Primary Organic Aerosol Research Articles

Evolution of size and composition of fine particulate matter in the Delhi megacity during later winter

This study presents the first multi-site evolution analysis of fine Organic Aerosols (OA) and inorganics in the Delhi megacity (National Capital Region (NCR)) using high-resolution-particle time of flight (HR-PToF) size distribution obtained from Aerodyne HR-ToF-AMS. It provides a comprehensive view of the atmospheric dynamic processes responsible for the aerosol size and composition transformation. The measurements were performed at two different sampling sites (1) Indian Institute of Technology, Delhi (IITD), and (2) Manav Rachna International University, Faridabad (MRIU) during a late winter period (February to March 2018). Among organics, primary OA (POA) showed particle growth, whereas it was absent in secondary OA proxies. IITD was observed to have a distinct growth pattern as compared to MRIU because of high vehicular density and heterogeneity, and the presence of growth-promoting factors such as acidity and RH conditions. IITD aerosols were observed to be more acidic (ANR∼ 0.75) compared to MRIU (ANR∼1) and showed a distinct diurnal bin-wise increase during the photochemically active period (PAP). Such high acidic conditions are responsible for promoting acid-catalyzed SOA productions over the broader size bins, especially during the PAPs. Primary OA (POA) such as HOA and BBOA proxies show a diurnal growth from ∼440 to 970 nm and from ∼370 to 550 nm, at IITD and from ∼270 to 400 nm and ∼430–470 nm, at MRIU respectively. Further, OA families (amines and hydrocarbons), and inorganics such as chloride and nitrate also showed distinct concurrent diurnal growth patterns at IITD (from an MMDs of ∼380–520 nm to 650–960 nm). We have also observed a positive correlation between OA and inorganics growth and the mass fraction (MF = SOA/OA) of SOA at both sites of NCR. For 0.1 (MF) increase in SOA, the sizes of HOA, chloride, primary CH family and amines (CHN family), and secondary amines (CHON family) are increased by ∼93, 80, 64, 66, and 47 nm at IITD and ∼14, 35, 8, 11, and 16 nm at MRIU respectively. The concurrent growth of these species with the increase in the SOA concentration indicates the existence of a similar size evolution mechanism at both NCR sites, further promoting the formation of internally mixed aerosols during some phase of their evolution. This suggests that condensation is significantly governing the growth mechanism in NCR. Our study indicates the inclusion of such dynamic growth patterns arising from local prevailing conditions into the models for a better understanding of atmospheric aerosol evolution and estimation of fine particulate matter budget.

Modeling Volatility-Based Aerosol Phase State Predictions in the Amazon Rainforest

Organic aerosol (OA) is a complex matrix of various constituents—fresh (primary organic aerosols—POA) and aged via oxidation (secondary organic aerosols—SOA), generated from biogenic, anthropogenic, and biomass burning sources. The viscosity of OA can be critical in influencing new particle formation, reactive uptake processes that impact evaporation-growth kinetics, and the lifetime of particles in the atmosphere. This work utilizes a well-defined relationship between volatility and viscosity for pure compounds, which we incorporated within the Weather Research and Forecasting Model coupled to chemistry (WRF-Chem) to simulate the phase state and viscosity of bulk OA during the dry-to-wet transition season (September–October) in the Amazon rainforest during 2014. Our simulations indicate spatial and temporal heterogeneity in aerosol phase state often not captured by global-scale models. We show the strong role of water associated with organic aerosol (ws) as the dominant factor that can be used to quantitatively estimate OA viscosity. Analysis of WRF-Chem simulations across the entire atmospheric column indicates a strong inverse log-linear relationship between ws and OA viscosity with a correlation coefficient approaching 1, in the background and biomass burning-influenced conditions. At high altitudes where relative humidity (RH) and temperatures are low, our simulations indicate that OA exists in a semisolid-/solid-like phase state, consistent with previous studies. OA hygroscopicity is strongly correlated (ca. −0.8) with OA viscosity at RH ca. 30–50%, but this RH range is found mostly at low OA concentrations and the middle troposphere (ca. 6–10 km altitudes) in our simulated domain. OA hygroscopicity is uncorrelated with viscosity at higher-RH (near surface) and lower-RH (upper troposphere) regimes. At the urban site near surface, where day–night differences in RH are significant, RH is found to drive the phase state. At the background forested site near surface, where day–night RH differences are small, biomass burning-influenced OA is semisolid and a significant OA associated with background conditions is liquid-like. Simulations indicate a long tail of OA viscosity frequency distributions extending in the semisolid/solid regimes over background biogenic-influenced conditions due to the role of low-volatility OA components such as monoterpene oxidation products.

