Source Of Organic Aerosol Research Articles

충남 서산에서 가을에 측정한 초미세먼지의 오염 특성 조사

In this study, chemical characteristics of PM2.5 collected between October 1 and November 4, 2019 at Chungcheong region air quality research center in Seosan, were studied to understand reasons leading to PM2.5 increases. 24-hr integrated PM2.5 samples were analysed for organic and elemental carbon (OC and EC), water-soluble OC (WSOC), and eight water-soluble inorganic ions. Over the study period, increase in PM2.5 concentration was attributed to enhancement of organic mass (OM=1.8×OC) and NO₃- concentrations. Relationships of OC and WSOC with EC, K+, Cl-, and secondary NO₃- showed good-to-strong correlations, suggesting primary emissions (e.g., traffic and biomass burning sources) and secondary organic aerosol (OA) formation contributed to WSOC and OC concentrations. Moreover, high WSOC/OC (mean: 0.54) and OC/EC (mean: 9.0) ratios support the existence of various OA sources at the site. Four PM2.5 pollution episodes (October, 10 (event I), 17 (event II), 20~22 (event III), and November 02 (event IV)), which exceeded 24-hr PM2.5 Korean standard of 35 μg/m³, occurred and were related to concentration increases in OM and secondary ionic species. Based on synoptic weather patterns, PM2.5 forecast results, and air mass transport pathways, it was concluded that events I, II, and IV were significantly influenced by locally produced pollutions, while event III was impacted by both long-range transport of air pollutants and local emissions, with the highest concentration of SO₄2- (7.3 μg/m³). Among the four events, highest OM and NO₃- concentrations were found in the events IV and III, respectively. Results from this study suggest that strategies to reduce nitrogen oxides and organic aerosols in the study region are formulated to control PM2.5 levels.

Source apportionment of fine organic carbon (OC) using receptor modelling at a rural site of Beijing: Insight into seasonal and diurnal variation of source contributions

This study was designed to investigate the seasonal characteristics and apportion the sources of organic carbon during non-haze days (<75 μg m−3) and haze (≥75 μg m−3) events at Pinggu, a rural Beijing site. Time-resolved concentrations of carbonaceous aerosols and organic molecular tracers were measured during the winter of 2016 and summer 2017, and a Chemical Mass Balance (CMB) model was applied to estimate the average source contributions. The concentration of OC in winter is comparable with previous studies, but relatively low during the summer. The CMB model apportioned seven separate primary sources, which explained on average 73.8% on haze days and 81.2% on non-haze days of the organic carbon in winter, including vegetative detritus, biomass burning, gasoline vehicles, diesel vehicles, industrial coal combustion, residential coal combustion and cooking. A slightly lower percentage of OC was apportioned in the summer campaign with 64.5% and 78.7% accounted for. The other unapportioned OC is considered to consist of secondary organic carbon (SOC). During haze episodes in winter, coal combustion and SOC were the dominant sources of organic carbon with 23.3% and 26.2%, respectively, followed by biomass burning emissions (20%), whereas in summer, industrial coal combustion and SOC were important contributors. Diurnal contribution cycles for coal combustion and biomass burning OC showed a peak at 6–9 pm, suggesting domestic heating and cooking were the main sources of organic aerosols in this rural area. Backward trajectory analysis showed that high OC concentrations were measured when the air mass was from the south, suggesting that the organic aerosols in Pinggu were affected by both local emissions and regional transport from central Beijing and Hebei province during haze episodes. The source apportionment by CMB is compared with the results of a Positive Matrix Factorization (PMF) analysis of ACSM data for non-refractory PM1, showing generally good agreement.

Molecular characteristics of organic compositions in fresh and aged biomass burning aerosols

Biomass burning (BB) is the most important source of primary organic aerosols (OA) in the atmosphere that has significant impact on local/regional air quality and human health. However, few studies paid attention to the evolution of molecular characteristics of BB OA in the atmospheric aging processes. In this study, both fresh and aged PM2.5 aerosols from burning of rice, maize, and wheat straws were collected from a combined system of combustion chamber and oxidation flow reactor, and were analyzed for >100 organic species. The emission factors (EFs) of anhydrosugars and some fatty acids showed slight variations between fresh and aged samples, indicating that these compounds are relatively stable. However, the EFs of n-alkanes, fatty alcohols, and parent-PAHs decreased 8–57% from fresh to aged samples, suggesting that they can undergo further oxidation to form other organic materials in the atmosphere. Phthalic acids, nitrophenols and isoprene-derived products were mainly secondarily formed by aging processes. Thus their EFs increased by 2–23 times from fresh to aged samples. Levoglucosan was the most abundant individual organic tracer, and its EF varied slightly between fresh and aged samples, proving its indicative role on BB emission. Moreover, the ratio of vanillic acid to levoglucosan and p-hydroxybenzoic acid to levoglucosan increased 2–13 times from fresh to aged samples. Therefore they can be used to investigate the impact of aging processes on BB aerosols in the atmosphere. RO2 + HO2 pathway derived 2-methyltetrols (2-MTs) predominated the EFs of isoprene-derived products (SOAi) in the fresh samples. However, RO2 + NO pathway derived 2-methylglyceric acid (2-MGA) increased by >30 times and became comparable with 2-MTs in aged particles. The ratio of 2-MGA/2-MTs increased from 0.06–0.27 in fresh samples to 0.94–1.18 in aged samples, because the high loading of NOx in BB smoke enhanced the formation of SOAi through RO2 + NO reactions.

