Aerosol Species Research Articles

Phase State and Relative Humidity Regulate the Heterogeneous Oxidation Kinetics and Pathways of Organic-Inorganic Mixed Aerosols.

Inorganic species always coexist with organic materials in atmospheric particles and may influence the heterogeneous oxidation of organic aerosols. However, very limited studies have explored the role of the inorganics in the chemical evolution of organic species in mixed aerosols. This study examines the heterogeneous oxidation of glutaric acid-ammonium sulfate and 1,2,6-hexanetriol-ammonium sulfate aerosols by hydroxyl radicals (OH) under varied organic mass fractions (forg) and relative humidity in a flow tube reactor. Coupling the oxidation kinetics and product measurements with kinetic model simulations, we found that under both low relative humidity (RH, 30-35%) and high RH conditions (85%), the decreased forg from 0.7 to 0.2 accelerates the oxidation of the organic materials by a factor of up to 11. We suggest that the faster oxidation kinetics under low-RH conditions is due to full or partial phase separation, with the organics greatly enriched at the particle outer region, while enhanced "salting-out" of the organics and OH adsorption caused by higher inorganics could explain the observations under high-RH conditions. Analysis of the oxidation products reveals that the dilution of organics by the inorganic salts and corresponding water uptake under high-RH conditions will favor alkoxy radical fragmentation by a factor of 3-4 and inhibit its secondary chain propagation chemistry. Our results suggest that atmospheric organic aerosol oxidation lifetime and composition are strongly impacted by the coexistent inorganic salts.

Organic enrichment in droplet residual particles relative to out of cloud over the northwestern Atlantic: analysis of airborne ACTIVATE data

Abstract. Cloud processing is known to generate aerosol species such as sulfate and secondary organic aerosol, yet there is a scarcity of airborne data to examine this issue. The NASA Aerosol Cloud meTeorology Interactions oVer the western ATlantic Experiment (ACTIVATE) was designed to build an unprecedented dataset relevant to aerosol–cloud interactions with two coordinated aircraft over the northwestern Atlantic, with aerosol mass spectrometer data used from four deployments between 2020–2021 to contrast aerosol composition below, in (using a counterflow virtual impactor) and above boundary layer clouds. Consistent features in all time periods of the deployments (January–March, May–June, August–September) include the mass fraction of organics and relative amount of oxygenated organics (m/z 44) relative to total organics (f44) increasing in droplet residuals relative to below and above cloud. Detailed analysis comparing data below and in cloud suggests a possible role for in-cloud aqueous processing in explaining such results; an intriguing aspect though requiring more attention is that only approximately a quarter of the cloud cases (29 of 110) showed higher organic mass fractions either below or above cloud. Of those 29 cases, the majority (25) showed higher organic mass fraction below cloud base where the cloud processing signature is presumably more evident as compared to above cloud. These results are consistent with the few past studies analyzing droplet residuals pointing to higher organic enrichment than in adjacent cloud-free areas. The data findings are important as other datasets (e.g., reanalysis) suggest that sulfate is both more abundant than organics (in contrast to this work) and more closely related to drop number concentrations in the winter when aerosol–cloud interactions are strongest. Here we show that organics are more abundant than sulfate in the droplet residuals and that aerosol interaction with clouds potentially decreases particle hygroscopicity due to the increase in organic:sulfate ratio for droplet residuals relative to surrounding cloud-free air. These results are important in light of the growing importance of organics over the northwestern Atlantic in recent decades relative to sulfate owing to the success of regulatory activity over the eastern United States to cut sulfur dioxide emissions.

Aerosol characteristics over Indo-Gangetic Plain from ground-based AERONET and MERRA-2/CAMS model simulations