The roles of aqueous-phase chemistry and photochemical oxidation in oxygenated organic aerosols formation

The formation mechanism and evolution process of secondary organic aerosol (SOA) remain poorly understood due to measurement uncertainties and chemical complexities. Here, we present the characterization of non-refractory fine particles (NR-PM2.5) analyzed by means of a time-of-flight ACSM (ToF-ACSM) at a rural site in the North China Plain during winter. Our results show that air quality in rural areas was heavily polluted by primary organic aerosols (POA), which accounted for 83% of total organic aerosol (OA). The oxygenated organic aerosols (OOA) were mainly generated from local emissions. As pieces of evidence, firstly, less-oxidized OOA (LO-OOA) had good correlations with primary species like biomass burning OA (BBOA) (R2= 0.54), EC (R2= 0.46), and chloride (R2= 0.46), implying LO-OOA was formed with the POA emission processes; secondly, there was a significant increase in OOA concentration after sunrise, indicating a lot of local generation during the daytime; thirdly, the potential source region of OOA was restricted in that of POA, implying that OOAs were converted from where primary emission exists. The formation processes of LO-OOA and more-oxidized OOA (MO-OOA) are different. Aqueous-phase chemistry had a dominant effect on the formation of LO-OOA due to the better correlation between aerosol liquid water content (ALWC) with LO-OOA (R2= 0.54) than MO-OOA (R2= 0.15). In comparison, both aqueous-phase and photochemical processes acted on the MO-OOA formation, when odd oxygen (Ox = O3+NO2) was low (Ox < 35 ppb), MO-OOA concentration increased with the increment of ALWC. However, at high Ox level (Ox > 35 ppb), photochemical oxidation played an essential role in MO-OOA formation.

Assessment of the emission mitigation effect on the wintertime air quality in the Guanzhong Basin, China from 2013 to 2017

With the completion of the Air Pollution Prevention and Control Action Plan (Action Plan) in the Guanzhong Basin (GZB), the wintertime fine particulate matters (PM2.5) concentration has decreased by 50.0 μg m−3 (33.4%) from 2013 to 2017. Considering the significant impacts of meteorological conditions on particulate pollution, the effectiveness of anthropogenic emissions abatement on the PM2.5 reduction in the GZB remain unclear. In this study, the WRF-Chem model was used to quantitatively evaluate the effectiveness of emissions mitigation on the particulate pollution in the GZB in December from 2013 to 2017. The model typically showed an affordable consistence with observations and simulation in meteorological parameters, atmospheric pollutants, and aerosol components. Sensitivity results revealed that emissions reduction decreases PM2.5 concentrations by around 17% in the GZB, about half of the observed PM2.5 decreased in December from 2013 to 2017, showing significant role of meteorological conditions in modulating particulate pollution. Emissions mitigation also decreased SO2, CO and O3 concentrations by around 55%, 17%, and 7%, respectively, but increased NO2 concentrations by 27%. Additionally, the PM2.5 decrease in the GZB is mainly contributed by the reduction of sulfate and primary organic aerosols, caused by implementation of stringent SO2 mitigation measures and reduced coal use. However, the mitigation of elemental carbon, dust and nitrate aerosols are not significant, particularly with regarding to nitrate aerosols, which is influenced by increase of NO2 and decrease of sulfate. Specified emissions mitigation strategies need to be designed to further lower the PM2.5 level in the GZB.

Phase Behavior of Hydrocarbon-like Primary Organic Aerosol and Secondary Organic Aerosol Proxies Based on Their Elemental Oxygen-to-Carbon Ratio.

A large fraction of atmospheric aerosols can be characterized as primary organic aerosol (POA) and secondary organic aerosol (SOA). Knowledge of the phase behavior, that is, the number and type of phases within internal POA + SOA mixtures, is crucial to predict their effect on climate and air quality. For example, if POA and SOA form a single phase, POA will enhance the formation of SOA by providing organic mass to absorb SOA precursors. Using microscopy, we studied the phase behavior of mixtures of SOA proxies and hydrocarbon-like POA proxies at relative humidity (RH) values of 90%, 45%, and below 5%. Internal mixtures of POA and SOA almost always formed two phases if the elemental oxygen-to-carbon ratio (O/C) of the POA was less than 0.11, which encompasses a large fraction of atmospheric hydrocarbon-like POA from fossil fuel combustion. SOA proxies mixed with POA proxies having 0.11 ≤ O/C ≤ 0.29 mostly resulted in particles with one liquid phase. However, two liquid phases were also observed, depending on the type of SOA and POA surrogates, and an increase in phase-separated particles was observed when increasing the RH in this O/C range. The results have implications for predicting atmospheric SOA formation and policy strategies to reduce SOA in urban environments.

Measurement report: Cloud condensation nuclei activity and its variation with organic oxidation level and volatility observed during an aerosol life cycle intensive operational period (ALC-IOP)

