C at the β-site, and –C=C at the β/γ-site of the −ONO2 group are determined to be the key structural factors for the fast hydrolysis kinetics. An important feature for the hydrolysis of organic nitrates with such structural factors is proceeding via a carbocation intermediate. The formed carbocation could further mediate the organic aerosol chemistry, affecting the composition and properties of organic aerosols. This study provides a basis to further develop predictive models for hydrolysis kinetics of organic nitrates.

Effects of simulated secondary organic aerosol water on PM1 levels and composition over the US

Abstract. Water is a key component of atmospheric aerosol, affecting many aerosol processes including gas-to-particle partitioning of semi-volatile compounds. Water related to secondary organic aerosol (SOAW) is often neglected in atmospheric chemical transport models and is not considered in gas-to-particle partitioning calculations for inorganic species. We use a new inorganic aerosol thermodynamics model, ISORROPIA-lite, which considers the effects of SOAW, to perform chemical transport model simulations for 1 year over the continental United States to quantify its effects on aerosol mass concentration and composition. SOAW can increase average fine aerosol water levels by up to a factor of 2 when secondary organic aerosol (SOA) is a major PM1 component. This is often the case in the south-eastern US, where SOA concentrations are higher. Although the annual average impact of this added water on total dry PM1 concentrations due to increased partitioning of nitrate and ammonium is small (up to 0.1 µg m−3), total dry PM1 increases of up to 2 µg m−3 (with nitrate levels increases of up to 200 %) can occur when RH levels and PM1 concentrations are high.

Molecular Composition of Anthropogenic Oxygenated Organic Molecules and Their Contribution to Organic Aerosol in a Coastal City.

Organic aerosols (OA) have gained attention as a substantial component of atmospheric aerosols owing to their impact on atmospheric visibility, climate, and human health. Although oxygenated organic molecules (OOMs) are essential contributors to OA formation, the sources, transformations, and fates of the OOMs are not fully understood. Herein, anthropogenic OOMs (AOOMs), anthropogenic volatile organic compounds (AVOCs), and OA were concurrently measured in Xiamen, a coastal city in southeastern China. Our results show that the AOOMs exhibited a high nitrogen content (76%) and a low oxidation degree. Strong photochemical processes of aromatic VOCs were the predominant sources of AOOMs. Also, NOx concentrations and the occurrence of multigeneration OH radical oxidations were the critical factors that might influence the formation of AOOMs. Finally, the newly developed aerosol dynamic model's results show that more than 35% of the OA mass growth rate is attributed to the gas-particle partitioning of AOOMs. Further sensitivity testing demonstrates that the contribution of AOOMs to OA growth is significantly enhanced during high-particulate-concentration periods, especially under low-temperature conditions. This study emphasizes the vital role of photochemically produced AOOMs derived from AVOCs in OA growth in a coastal urban atmosphere.

Evaluation of MERRA-2 Black Carbon Characteristics and Potential Sources over China

Black carbon (BC), an important component of atmospheric aerosol, plays a significant role in regional climate, hydrological cycle, variation of monsoon rainfall, and human health. The 40-year detailed atmospheric BC over China from 1981 to 2020 is systematically investigated through the MERRA-2 reanalysis dataset. MERRA-2 BC generally showed a good correlation (R = 0.68) compared with 673 monthly samples from ground-based observation at 35 stations around China. The overall annual average of MERRA-2 BC concentration over China is 1.15 μg/m3, with a fast growth rate during 1981–2007 and a relatively slow decrease after that. The winter season has the highest mean concentration of BC, followed by autumn and spring, whereas summer shows relatively weaker values. The order of annual average BC concentrations during 1981–2020 is Beijing-Tianjin-Hebei region (BTH, 4.02 μg/m3) &gt; Sichuan Basin (SB, 3.94 μg/m3) &gt; Yangtze River Delta (YRD, 2.68 μg/m3) &gt; Pearl River Delta (PRD, 1.47 μg/m3). The monthly mean BC concentrations over the BTH, YRD, PRD and SB are estimated to be smallest 3.18 μg/m3 in May, 1.94 μg/m3 in August, 0.82 μg/m3 in July, 3.04 μg/m3 in June, respectively, whilst largest consistently in December with 5.09 μg/m3, 3.83 μg/m3, 2.12 μg/m3, and 5.41 μg/m3, respectively. Our study indicates the primary potential source areas for BC are concentrated in the research city and its surroundings. Beijing and Chengdu are more BC-polluted areas than Shanghai and Guangzhou. Long-distance, regional transfer from south BTH contributes importantly to BC pollution in Beijing under the influence of prevailing southerly winds. The geographical location of Chengdu causes the transport and accumulation of BC inside the SB.