A comprehensive investigation of physical, optical, and chemical characteristics of columnar aerosols over two locations with distinct environmental settings in the Indo-Gangetic Plain (IGP) region, namely, Kanpur (urban and industrial area) and Gandhi College (rural area), is conducted using high-quality aerosol datasets obtained from ground-based Aerosol Robotic Network (AERONET) observations during the recent five year period (2015–2019). This study utilizes all the crucial columnar aerosol parameters necessary for accurately estimating aerosol radiative forcing. Quantification of contribution by different aerosol species originating from natural and anthropogenic sources to the total aerosol optical depth (AOD) and single scattering albedo (SSA) is important to understand the specific mechanisms that influence the aerosol composition, thereby reducing the uncertainty in aerosol radiative forcing. For the first time, two highly spatially resolved models' (Modern-Era Retrospective Analysis for Research and Applications-2 (MERRA-2) and Copernicus Atmosphere Monitoring Service (CAMS)) simulated absorbing species-wise (black carbon (BC), dust, and brown carbon (BrC)) AOD, and absorption AOD (AAOD) are compared and contrasted against the AERONET observations over the IGP region in a systematic manner. MERRA-2 AODs are mostly lower, whereas CAMS AODs are consistently higher than the AERONET AODs. A comparison of collocated time and space observations with models clearly suggests that improvements in emission inventories on a seasonal scale are essential. MERRA-2 SSA is noted lower than the AERONET SSA during the winter season due to overestimation in BC AOD. During winter in >70% of MERRA-2 simulated SSA the difference is higher than ±0.03 (the uncertainty range of AERONET SSA) whereas during pre-monsoon and monsoon seasons >60% of MERRA-2 SSA lies within the uncertainty range of AERONET SSA. Both models show a gradient in AODDust decreasing from west to east in the IGP. However, observations do not often exhibit the gradient in dust, which is validated by air mass back trajectory analyses as air masses travel through different pathways to IGP and reverse the west to east gradient in AODDust. This quantitative and comparative collocated analysis of observed aerosol characteristics with models on a seasonal scale will enable a better estimation of aerosol radiative forcing, and can help improve aerosol processes and parameterizations in models.

Measurement report: Closure analysis of aerosol–cloud composition in tropical maritime warm convection

Abstract. Cloud droplet chemical composition is a key observable property that can aid understanding of how aerosols and clouds interact. As part of the Clouds, Aerosols and Monsoon Processes – Philippines Experiment (CAMP2Ex), three case studies were analyzed involving collocated airborne sampling of relevant clear and cloudy air masses associated with maritime warm convection. Two of the cases represented a polluted marine background, with signatures of transported East Asian regional pollution, aged over water for several days, while the third case comprised a major smoke transport event from Kalimantan fires. Sea salt was a dominant component of cloud droplet composition, in spite of fine particulate enhancement from regional anthropogenic sources. Furthermore, the proportion of sea salt was enhanced relative to sulfate in rainwater and may indicate both a propensity for sea salt to aid warm rain production and an increased collection efficiency of large sea salt particles by rain in subsaturated environments. Amongst cases, as precipitation became more significant, so too did the variability in the sea salt to (non-sea salt) sulfate ratio. Across cases, nitrate and ammonium were fractionally greater in cloud water than fine-mode aerosol particles; however, a strong covariability in cloud water nitrate and sea salt was suggestive of prior uptake of nitrate on large salt particles. A mass-based closure analysis of non-sea salt sulfate compared the cloud water air-equivalent mass concentration to the concentration of aerosol particles serving as cloud condensation nuclei for droplet activation. While sulfate found in cloud was generally constrained by the sub-cloud aerosol concentration, there was significant intra-cloud variability that was attributed to entrainment – causing evaporation of sulfate-containing droplets – and losses due to precipitation. In addition, precipitation tended to promote mesoscale variability in the sub-cloud aerosol through a combination of removal, convective downdrafts, and dynamically driven convergence. Physical mechanisms exerted such strong control over the cloud water compositional budget that it was not possible to isolate any signature of chemical production/loss using in-cloud observations. The cloud-free environment surrounding the non-precipitating smoke case indicated sulfate enhancement compared to convective mixing quantified by a stable gas tracer; however, this was not observed in the cloud water (either through use of ratios or the mass closure), perhaps implying that the warm convective cloud timescale was too short for chemical production to be a leading-order budgetary term and because precursors had already been predominantly exhausted. Closure of other species was truncated by incomplete characterization of coarse aerosol (e.g., it was found that only 10 %–50 % of sea salt mass found in cloud was captured during clear-air sampling) and unmeasured gas-phase abundances affecting closure of semi-volatile aerosol species (e.g., ammonium, nitrate and organic) and soluble volatile organic compound contributions to total organic carbon in cloud water.

Changes in primary and secondary aerosols during a controlled Chinese New Year

Large reductions in anthropogenic emissions during the Chinese New Year (CNY) holiday in Beijing have been well reported. However, the changes during the CNY of 2021 are different because most people stayed in Beijing to control the spread of coronavirus disease (COVID-19). Here a high-resolution aerosol mass spectrometer (HR-AMS) was deployed for characterization of the changes in size-resolved aerosol composition and sources during the CNY. We found that the reductions in traffic-related NOx and fossil fuel-related organic aerosol (OA), and cooking OA (1.3–12.7%) during the CNY of 2021 were much smaller than those in previous CNY holidays of 2013, 2015, and 2020. In contrast, the mass concentrations of secondary aerosol species except nitrate showed ubiquitous increases (17.6–30.4%) during the CNY of 2021 mainly due to a 4-day severe haze episode. OA composition also changed substantially during the CNY of 2021. In particular, we observed a large increase by nearly a factor of 2 in oxidized primary OA likely from biomass burning, and a decrease of 50.1% in aqueous-phase secondary OA. A further analysis of the severe haze episode during the CNY illustrated a rapid transition of secondary formation from photochemical to aqueous-phase processing followed by a scavenging process, leading to significant changes in aerosol composition, size distributions, and oxidation degree of OA. A parameterization relationship between oxygen-to-carbon (O/C) and f44 (fraction of m/z 44 in OA) from a collocated capture vaporizer aerosol chemical speciation monitor (CV-ACSM) was developed, which has a significant implication for characterization of OA evolution and the impacts on hygroscopicity due to the rapidly increased deployments of CV-ACSM worldwide.