Abstract. Cloud condensation nuclei (CCN) spectrum and the CCN activated fraction of size-resolved aerosols (SR-CCN) were measured at a rural site on Long Island during the Department of Energy (DOE) aerosol life cycle intensive operational period (ALC-IOP) from 15 July to 15 August 2011. During the last week of the ALC-IOP, the dependence of the activated fraction on aerosol volatility was characterized by sampling downstream of a thermodenuder (TD) operated at temperatures up to 100 ∘C. Here we present aerosol properties, including aerosol total number concentration, CCN spectrum, and the CCN hygroscopicity, for air masses of representative origins during the ALC-IOP. The hygroscopicity of organic species in the aerosol is derived from CCN hygroscopicity and chemical composition. The dependence of organic hygroscopicity on the organic oxidation level (e.g., atomic O:C ratio) agrees well with theoretical predictions and results from previous laboratory and field studies. The derived κorg and O:C ratio first increase as TD temperature increases from 20 ∘C (i.e., ambient temperature) to 50 or 75 ∘C and then decrease as TD temperature further increases to 100 ∘C. The initial increases of O:C and κorg with TD temperature below 50 ∘C are likely due to evaporation of more volatile organics with relatively lower O:C and hygroscopicity such as primary organic aerosol. At the high TD temperatures, the decreases of O:C and κorg indicate that evaporated organics were more oxygenated and had lower molecular weights. These trends are different from previous laboratory experiments and field observations, which reported that organic O:C increased monotonically with increasing TD temperature, whereas κorg decreased with the TD temperature. One possible reason is that previous studies were either focused on laboratory-generated secondary organic aerosol (SOA) or based on field observations at locations more dominated by SOA.

Global health burden of PM2.5, black and organic carbon aerosols

BACKGROUND AND AIM: Exposure to ambient particulate matter with a diameter smaller than 2.5µm (PM2.5) poses a major global health risk, commonly assessed with exposure-response functions that presume equivalent toxicity for different PM2.5 constituents. In this study, we assume anthropogenic organic aerosols and black carbon to be more health hazardous than other PM2.5 components as indicated by recent epidemiological and toxicological studies. METHODS: We used a data-informed global atmospheric chemistry model and exposure-response functions of the Global Burden of Disease study in 2020 to estimate the health burden of ambient PM2.5, and to attribute source categories. We also calculated the contributions of black carbon (BC), primary organic aerosols (POA) and anthropogenic secondary organic aerosols (aSOA). RESULTS:We estimated 4.23(95% confidence interval 3.0-6.14) million excess deaths per year from exposure to ambient PM2.5 of which, ∼67% may be attributed to anthropogenic sources assuming uniform toxicity for all types of PM2.5. Globally, 92%, 5% and 3% of excess deaths occur among adults, neonates and children, respectively, although these proportions vary largely by region. We find that domestic energy use, mostly from the burning of solid biofuels, is the largest contributor to BC, POA and aSOA globally. Considering these species to be twice as toxic as other compounds, domestic energy use emerges as the leading source of excess mortality from PM2.5 exposure, notably in Asia and Africa but also, in North America and Europe, where fossil fuel use in energy generation and transportation is the largest source category of anthropogenic PM2.5, mitigating emissions from domestic burning would have major health benefits. CONCLUSIONS:We suggest that relative toxicities of anthropogenic PM2.5 components and their sources should be considered in air quality policies. Our results offer a basis for country-specific mitigation measures, which will be more effective in improving air quality and public health than the conventional PM2.5 abatement measures. KEYWORDS: Particulate matter, Particle components, Policy research

Photodegradation of atmospheric chromophores: changes in oxidation state and photochemical reactivity

Abstract. Atmospheric chromophoric organic matter (COM) plays a fundamental role in photochemistry and aerosol aging. However, the effects of photodegradation on chemical components and photochemical reactivity of COM remain unresolved. Here, we report the potential effects of photodegradation on carbon contents, optical properties, fluorophore components and photochemical reactivity in aerosol. After 7 d of photodegradation, fluorescent intensity and the absorption coefficient of COM decrease by 71.4 % and 32.0 %, respectively. Photodegradation makes a difference to the chemical component of chromophore and the degree of aerosol aging. Low-oxidation humic-like substance (HULIS) is converted into high-oxidation HULIS due to photooxidation. Photodegradation also changes the photochemical reactivity. The generation of triplet-state COM (3COM*) decreases slightly in ambient particulate matter (ambient PM) but increases in primary organic aerosol (POA) following photodegradation. The results highlight that the opposite effect of photodegradation on photochemical reactivity in POA and ambient PM. However, the generation of singlet-oxygen (1O2) decreases obviously in POA and ambient PM, which could be attributed to photodegradation of precursors of 1O2. The combination of optical property, chemical component and reactive oxygen species has an important impact on the air quality. The new insights on COM photodegradation in aerosol reinforce the importance of studying dissolved organic matter (DOM) related with the photochemistry and aerosol aging.

Characterization of primary and aged wood burning and coal combustion organic aerosols in an environmental chamber and its implications for atmospheric aerosols