Assessment of submicron aerosol liquid water content and mass-based growth factors in South Asian outflow over the Indian Ocean

Aerosol-bound water, a ubiquitous and abundant component of atmospheric aerosols, has an impact on regional climate, visibility, human health, the hydrological cycle, and atmospheric chemistry. Yet, the intricate relationship between aerosol liquid water (ALWC) and chemical composition and relative humidity (RH) was not well understood. The present study explores ALWC derived from the ISORROPIA II model using real-time, high-resolution data of non-refractory submicron chemical species and meteorological parameters (temperature and RH) collected over the Indian Ocean as part of the ICARB (Integrated Campaign for Aerosols, Gases, and Radiation Budget)-2018 experiment. Results show that ALWC values over the South Eastern Arabian Sea (SEAS) were found to be higher by 4–6 times than those observed over the Equatorial Indian Ocean (EIO) due to a large decrease in aerosol loading from SEAS to EIO. ALWC peaked in the early morning hours (4:00–7:00), with greater values during the nighttime and lower values during the daytime across SEAS, which is comparable with RH variation. While the ratio of organics-to-SO42− mass fraction linearly decreased with increasing mass-based growth factors (MGFs) over EIO, such a scenario was not observed over SEAS. The latitudinal gradient of mass fraction of ALWC had shown a decrease towards EIO, consistent with organic fraction. The extinction coefficient of the dry mass of submicron particles is noticeably increased by 40 % by ALWC over SEAS and EIO. Moreover, ALWC could enhance the aerosol negative forcing by an average of 66 % (64 %) over SEAS (EIO) at the top of the atmosphere during the cruise period. These inferences imply that ALWC is the key factor in assessing the role of aerosols on atmospheric radiative forcing. Overall, the present study highlights the serious need to consider the ALWC in climate forcing simulations, particularly in moist tropical environments where their effect can be significant.

Glass Transition Temperatures of Organic Mixtures from Isoprene Epoxydiol-Derived Secondary Organic Aerosol.

The phase states and glass transition temperatures (Tg) of secondary organic aerosol (SOA) particles are important to resolve for understanding the formation, growth, and fate of SOA as well as their cloud formation properties. Currently, there is a limited understanding of how Tg changes with the composition of organic and inorganic components of atmospheric aerosol. Using broadband dielectric spectroscopy, we measured the Tg of organic mixtures containing isoprene epoxydiol (IEPOX)-derived SOA components, including 2-methyltetrols (2-MT), 2-methyltetrol-sulfate (2-MTS), and 3-methyltetrol-sulfate (3-MTS). The results demonstrate that the Tg of mixtures depends on their composition. The Kwei equation, a modified Gordon-Taylor equation with an added quadratic term and a fitting parameter representing strong intermolecular interactions, provides a good fit for the Tg-composition relationship of complex mixtures. By combining Raman spectroscopy with geometry optimization simulations obtained using density functional theory, we demonstrate that the non-linear deviation of Tg as a function of composition may be caused by changes in the extent of hydrogen bonding in the mixture.

Characteristics, seasonal variations, and dry deposition fluxes of carbonaceous and water-soluble organic components in atmospheric aerosols over China's marginal seas

A total of 37 atmospheric aerosol samples were collected over the Yellow and Bohai Seas (YBS) during four cruises in autumn, winter, spring and summer from 2017 to 2018. The concentrations of organic carbon (OC) and water-soluble organic carbon (WSOC) ranged from 1.04 to 15.43 μg m−3 and 0.77–5.49 μg m−3, respectively, with higher values in autumn and winter than in spring and summer. WSOC contributed 68.49 % to OC in summer and 34.55 % in winter and was affected by temperature and relative humidity. Dicarboxylic acid showed a predominance of oxalic acid followed by malonic and then succinic acids. The contributions of secondary sources to OC and WSOC were 54 % and 65.3 %, respectively, indicating the importance of secondary aging in improving the water solubility of OC. The dry deposition flux of WSOC over the YBS was estimated to be 0.87 mg m−2 d−1, which might play a potential role in the marine carbon cycle.

Nitration of Phenols by Reaction with Aqueous Nitrite: A Pathway for the Formation of Atmospheric Brown Carbon

Nitrophenols are a major component of light-absorbing atmospheric organic aerosols, commonly referred to as brown carbon (BrC). Most nitrophenol formation pathways involve reactions of phenolic compounds with OH, NO3, and NO2 in the gas phase. In this study, an aqueous nitrophenol production pathway is investigated that can proceed in the dark without apparent OH radical formation. Using high-performance liquid chromatography–mass spectrometry, we demonstrate that catechol reacts in acidic solutions with dissolved nitrite to form nitrocatechol. The rate of nitration increases significantly from pH 4.4 to pH 3.4 such that nitrocatechol is susceptible to second-generation reactions under the most acidic conditions producing chromophores that absorb in the visible region (peak at 425 nm). Increases in the N:C ratio of the reaction solution, as detected by aerosol mass spectrometry, and enhanced absorption from 300 to 500 nm of wood and peat smoke aqueous extracts exposed to nitrite suggest that this is a general nitration pathway. The atmospheric conditions under which this BrC formation process may occur are discussed.