Assessment of NAAPS-RA performance in Maritime Southeast Asia during CAMP2Ex

Abstract. Monitoring and modeling aerosol particle life cycle in Southeast Asia (SEA) is challenged by high cloud cover, complex meteorology, and the wide range of aerosol species, sources, and transformations found throughout the region. Satellite observations are limited, and there are few in situ observations of aerosol extinction profiles, aerosol properties, and environmental conditions. Therefore, accurate aerosol model outputs are crucial for the region. This work evaluates the Navy Aerosol Analysis and Prediction System Reanalysis (NAAPS-RA) aerosol optical thickness (AOT) and light extinction products using airborne aerosol and meteorological measurements from the Cloud, Aerosol, and Monsoon Processes Philippines Experiment (CAMP2Ex) conducted in 2019 during the SEA southwest monsoon biomass burning season. Modeled AOTs and extinction coefficients are compared to those retrieved with a high spectral resolution lidar (HSRL-2). Agreement between simulated and retrieved AOT (R2= 0.78, relative bias =-5 %, normalized root mean square error (NRMSE) = 48 %) and aerosol extinction coefficients (R2= 0.80, 0.81, and 0.42; relative bias = 3 %, −6 %, and −7 %; NRMSE = 47 %, 53 %, and 118 % for altitudes between 40–500, 500–1500, and >1500 m, respectively) is quite good considering the challenging environment and few opportunities for assimilations of AOT from satellites during the campaign. Modeled relative humidities (RHs) are negatively biased at all altitudes (absolute bias =-5 %, −8 %, and −3 % for altitudes <500 500–1500 and >1500 m, respectively), motivating interest in the role of RH errors in AOT and extinction simulations. Interestingly, NAAPS-RA AOT and extinction agreement with the HSRL-2 does not change significantly (i.e., NRMSE values do not all decrease) when RHs from dropsondes are substituted into the model, yet biases all move in a positive direction. Further exploration suggests changes in modeled extinction are more sensitive to the actual magnitude of both the extinction coefficients and the dropsonde RHs being substituted into the model as opposed to the absolute differences between simulated and measured RHs. Finally, four case studies examine how model errors in RH and the hygroscopic growth parameter, γ, affect simulations of extinction in the mixed layer (ML). We find NAAPS-RA overestimates the hygroscopicity of (i) smoke particles from biomass burning in the Maritime Continent (MC) and (ii) anthropogenic emissions transported from East Asia. This work mainly provides insight into the relationship between errors in modeled RH and simulations of AOT and extinction in a humid and tropical environment influenced by a myriad of meteorological conditions and particle types. These results can be interpreted and addressed by the modeling community as part of the effort to better understand, quantify, and forecast atmospheric conditions in SEA.

Long-range transport of airborne bacteria over East Asia: Asian dust events carry potentially nontuberculous Mycobacterium populations.

The nontuberculous mycobacterial pulmonary disease (NTM-PD) caused by Mycobacterium species has increased in prevalence all over the world. The distributions of NTM-PD are possibly determined by the westerly wind traveling at high altitudes over East Asia. However, the long-range transport of Mycobacterium species has not been demonstrated by analyzing the bacterial communities in aerosols such as desert mineral particles and anthropogenic pollutants transported by the westerly wind. Here, airborne bacterial compositions were investigated including Mycobacterium species in high-elevation aerosols, which were captured in the snow cover at 2,450m altitude on Mt. Tateyama. This was further compared to the ground-level or high-altitude aerosols collected at six sampling sites distributed from Asian-dust source region (Tsogt-Ovoo) to downwind areas in East Asia (Asian continental cities; Erenhot, Beijing, Yongin, Japanese cities; Yonago, Suzu, Noto Peninsula). The cell concentrations and taxonomic diversities of airborne bacteria decreased from the Asian continent to the Japan area. Terrestrial bacterial populations belonging to Firmicutes and Actinobacteria showed higher relative abundance at high-elevation and Japanese cities. Additionally, Mycobacterium species captured in the snow cover on Mt. Tateyama increased in relative abundance in correspondence to the increase of black carbon concentrations. The relative abundance of Mycobacterium sequences was higher in the aerosol samples of Asian continental cities and Japanese cities than in the desert area. Presumably, anthropogenic pollution over East Asia carries potential Mycobacterium species, which induce NTM-PD, thereby impacting upon the public health.