Abstract. Particulate matter (PM) affects visibility, climate, and public health. Organic matter (OM), a uniquely complex portion of PM, can make up more than half of total atmospheric fine PM mass. We investigated the effect of aging on secondary organic aerosol (SOA) concentration and composition for wood burning (WB) and coal combustion (CC) emissions, two major atmospheric OM sources, using mid-infrared (MIR) spectroscopy and aerosol mass spectrometry (AMS). For this purpose, primary emissions were injected into an environmental chamber and aged using hydroxyl (diurnal aging) and nitrate (nocturnal aging) radicals to reach an atmospherically relevant oxidative age. A time-of-flight AMS instrument was used to measure the high-time-resolution composition of non-refractory fine PM, while fine PM was collected on PTFE filters before and after aging for MIR analysis. AMS and MIR spectroscopy indicate an approximately 3-fold enhancement of organic aerosol (OA) concentration after aging (not wall-loss corrected). The OM:OC ratios also agree closely between the two methods and increase, on average, from 1.6 before aging to 2 during the course of aging. MIR spectroscopy, which is able to differentiate among oxygenated groups, shows a distinct functional group composition for aged WB (high abundance of carboxylic acids) and CC OA (high abundance of non-acid carbonyls) and detects aromatics and polycyclic aromatic hydrocarbons (PAHs) in emissions of both sources. The MIR spectra of fresh WB and CC aerosols are reminiscent of their parent compounds with differences in specific oxygenated functional groups after aging, consistent with expected oxidation pathways for volatile organic compounds (VOCs) of each emission source. The AMS mass spectra also show variations due to source and aging that are consistent with the MIR functional group (FG) analysis. Finally, a comparison of the MIR spectra of aged chamber WB OA with that of ambient samples affected by residential wood burning and wildfires reveals similarities regarding the high abundance of organics, especially acids, and the visible signatures of lignin and levoglucosan. This finding is beneficial for the source identification of atmospheric aerosols and interpretation of their complex MIR spectra.

Eight years of sub-micrometre organic aerosol composition data from the boreal forest characterized using a machine-learning approach

Abstract. The Station for Measuring Ecosystem–Atmosphere Relations (SMEAR) II, located within the boreal forest of Finland, is a unique station in the world due to the wide range of long-term measurements tracking the Earth–atmosphere interface. In this study, we characterize the composition of organic aerosol (OA) at SMEAR II by quantifying its driving constituents. We utilize a multi-year data set of OA mass spectra measured in situ with an Aerosol Chemical Speciation Monitor (ACSM) at the station. To our knowledge, this mass spectral time series is the longest of its kind published to date. Similarly to other previously reported efforts in OA source apportionment from multi-seasonal or multi-annual data sets, we approached the OA characterization challenge through positive matrix factorization (PMF) using a rolling window approach. However, the existing methods for extracting minor OA components were found to be insufficient for our rather remote site. To overcome this issue, we tested a new statistical analysis framework. This included unsupervised feature extraction and classification stages to explore a large number of unconstrained PMF runs conducted on the measured OA mass spectra. Anchored by these results, we finally constructed a relaxed chemical mass balance (CMB) run that resolved different OA components from our observations. The presented combination of statistical tools provided a data-driven analysis methodology, which in our case achieved robust solutions with minimal subjectivity. Following the extensive statistical analyses, we were able to divide the 2012–2019 SMEAR II OA data (mass concentration interquartile range (IQR): 0.7, 1.3, and 2.6 µg m−3) into three sub-categories – low-volatility oxygenated OA (LV-OOA), semi-volatile oxygenated OA (SV-OOA), and primary OA (POA) – proving that the tested methodology was able to provide results consistent with literature. LV-OOA was the most dominant OA type (organic mass fraction IQR: 49 %, 62 %, and 73 %). The seasonal cycle of LV-OOA was bimodal, with peaks both in summer and in February. We associated the wintertime LV-OOA with anthropogenic sources and assumed biogenic influence in LV-OOA formation in summer. Through a brief trajectory analysis, we estimated summertime natural LV-OOA formation of tens of ng m−3 h−1 over the boreal forest. SV-OOA was the second highest contributor to OA mass (organic mass fraction IQR: 19 %, 31 %, and 43 %). Due to SV-OOA's clear peak in summer, we estimate biogenic processes as the main drivers in its formation. Unlike for LV-OOA, the highest SV-OOA concentrations were detected in stable summertime nocturnal surface layers. Two nearby sawmills also played a significant role in SV-OOA production as also exemplified by previous studies at SMEAR II. POA, taken as a mix of two different OA types reported previously, hydrocarbon-like OA (HOA) and biomass burning OA (BBOA), made up a minimal OA mass fraction (IQR: 2 %, 6 %, and 13 %). Notably, the quantification of POA at SMEAR II using ACSM data was not possible following existing rolling PMF methodologies. Both POA organic mass fraction and mass concentration peaked in winter. Its appearance at SMEAR II was linked to strong southerly winds. Similar wind direction and speed dependence was not observed among other OA types. The high wind speeds probably enabled the POA transport to SMEAR II from faraway sources in a relatively fresh state. In the event of slower wind speeds, POA likely evaporated and/or aged into oxidized organic aerosol before detection. The POA organic mass fraction was significantly lower than reported by aerosol mass spectrometer (AMS) measurements 2 to 4 years prior to the ACSM measurements. While the co-located long-term measurements of black carbon supported the hypothesis of higher POA loadings prior to year 2012, it is also possible that short-term (POA) pollution plumes were averaged out due to the slow time resolution of the ACSM combined with the further 3 h data averaging needed to ensure good signal-to-noise ratios (SNRs). Despite the length of the ACSM data set, we did not focus on quantifying long-term trends of POA (nor other components) due to the high sensitivity of OA composition to meteorological anomalies, the occurrence of which is likely not normally distributed over the 8-year measurement period. Due to the unique and realistic seasonal cycles and meteorology dependences of the independent OA subtypes complemented by the reasonably low degree of unexplained OA variability, we believe that the presented data analysis approach performs well. Therefore, we hope that these results encourage also other researchers possessing several-year-long time series of similar data to tackle the data analysis via similar semi- or unsupervised machine-learning approaches. This way the presented method could be further optimized and its usability explored and evaluated also in other environments.