Field evidence for enhanced generation of reactive oxygen species in atmospheric aerosol containing quinoline components

Organic constituents of atmospheric particular matter (PM) contribute significantly to prompt generation of reactive oxygen species (ROS) in particle phase, which is often quantified in terms of its oxidative potential (OP). In this study, we used complementary methods of the advanced molecular characterization and the OP quantitation to explore potential of different organic species to enhance ROS generation in ambient aerosol samples. We used seven PM2.5 samples collected in the Midwest US, and extracted them sequentially into a set of solvents with different polarity: first non-polar hexane (HEX), then moderately polar dichloromethane (DCM) and finally polar deionized (DI) water. The DI extracts were further separated using solid phase extraction to isolate water-soluble organic carbon (WSOC) from inorganic ions. The OP of obtained extracts was analyzed using dithiothreitol (DTT) assay and reported here in terms of the DTT consumption rate (called DTT activity). The molecular composition of the same extracts was analyzed using a tandem platform of high-performance liquid chromatography (HPLC) coupled with a photodiode array detector (PDA) and a high-resolution mass spectrometer (HRMS). Highest DTT activities were observed in WSOC fractions (>1.1 μM min−1) followed by DCM (0.75–1.1 μM min−1) and HEX (<0.75 μM min−1) fractions, respectively. These results were complemented by the HPLC-PDA-HRMS molecular characterization data indicating numerous redox-active polar organics detected in the WSOC fractions. In particular, chemical component with elemental formula of C11H11N - attributed to dimethyl quinoline (DMQ) - was found systematically across all DTT-active fractions. The unprotonated nitrogen atom in the pyridine ring of quinolines facilitates electron transfer in the redox reactions, catalyzing generation of ROS in the quinoline containing samples. This is the first study that unambiguously identifies quinoline as a promoter of ROS generation determined within complex mixtures of ambient organic aerosols.

On the Relevance of Aerosols to Snow Cover Variability Over High Mountain Asia

AbstractWhile meteorology and aerosols are identified as key drivers of snow cover (SC) variability in High Mountain Asia, complex non‐linear interactions between them are not adequately quantified. Here, we attempt to unravel these interactions through a simple relative importance (RI) analysis of meteorological and aerosol variables from ERA5/CAMS‐EAC4 reanalysis against satellite‐derived SC from Moderate Resolution Imaging Spectroradiometer across 2003–2018. Our results show a statistically significant 7% rise in the RI of aerosol‐meteorology interactions (AMI) in modulating SC during late snowmelt season (June and July), notably over low snow‐covered (LSC) regions. Sensitivity tests further reveal that the importance of meteorological interactions with individual aerosol species are more prominent than total aerosols over LSC regions. We find that the RI of AMI for LSC regions is clearly dominated by carbonaceous aerosols, on top of the expected importance of dynamic meteorology. These findings clearly highlight the need to consider AMI in hydrometeorological monitoring, modeling, and reanalyses.

Prediction of health effects of Asian dust in Japan

BACKGROUND AND AIM The health effects of cross-border air pollutants and Asian dust are of significant concern in Japan. Currently, models predicting the arrival of aerosols have not investigated the association between arrival predictions and health effects. We investigated the association between subjective health symptoms and data acquired from the Japan Meteorological Agency&amp;#x27;s (JMA&amp;#x27;s) Model of Aerosol Species in the Global Atmosphere (MASINGAR) aerosol model with the objective of ascertaining if the data could be applied for predicting health effects. METHODS Subjective symptom scores were collected using self-administered questionnaires and used with the JMA model’s surface concentration data to conduct a risk evaluation using a multiple linear mixed model, from 2013 to 2015. Altogether, 160 individuals provided 16226 responses. Data regarding climate (temperature, humidity, and atmospheric pressure) and environmental factors (NO2, SO2, and Ox) were used as covariates. We calculated the association between the surface dust concentration and symptoms. RESULTS A strong association was also observed for nasal and cough symptoms (P for trend &amp;#x3c; 0.001). The differences in scores of nasal symptoms (sneezing and runny) of the highest quartile [Q4] vs. the lowest [Q1] were 0.039 (95% confidence interval (CI): 0.02–0.01, p &amp;#x3c; 0.05) and 0.046 (95% CI: 0.002–0.02, p &amp;#x3c; 0.05), respectively. The differences in scores of cough symptoms were 0.036 (95% confidence interval (CI): 0.002–0.01, p &amp;#x3c; 0.05). CONCLUSIONS This study suggests that predictive models for pollutants’ arrival can be used to capability to foresee and possibly prevent the health impact of long-range transport of air pollutants, recommending the potential role of aerosol forecast models in health care. MASINGAR is the Global Spectral Model (GSM), this has the potential that can contribute to health predictions all over the world. KEYWORDS Asian dust, Health forecast, Allergic symptoms, Air pollution