Measurement report: Emissions of intermediate-volatility organic compounds from vehicles under real-world driving conditions in an urban tunnel

Abstract. Intermediate-volatility organic compounds (IVOCs) emitted from vehicles are important precursors to secondary organic aerosols (SOAs) in urban areas, yet vehicular emission of IVOCs, particularly from on-road fleets, is poorly understood. Here we initiated a field campaign to collect IVOCs with sorption tubes at both the inlet and the outlet in a busy urban tunnel (&gt;30 000 vehicles per day) in south China for characterizing emissions of IVOCs from on-road vehicles. The average emission factor of IVOCs (EFIVOCs) was measured to be 16.77±0.89 mg km−1 (average ±95 % CI, confidence interval) for diesel and gasoline vehicles in the fleets, and based on linear regression, the average EFIVOCs was derived to be 62.79±18.37 mg km−1 for diesel vehicles and 13.95±1.13 mg km−1 for gasoline vehicles. The EFIVOCs for diesel vehicles from this study was comparable to that reported previously for non-road engines without after-treatment facilities, while the EFIVOCs for gasoline vehicles from this study was much higher than that recently tested for a China V gasoline vehicle. IVOCs from the on-road fleets did not show significant correlation with the primary organic aerosol (POA) or total non-methane hydrocarbons (NMHCs) as results from previous chassis dynamometer tests. Estimated SOA production from the vehicular IVOCs and VOCs surpassed the POA by a factor of ∼2.4, and IVOCs dominated over VOCs in estimated SOA production by a factor of ∼7, suggesting that controlling IVOCs is of greater importance to modulate traffic-related organic aerosol (OA) in urban areas. The results demonstrated that although on-road gasoline vehicles have much lower EFIVOCs, they contribute more IVOCs than on-road diesel vehicles due to its dominance in the on-road fleets. However, due to greater diesel than gasoline fuel consumption in China, emission of IVOCs from diesel engines would be much larger than that from gasoline engines, signaling the overwhelming contribution of IVOC emissions by non-road diesel engines in China.

Secondary aerosol formation from a Chinese gasoline vehicle: Impacts of fuel (E10, gasoline) and driving conditions (idling, cruising)

Chassis dynamometer experiments were conducted to investigate the effect of vehicle speed and usage of ethanol-blended gasoline (E10) on formation and evolution of gasoline vehicular secondary organic aerosol (SOA) using a Gothenburg Potential Aerosol Mass (Go: PAM) reactor. The SOA forms rapidly, and its concentration exceeds that of primary organic aerosol (POA) at an equivalent photochemical age (EPA) of ~1 day. The particle effective densities grow from 0.62 ± 0.02 g cm−3 to 1.43 ± 0.07 g cm−3 with increased hydroxyl radical (OH) exposure. The maximum SOA production under idling conditions (4259–7394 mg kg-fuel−1) is ~20 times greater than under cruising conditions. There was no statistical difference between SOA formation from pure gasoline and its formation from E10. The slopes in Van Krevelen diagram indicate that the formation pathways of bulk SOA includes the addition of both alcohol/peroxide functional groups and carboxylic acid formation from fragmentation. A closure estimation of SOA based on bottom-up and top-down methods shows that only 16%–38% of the measured SOA can be explained by the oxidation of measured volatile organic compounds (VOCs), suggesting the existence of missing precursors, e.g. unmeasured VOCs and probably semivolatile or intermediate volatile organic compounds (S/IVOCs). Our results suggest that applying parameters obtained from unified driving cycles to model SOA concentrations may lead to large discrepancies between modeled and ambient vehicular SOA. No reduction in vehicular `SOA production is realized by replacing normal gasoline with E10.

Quantification of solid fuel combustion and aqueous chemistry contributions to secondary organic aerosol during wintertime haze events in Beijing

Abstract. In recent years, intense haze events in megacities such as Beijing have received significant attention. Although secondary organic aerosol (SOA) has been identified as a major contributor to such events, knowledge of its sources and formation mechanisms remains uncertain. We investigate this question through the first field deployment of the extractive electrospray ionisation time-of-flight mass spectrometer (EESI-TOF) in Beijing, together with an Aerodyne long-time-of-flight aerosol mass spectrometer (L-TOF AMS). Measurements were performed during autumn and winter 2017, capturing the transition from non-heating to heating seasons. Source apportionment resolved four factors related to primary organic aerosols (traffic, cooking, biomass burning, and coal combustion), as well as four related to SOA. Of the SOA factors, two were related to solid fuel combustion (SFC), one to SOA generated from aqueous chemistry, and one to mixed/indeterminate sources. The SFC factors were identified from spectral signatures corresponding to aromatic oxidation products, while the aqueous SOA factor was characterised by signatures of small organic acids and diacids and unusually low CO+/CO2+ fragment ratios measured by the AMS. Solid fuel combustion was the dominant source of SOA during the heating season. However, a comparably intense haze event was also observed in the non-heating season and was dominated by the aqueous SOA factor. During this event, aqueous chemistry was promoted by the combination of high relative humidity and air masses passing over high-NOx regions to the south and east of Beijing, leading to high particulate nitrate. The resulting high liquid water content was highly correlated with the concentration of the aqueous SOA factor. These results highlight the strong compositional variability between different haze events, indicating the need to consider multiple formation pathways and precursor sources to describe SOA during intense haze events in Beijing.

Primary emissions and secondary production of organic aerosols from heated animal fats

Cooking is an important source of primary organic aerosol (POA) in urban areas, and it may also generate abundant non-methane organic gases (NMOGs), which form oxidized organic aerosol (OOA) after atmospheric oxidation. Edible fats play an important role in a balanced diet and are part of various types of cooking. We conducted laboratory studies to examine the primary emissions of POA and NMOGs and OOA formation using an oxidation flow reactor (OFR) for three animal fats (i.e., lard, beef and chicken fats) heated at two different temperatures (160 and 180 °C). Positive matrix factorization (PMF) revealed that OOA formed together with POA loss after photochemical aging, suggesting the conversion of some POA to OOA. The maximum OOA production rates (PRs) from heated animal fats, occurring under OH exposures (OHexp) of 8.3–15 × 1010 molecules cm−3 s, ranged from 8.9 to 24.7 μg min−1, 1.6–14.5 times as high as initial POA emission rates (ERs). NMOG emissions from heated animal fats were dominated by aldehydes, which contributed 14–71% of the observed OOA. We estimated that cooking-related OOA could contribute to as high as ~10% of total organic aerosol (OA) in an urban area in Hong Kong, where cooking OA (COA) dominated the POA. This study provides insights into the potential contribution of cooking to urban OOA, which might be especially pronounced when cooking contributions dominate the primary emissions.

Rapid transformation of ambient absorbing aerosols from West African biomass burning

Abstract. Seasonal biomass burning (BB) over West Africa is a globally significant source of carbonaceous particles in the atmosphere, which have important climate impacts but are poorly constrained. Here, the evolution of smoke aerosols emitted from flaming-controlled burning of agricultural waste and wooded savannah in the Senegal region was characterized over a timescale of half-day advection from the source during the MOYA-2017 (Methane Observation Yearly Assessment-2017) aircraft campaign. Plumes from such fire types are rich in black carbon (BC) emissions. Concurrent measurements of chemical composition, organic aerosol (OA) oxidation state, bulk aerosol size and BC mixing state reveal that emitted BB submicron aerosols changed dramatically with time. Various aerosol optical properties (e.g. absorption Ångström exponent – AAE – and mass absorption coefficients – MACs) also evolved with ageing. In this study, brown carbon (BrC) was a minor fractional component of the freshly emitted BB aerosols (&lt; 0.5 h), but the increasing AAE with particle age indicates that BrC formation dominated over any loss process over the first ∼ 12 h of plume transport. Using different methods, the fractional contribution of BrC to total aerosol absorption showed an increasing trend with time and was ∼ 18 %–31 % at the optical wavelength of 405 nm after half-day transport. The generated BrC was found to be positively correlated with oxygenated and low-volatility OA, likely from the oxidation of evaporated primary OA and secondary OA formation. We found that the evolution of BrC with particle age was different in this region compared with previous BB field studies that mainly focused on emissions from smouldering fires, which have shown a high contribution from BrC at the source and BrC net loss upon ageing. This study suggests an initial stage of BrC absorption enhancement during the evolution of BB smoke. Secondary processing is the dominant contributor to BrC production in this BB region, in contrast to the primary emission of BrC previously reported in other BB studies. The total aerosol absorption normalized to BC mass (MACmeas-BC) was also enhanced with ageing due to the lensing effect of increasingly thick coatings on BC and the absorption by BrC. The effect of ageing on aerosol absorption, represented by the absorption enhancement (EAbs-MAC), was estimated over timescales of hours. MOYA-2017 provides novel field results. The comparisons between MOYA-2017 and previous field studies imply that the evolution of absorbing aerosols (BC and BrC) after emission varies with source combustion conditions. Different treatments of absorbing aerosol properties from different types of fires and their downwind evolution should be considered when modelling regional radiative forcing. These observational results will be very important for predicting climate effects of BB aerosol in regions controlled by flaming burning of agricultural waste and savannah-like biomass fuels.