Substantial Uncertainties in Arctic Aerosol Simulations by Microphysical Processes Within the Global Climate‐Aerosol Model CAM‐ATRAS

AbstractAerosols can modulate the Arctic climate through their interactions with radiation, clouds, and snow and ice surfaces. Atmospheric simulations of Arctic aerosols remain highly uncertain, for which the importance of aerosol microphysical properties and processes has not been properly evaluated. To identify the cause of this large uncertainty, we evaluate the variability ranges of aerosols in the Arctic resulting from uncertainties in various aerosol microphysical properties/processes, including particle size distributions at emission, particle mixing states, activation efficiency, and wet removal processes, by using a global climate‐aerosol model Community Atmosphere Model with the Aerosol Two‐dimensional bin module for foRmation and Aging Simulation. We find that the combined uncertainties associated with these multiple microphysical properties/processes yield a factor of 10–50 differences (maximum‐to‐minimum ratio) in the concentrations and radiative effects of aerosols in the Arctic. Black carbon shows the highest variability among aerosol species because its lower hygroscopicity and higher critical supersaturation cause the fraction of activation and wet removal during transport to be highly sensitive to the model treatment of aerosol and cloud microphysics. Aerosol‐radiation‐cloud interactions at the top of atmosphere vary from −0.40 to +0.30 W m−2 in the Arctic (from the preindustrial to present day) and can be positive or negative depending on the treatment of microphysical properties/processes. These results indicate that microphysical properties/processes are more important than previously thought in aerosol simulations in the Arctic and demonstrate that a better understanding and more sophisticated model representation of aerosol microphysical properties/processes are required to improve the accuracy of Arctic aerosol simulations and their impacts on climate.

Estimates of PM2.5 concentrations spatiotemporal evolution across China considering aerosol components in the context of the Reform and Opening-up

With astonishing and rapid development in China since the Reform and Opening-up in 1978, serious air pollution has become a great challenge. A better understanding of the response of PM2.5 pollution to socioeconomic development after the Reform and Opening-up policy is benefit for pollution control. However, heterogeneous influences of biophysical and socioeconomic activities on PM2.5 pollution pose great challenges in statistical simulation of PM2.5. Few statistical model regards aerosol species as the explanatory variables for heterogeneous formation mechanism to retrieve PM2.5 concentration. In this research, monthly PM2.5 concentration in China during 1980–2020 was reconstructed by a novel statistical strategy considering aerosol components (AC-RF). Three cross-validation (CV) methods, sample-based CV, spatial-based CV and temporal-based CV results indicated satisfactory performance of AC-RF model with correlation coefficient (R) of 0.92, 0.90, 0.86, respectively. A three-stage concluded on PM2.5 concentration annual variation in China was drawn as followed: Before 2000, PM2.5 level in China represented smooth evolution and mainly influenced by natural events with polluted region locating in Xinjiang province, North China and Central China. Since 2000, PM2.5 concentration increased to high level in the context of rapid socioeconomic development. Severe air pollution covered Jing-Jin-Ji agglomeration, Central China and Sichuan Basin. During 2012–2020, PM2.5 declined and polluted region shrank, which was benefited by the strictest-ever air pollution control measures. Based on aerosol components analysis, sulfate aerosol exhibited the most significant increase trend in recent 40 years and black aerosol variation is the most closely related to PM2.5 pollution. In conclusion, unsustainable development is the culprit for air quality deterioration. Strict and continuous air pollution control strategies are effective for air quality improvement.