Physical and chemical properties of urban aerosols in São Paulo, Brazil: links between composition and size distribution of submicron particles

Abstract. In this work, the relationships between size and composition of submicron particles (PM1) were analyzed at an urban site in the Metropolitan Area of São Paulo (MASP), a megacity with about 21 million inhabitants. The measurements were carried out from 20 December 2016 to 15 March 2017. The chemical composition was measured with an Aerodyne Aerosol Chemical Speciation Monitor and size distribution with a TSI Scanning Mobility Particle Sizer 3082. PM1 mass concentrations in the MASP had an average mass concentration of 11.4 µg m−3. Organic aerosol (OA) dominated the PM1 composition (56 %), followed by sulfate (15 %) and equivalent black carbon (eBC, 13 %). Four OA classes were identified using positive matrix factorization: oxygenated organic aerosol (OOA, 40 % of OA), biomass burning organic aerosol (BBOA, 13 %), and two hydrocarbon-like OA components (a typical HOA related to vehicular emissions (16 %) and a second HOA (21 %) representing a mix of anthropogenic sources). Particle number concentrations averaged 12 100±6900 cm−3, dominated by the Aitken mode. The accumulation mode increased under relatively high-PM1 conditions, suggesting an enhancement of secondary organic aerosol (SOA) production. Conversely, the contribution of nucleation-mode particles was less dependent on PM1 levels, consistent with vehicular emissions. The relationship between aerosol size modes and PM1 composition was assessed by multilinear regression (MLR) models. Secondary inorganic aerosols were partitioned between Aitken and accumulation modes, related to condensation particle growth processes. Submicron mass loading in the accumulation mode was mostly associated with highly oxidized OOA and also traffic-related emissions. To the authors' knowledge, this is the first work that uses the MLR methodology to estimate the chemical composition of the different aerosol size modes. The chemical composition with size-dependent PM provides innovative information on the properties of both primary and secondary organic aerosols, as well as inorganic aerosols in a complex urban environment. The results emphasize the relevance of vehicular emissions to the air quality at MASP and highlight the key role of secondary processes on the PM1 ambient concentrations in the region since 56 % of PM1 mass loading was attributed to SOA and secondary inorganic aerosol.

Regional modeling of secondary organic aerosol formation over eastern China: The impact of uptake coefficients of dicarbonyls and semivolatile process of primary organic aerosol

Capturing the secondary organic aerosol (SOA) concentration using the chemical transport model is difficult due to a large knowledge gap of its formation mechanism. Previous studies demonstrated the uptake of dicarbonyls and semivolatile process of primary organic aerosol (POA) emissions are the significant sources of SOA. However, the uptake coefficients of dicarbonyls have large uncertainties and the SOA from the semivolatile process of POA emission remains unclear. We applied the revised reactive uptake parameterization, with “salting effects” for dicarbonyls, and updated approaches for POA to the Community Multiscale Air Quality Modeling System (CMAQ) simulations for October 2014 to study their impacts on modeling the SOA formation over eastern China. We introduce a method of quantifying crystalized or deliquescent aerosols to further improve the parameterization. The revised glyoxal uptake coefficients results in higher glyoxal SOA in the Beijing-Tianjin-Hebei region, where is typically under low relative humidity (RH) and high aerosol pH conditions. It gives lower glyoxal SOA in the Pearl River Delta region, where is typically under high RH and low pH conditions. The updated parameterization gives negligible methylglyoxal SOA due to the low uptake coefficients. The implementation of semivolatile process of POA and the approach for potential SOA from combustion sources will largely decrease the predicted POA and increase the modeled SOA concentrations over eastern China. The increased SOA from POA emissions could improve the model performance for organic carbon and SOA. It slightly improves the performance in PM2.5 modeling by compensating the reduction of modeled POA. This study indicates the mixed impact of a parameterization considering “salting effects” on modeling the dicarbonyls SOA in key regions of eastern China. It also demonstrates the improved performance by implementing the POA approaches in aerosol modeling using CMAQ. Meanwhile, the uncertainty in the revised reactive uptake parameterization and POA approaches is discussed.

Increase in secondary organic aerosol in an urban environment

Abstract. The evolution of fine aerosol (PM1) species as well as the contribution of potential sources to the total organic aerosol (OA) at an urban background site in Barcelona, in the western Mediterranean basin (WMB) was investigated. For this purpose, a quadrupole aerosol chemical speciation monitor (Q-ACSM) was deployed to acquire real-time measurements for two 1-year periods: May 2014–May 2015 (period A) and September 2017–October 2018 (period B). Total PM1 concentrations showed a slight decrease (from 10.1 to 9.6 µg m−3 from A to B), although the relative contribution of inorganic and organic compounds varied significantly. Regarding inorganic compounds, SO42-, black carbon (BC) and NH4+ showed a significant decrease from period A to B (−21 %, −18 % and −9 %, respectively), whilst NO3- concentrations were higher in B (+8 %). Source apportionment revealed OA contained 46 % and 70 % secondary OA (SOA) in periods A and B, respectively. Two secondary oxygenated OA sources (OOA) were differentiated by their oxidation status (i.e. ageing): less oxidized (LO-OOA) and more oxidized (MO-OOA). Disregarding winter periods, when LO-OOA production was not favoured, LO-OOA transformation into MO-OOA was found to be more effective in period B. The lowest LO-OOA-to-MO-OOA ratio, excluding winter, was in September–October 2018 (0.65), implying an accumulation of aged OA after the high temperature and solar radiation conditions in the summer season. In addition to temperature, SOA (sum of OOA factors) was enhanced by exposure to NOx-polluted ambient and other pollutants, especially to O3 and during afternoon hours. The anthropogenic primary OA sources identified, cooking-related OA (COA), hydrocarbon-like OA (HOA), and biomass burning OA (BBOA), decreased from period A to B in both absolute concentrations and relative contribution (as a whole, 44 % and 30 %, respectively). However, their concentrations and proportion to OA grew rapidly during highly polluted episodes. The influence of certain atmospheric episodes on OA sources was also assessed. Both SOA factors were boosted with long- and medium-range circulations, especially those coming from inland Europe and the Mediterranean (triggering mainly MO-OOA) and summer breeze-driven regional circulation (mainly LO-OOA). In contrast, POA was enhanced either during air-renewal episodes or stagnation anticyclonic events.