Chemical components of PM2.5 in different seasons in Harbin, China

The seasonal characteristics of fine particulate matter (PM2.5) were investigated from October 2020 to April 2021 (spreading fall, winter and spring) in Harbin, a city located in northeast China. The mass concentrations of PM2.5 in winter were significantly higher than those in fall and spring. Moreover, our results indicated that various aerosol species had obvious seasonality. The proportions of secondary components were higher in winter than other two seasons. In contrast, the ratios of nitrate to sulfate (NO3−/SO42−) showed lower levels in winter, which was because both the ratios of nitrogen dioxide to sulfur dioxide (NO2/SO2) and the ratios of nitrogen oxidation ratio to sulfur oxidation ratio (NOR/SOR) exhibited lower values in winter than in fall and spring. With PM2.5 increased, the NO3−/SO42− ratios showed increasing trends in all three seasons, which was mainly attributed to the increase of NOR/SOR ratios in fall and spring, and the increase of both NO2/SO2 and NOR/SOR ratios in winter. This result highlighted that nitrate was more important than sulfate as a driver for the growth of PM2.5 during the period of heavy air pollution. Additionally, the sources of organic aerosol (OA) in different seasons were also distinctly different. Overall, the sum of biomass burning OA (BBOA) and secondary OA (SOA) contributed >70% of OA in three seasons. The fractional contributions of BBOA to total OA, notably, exhibited higher levels in fall and spring, because of intensive open agricultural fires. The SOA fractions in OA were larger in winter, likely due to higher relative humidity which facilitated the secondary formation. A large increase in the proportions of BBOA was observed during polluted days in fall and spring compared to clean days. In comparison, during heavily-polluted periods, secondary formation made a dominant contribution to organic matter in winter.

Apportioning PM1 in a contrasting receptor site in the Mediterranean region: Aerosol sources with an updated sulfur speciation

A multi-parametric experimental campaign was performed in Agri Valley (Basilicata, southern Italy) from July 2017 to January 2018. The investigated area, though basically rural and devoted to agricultural activities, hosts a huge on-shore oil reservoir, i.e. Centro Olio Val d'Agri (COVA), bringing substantial environmental modifications and impacts to the district landscape. Daily concentrations of PM1 aerosol samples, Equivalent Black Carbon and number size distributions were evaluated. Chemical aerosol speciation based on elemental and ion analyses were carried out and source apportionment by Positive Matrix Factorization (PMF) was applied to reconstruct PM1 source profile. The most significant emission sources found are torches from the oil treatment facility (37 % w/w), an unresolved factor constituted by soil resuspension, Saharan dust, and biomass burning (24 % w/w), ammonium sulphate (23 % w/w), emissions from the oil desulfurization (Claus process) (13 % w/w), and traffic + road dust (3 % w/w). SEM analysis on PM1 single particles allowed to confirm the finding from PMF including the occurrence of elemental sulfur associated with the Claus process. The novelty of the present study consists in the identification of this latter fingerprint.

Combined organic and inorganic source apportionment on yearlong ToF-ACSM dataset at a suburban station in Athens

Abstract. The current improvements in aerosol mass spectrometers in resolution and sensitivity, and the analytical tools for mass spectra deconvolution, have enabled the in-depth analysis of ambient organic aerosol (OA) properties. Although OA constitutes a major fraction of ambient aerosol, its properties are determined to a great extent by the mixing characteristics of both organic and inorganic components of ambient aerosol. This work applies a new methodology to a year-long ACSM dataset to assess the sources of organic and total non-refractory species in the Athens background aerosol and provides insights into the interactions between organic and inorganic species. The use of innovative tools for applying positive matrix factorization (PMF, rolling window) enables the study of the temporal variability of the contribution of these sources and seasonal changes in their composition. The mass spectra of both organic and inorganic aerosol were obtained by a time-of-flight aerosol mass spectrometer (ToF-ACSM) for PMF analysis. The results revealed five factors when organic aerosol was analysed separately. Three of them were primary OA factors: hydrocarbon-like organic aerosol (HOA), cooking-related organic aerosol (COA) and biomass burning organic aerosol (BBOA). The remaining two were secondary, less and more oxidized oxygenated organic aerosol (LO-OOA and MO-OOA respectively). The relative contributions of these factors were HOA 15 %, COA 18 %, BBOA 9 %, MO-OOA 34 % and LO-OOA 24 % (yearly averaged). When a combined organic and inorganic aerosol matrix was analysed, two additional factors were identified that were mainly composed of ammonium sulfate (83.5 %) and ammonium nitrate (73 %). Moreover, two secondary factors were resolved, containing both organics and inorganics and were named more (MOA) and less oxidized aerosol (LOA). The relative contributions on a yearly average of these factors were HOA 7 %, COA 9 %, BBOA 3 %, ammonium nitrate 3 %, ammonium sulfate 28 %, MOA 24 % and LOA 26 %.

Retrieving aerosols single scattering albedo from MODIS reflectances

Single scattering albedo (SSA) is a key parameter to estimate aerosol direct radiative forcing. However, retrieving SSA from satellite observations is still challenging. In this study, a new method optimizing the aerosol optical model based on four basic aerosol components is developed for retrieving SSA from Moderate Resolution Imaging Spectroradiometer (MODIS) data. The new method takes advantage of the relationship between aerosol composition and reflectance at multiple wavelengths to derive SSA, which considers the variation of aerosol species with time and location. A sensitivity study considering the uncertainties from the top of the atmosphere (TOA) apparent reflectance, aerosol optical depth (AOD) at 550 nm and land surface bidirectional reflectance distribution function (BRDF) parameters is performed to test the stability of the proposed method. The results demonstrate the high accuracy and robustness of the new method. The root mean square error (RMSE) is within 0.03 at 470 and 550 nm based on the sensitivity study. The aerosol components used in our method show better representativeness of real aerosol components than that used in the Second Simulation of a Satellite Signal in the Solar Spectrum - Vector (6SV) model. The aerosols SSA values are retrieved from real MODIS observations with the new method and compared with the AERONET SSA product at two polluted AERONET sites in Asia. A better consistency with the correlation coefficient (R) of 0.27– 0.55 and the RMSE within 0.04 at 470 and 550 nm wavelengths between MODIS SSA retrievals and the AERONET SSA product is obtained with the new method compared with that of deep blue (DB) SSA. The new method can help to better understand aerosol radiative forcing regionally and globally.

Regime shift in aerosol optical depth and long-term aerosol radiative forcing implications over the Arabian Peninsula Region

The Aerosol Optical Depth (AOD) and aerosol-induced radiative forcing trends inferred for the period 1995–2019 over the Arabian Peninsula region (APR) are extensively studied using the state-of-the-art Modern-Era Retrospective analysis for Research and Applications, version 2 (MERRA-2) reanalysis data. We examine the long-term AOD change for five major aerosol species: Dust (DU), Sea Salt (SS), Sulfate (SU), Black Carbon (BC), and Organic Carbon (OC) over the APR. The MERRA-2 AOD comparisons with surface measurements show that it is capable to reproduce the AOD features over APR. The total AOD over the region shows a high value in JJA with the combined effect of DU and SU being major contributors. The total AOD over APR shows an increasing trend at a rate of ∼0.05/decade. Along with an incline in DUAOD, the anthropogenic signature on total AOD also hikes contributed mainly by the SU and OC. The increase in AOD also results in a surge in aerosol-induced atmospheric forcing (ATM) with a trend of 0.13 Wm-2 year−1 and 0.15 Wm-2 year−1 during MAM and JJA respectively. Overall, the study gives a comprehensive picture of the capability of the MERRA-2 in long-term aerosol monitoring over APR, primarily situated in the “dust-belt” region.

Climatology of aerosol component concentrations derived from multi-angular polarimetric POLDER-3 observations using GRASP algorithm

Abstract. The study presents a climatology of aerosol composition concentrations obtained by a recently developed algorithm approach, namely the Generalized Retrieval of Atmosphere and Surface Properties (GRASP)/Component. It is applied to the whole archive of observations from the POLarization and Directionality of the Earth's Reflectances (POLDER-3). The conceptual specifics of the GRASP/Component approach is in the direct retrieval of aerosol speciation (component fraction) without intermediate retrievals of aerosol optical characteristics. Although a global validation of the derived aerosol component product is challenging, the results obtained are in line with general knowledge about aerosol types in different regions. In addition, we compare the GRASP-derived black carbon (BC) and dust components with those of the Modern-Era Retrospective Analysis for Research and Applications, version 2 (MERRA-2) product. Quite a reasonable general agreement was found between the spatial and temporal distribution of the species provided by GRASP and MERRA-2. The differences, however, appeared in regions known for strong biomass burning and dust emissions; the reasons for the discrepancies are discussed. The other derived components, such as concentrations of absorbing (BC, brown carbon (BrC), iron-oxide content in mineral dust) and scattering (ammonium sulfate and nitrate, organic carbon, non-absorbing dust) aerosols, represent scarce but imperative information for validation and potential adjustment of chemical transport models. The aerosol optical properties (e.g., aerosol optical depth (AOD), Ångström exponent (AE), single-scattering albedo (SSA), fine- and coarse-mode aerosol optical depth (AODF AND AODC)) derived from GRASP/Component were found to agree well with the Aerosol Robotic Network (AERONET) ground reference data, and were fully consistent with the previous GRASP Optimized, High Precision (HP) and Models retrieval versions applied to POLDER-3 data. Thus, the presented extensive climatology product provides an opportunity for understanding variabilities and trends in global and regional distributions of aerosol species. The climatology of the aerosol components obtained in addition to the aerosol optical properties provides additional valuable, qualitatively new insight about aerosol distributions and, therefore, demonstrates advantages of multi-angular polarimetric (MAP) satellite observations as the next frontier for aerosol inversion from advanced satellite observations. The extensive satellite-based aerosol component dataset is expected to be useful for improving global aerosol emissions and component-resolved radiative forcing estimations. The GRASP/Component products are publicly available (https://www.grasp-open.com/products/, last access: 15 March 2022) and the dataset used in the current study is registered under https://doi.org/10.5281/zenodo.6395384 (Li et al., 2022b).