Carbonaceous aerosol composition in air masses influenced by large-scale biomass burning: a case study in northwestern Vietnam

Abstract. We investigated concentrations of organic carbon (OC), elemental carbon (EC), and a wide range of particle-bound organic compounds in daily sampled PM2.5 at the remote Pha Din (PDI) – Global Atmosphere Watch (GAW) monitoring station in northwestern Vietnam during an intense 3-week sampling campaign from 23 March to 12 April 2015. The site is known to receive trans-regional air masses during large-scale biomass burning (BB) episodes. BB is a globally widespread phenomenon and BB emission characterization is of high scientific and societal relevance. Emissions composition is influenced by multiple factors (e.g., fuel and thereby vegetation type, fuel moisture, fire temperature, available oxygen). Due to regional variations in these parameters, studies in different world regions are needed. OC composition provides valuable information regarding the health- and climate-relevant properties of PM2.5. Yet, OC composition studies from PDI are missing in the scientific literature to date. Therefore, we quantified 51 organic compounds simultaneously by in situ derivatization thermal desorption gas chromatography and time-of-flight mass spectrometry (IDTD-GC-TOFMS). Anhydrosugars, methoxyphenols, n-alkanes, fatty acids, polycyclic aromatic hydrocarbons, oxygenated polycyclic aromatic hydrocarbons, nitrophenols, and OC were used in a hierarchical cluster analysis highlighting distinctive patterns for periods under low, medium, and high BB influence. The highest particle phase concentration of the typical primary organic aerosol (POA) and possible secondary organic aerosol (SOA) constituents, especially nitrophenols, were found on 5 and 6 April. We linked the trace gas mixing ratios of methane (CH4), carbon dioxide (CO2), carbon monoxide (CO), and ozone (O3) to the statistical classification of BB events based on OA composition and found increased CO and O3 levels during medium and high BB influence. Likewise, a backward trajectory analysis indicates different source regions for the identified periods based on the OA clusters, with cleaner air masses arriving from the northeast, i.e., mainland China and the Yellow Sea. The more polluted periods are characterized by trajectories from the southwest, with more continental recirculation of the medium cluster and more westerly advection for the high cluster. These findings highlight that BB activities in northern Southeast Asia significantly enhance the regional organic aerosol loading and also affect the carbonaceous PM2.5 constituents and the trace gases in northwestern Vietnam. The presented analysis adds valuable data on the carbonaceous and chemical composition of PM2.5, in particular of OC, in a region of scarce data availability, and thus offers a reference dataset from Southeast Asian large-scale BB for future studies. Such a reference dataset may be useful for the evaluation of atmospheric transport simulation models, or for comparison with other world regions and BB types, such as Australian bush fires, African savannah fires, or tropical peatland fires.

Modeled changes in source contributions of particulate matter during the COVID-19 pandemic in the Yangtze River Delta, China

Abstract. Within a short time after the outbreak of coronavirus disease 2019 (COVID-19) in Wuhan, Hubei, the Chinese government introduced a nationwide lockdown to prevent the spread of the pandemic. The quarantine measures have significantly decreased the anthropogenic activities, thus improving air quality. To study the impacts caused by the lockdown on specific source sectors and regions in the Yangtze River Delta (YRD), the Community Multiscale Air Quality (CMAQ) model was used to investigate the changes in source contributions to fine particulate matter (PM2.5) from 23 January to 28 February 2020, based on different emission control cases. Compared to case 1 (without emission reductions), the total PM2.5 mass for case 2 (with emission reductions) decreased by more than 20 % over the entire YRD, and the reduction ratios of its components were 15 %, 16 %, 20 %, 43 %, 34 %, and 35 % in primary organic aerosol (POA), elemental carbon (EC), sulfate, nitrate, ammonium, and secondary organic aerosol (SOA), respectively. The source apportionment results showed that PM2.5 concentrations from transportation decreased by 40 %, while PM2.5 concentrations from the residential and power sectors decreased by less than 10 % due to the lockdown. Although all sources decreased, the relative contribution changed differently. Contributions from the residential sector increased by more than 10 % to 35 %, while those in the industrial sector decreased by 33 %. Considering regional transport, the total PM2.5 mass of all regions decreased 20 %–30 % in the YRD, with the largest decreased value of 5.0 µg m−3 in Henan, Hebei, Beijing, and Tianjin (Ha-BTH). In Shanghai, the lower contributions from local emissions and regional transmission (mainly Shandong and Ha-BTH) led to the reduced PM2.5. This study suggests adjustments of control measures for various sources and regions.