Two-year-long high-time-resolution apportionment of primary and secondary carbonaceous aerosols in the Los Angeles Basin using an advanced total carbon–black carbon (TC-BC(λ)) method

In recent years, carbonaceous aerosols (CA) have been recognized as a significant contributor to the concentration of particles smaller than 2.5 μm (i.e., PM2.5), with a negative impact on public health and Earth's radiative balance. In this study, we present a method for CA apportionment based on high-time-resolution measurements of total carbon (TC), black carbon (BC), and spectral dependence of absorption coefficient using a recently developed Carbonaceous Aerosol Speciation System (CASS). Two-year-long CA measurements at two different locations within California's Los Angeles Basin are presented. CA was apportioned based on its optical absorption properties, organic or elemental carbon composition, and primary or secondary origin. We found that the secondary organic aerosols (SOA), on average, represent >50 % of CA in the study area, presumably resulting from the oxidation of anthropogenic and biogenic volatile organic components. Remarkable peaks of SOA in summer afternoons were observed, with a fractional contribution of up to 90 %. On the other hand, the peak of primary emitted CA, consisting of BC and primary organic aerosol (POA), contributed >80 % to the CA during morning rush hours on winter working days. The light absorption of BC dominated over the brown carbon (BrC), which contributed to 20 % and 10 % of optical absorption at the lower wavelength of 370 nm during winter nights and summer afternoons, respectively. The highest contribution of BrC, up to 50 %, was observed during the wildfire periods. Although the uncertainty levels can be high for some CA components (such as split between primary emitted and secondary formed BrC during winter nights), further research focused on the optical properties of CA at different locations may help to better constrain the parameters used in CA apportionment studies. We believe that the CASS system combined with the apportionment method presented in this study can offer simplified and cost-effective insights into the composition of carbonaceous aerosols.

Oxidative potential and hydroxyl radical generation capacity of ambient PM2.5 over a high-altitude site in northeastern Himalaya: Role of long-range transport

This study investigates the dithiothreitol (DTT)-based oxidative potential (OP) and corresponding hydroxyl radical (•OH) generations capacity of PM2.5 (particulate matter with aerodynamic diameter ≤ 2.5 μm) over a high-altitude site, Shillong (25.7 °N, 91.9 °E; 1064 m above mean sea level), located in the northeastern Himalaya. Measured OP and •OH are reported in two units: per m3 of filtered air (OPV and OHV) or per unit mass of PM2.5 in μg (OPM and OHM). Based on the characteristic ratios of chemical species in different sources, PM2.5 were classified into three source categories: Biomass Burning (BB) (N = 10), Secondary Organic Aerosols (SOA) (N = 12), and Mixed (N = 12). Consistently higher OP and •OH generation per m3 of air (OPV: 6.2 ± 1.0 (average ± SD, 1σ) nmol DTT min−1 m−3, and OHV: 1.2 ± 0.31 nmol •OH m−3) in all BB-dominated PM2.5 samples indicate relatively hazardous exposure dose from BB emissions among all sources. Characteristic OC/EC, WSOC/OC, and nss-K+/EC ratios evoked that SOA from biogenic precursors was a significant source for the observed OP and •OH in SOA-categorized samples. Distinctly different chemical composition of PM2.5 over Shillong (about 55% composed of organic matter) makes it relatively more (2–4 times) intrinsically redox-active compare to a reported study over another high-altitude site in a semi-arid region of India. Despite ∼1.7 times lower PM2.5 mass over Shillong (characterized by more aged PM2.5) compare to Patiala (30.3°N, 76.4°E; 250m amsl, a semi-urban city, characterized by fresher PM2.5 from mixed sources), the observed OPV over Shillong was about 1.2 times higher, and the OPM was about 2 times higher. It is attributed to the effect of atmospheric processing on particle's redox-activity. While examining the relationship of OPV and OHV with chemical species, it was observed that •OH generation capacity was more influenced by WSOC species' origin (primary or secondary) compare to DTT consumption. Such an observation restricts the practicality of particle-induced OP to be considered as the only metric for aerosol particle toxicity, and suggests also to consider simultaneous measurements of •OH generations. For the BB-dominated category, OC-normalized OP (OPOC) was correlated strongly with the fractions of N-containing water-soluble organic aerosols (i.e., a fraction of WSON and a fraction of familyCHO1N). Corresponding OC/EC, nss-K+/EC and nss-SO42−/EC ratios hint that coal combustion, in addition to BB, could be a significant source of redox-active WSON species in these samples. Such studies are important for identifying redox-active aerosol species and developing appropriate mitigation policies for healthy air.