Seasonal variations in the sources of organic aerosol in Xi'an, Northwest China: The importance of biomass burning and secondary formation

The Guanzhong basin is a part of the three top priority regions in China's blue sky action as of 2019. Understanding the chemical composition, sources, and atmospheric process of aerosol in this region is therefore imperative for improving air quality. In this study, we present, for the first time, the seasonal variations of organic aerosol (OA) in Xi'an, the largest city in the Guanzhong basin. Biomass burning OA (BBOA) and oxidized OA (OOA) contributed >50% of OA in both autumn and winter. The average concentrations of BBOA in autumn (14.8 ± 5.1 μg m−3) and winter (11.6 ± 6.8 μg m−3) were similar. The fractional contribution of BBOA to total OA, however, decreased from 31.9% in autumn to 15.3% in winter, because of enhanced contributions from other sources in winter. The OOA fraction in OA increased largely from 20.9% in autumn to 34.9% in winter, likely due to enhanced emissions of precursors and stagnant meteorological conditions which facilitate the accumulation and secondary formation. A large increase in OOA concentration was observed during polluted days, by a factor of ~4 in autumn and ~6 in winter compared to clean days. In both seasons, OOA formation was most likely dominated by photochemical oxidation when aerosol liquid water content was <30 μg m−3 or by aqueous-phase processes when Ox was <35 ppb. A higher concentration of BBOA was observed for air masses circulated within the Guanzhong basin (16.5–18.1 μg m−3), compared to air masses from Northwest and West (10.9–14.5 μg m−3). Furthermore, compared with OA fraction in non-refractory PM1 in other regions of China, BBOA (17–19%) and coal combustion OA (10–20%) were major emission sources in the Guanzhong Basin and the BTH region, respectively, whereas OOA (10–34%) was an important source in all studied regions.

Brown carbon in atmospheric fine particles in Yangzhou, China: Light absorption properties and source apportionment

Light absorbing organic carbon, a.k.a., brown carbon (BrC) is an important contributor to air quality deterioration and global radiative forcing. This work studied optical, chemical properties and sources of BrC in fine particles (PM2.5) collected in Yangzhou, China. The light absorption coefficient at 365 nm of methanol-soluble organics (Abs365,MSOC) and water-soluble organics (Abs365,WSOC) were 13.50 ± 7.03 M/m and 6.08 ± 4.30 M/m, respectively. Mass absorption efficiency at 365 nm (MAE365) of methanol-soluble BrC (1.12 ± 0.35 m2/g C) was also higher than water-soluble BrC (0.75 ± 0.29 m2/g C). For water-soluble BrC, both Abs365 and MAE365 generally decreased with increases of its oxygen-to‑carbon (O/C) ratios and oxidation states (OSc), indicative of photo-bleaching upon chemical ageing. Positive responses of Abs365,WSOC and MAE365,WSOC to nitrogen-to‑carbon (N/C) ratios and water-soluble organic nitrogen (ON) contents reveal that ON species are important BrC chromophores. A multiple linear regression model was applied to apportion Abs365,WSOC to contributions of different factors resolved from positive matrix factorization on water-soluble organic aerosols (OA), and obtained MAE365 values of different OA factors. Overall, primary OA sources including traffic (18.9%), biomass burning (23.7%), and cooking-related OA (10.5%) together dominated the Abs365,WSOC despite their total mass contribution was only about one third (31.9%). The largest single contributor of Abs365,WSOC, however, was the less-oxidized secondary OA (33.8%); the more-oxidized secondary OA factor dominated water-soluble OA mass (50.8%), yet its light absorptivity was the weakest and contributed only 13.1% of Abs365,WSOC.

Molecular composition and sources of water-soluble organic aerosol in summer in Beijing

Water-soluble organic aerosol (WSOA) constitutes a large fraction of OA and plays an important role in formation of secondary OA (SOA). Here we characterized the sources and molecular composition of WSOA in summer in Beijing using high-resolution aerosol mass spectrometer and orbitrap mass spectrometer equipped with electrospray ionization. Our results showed that WSOA was the major fraction of OA on average accounting for 69% in summer, which is much higher than that (47%) in winter. However, the oxidation degree of WSOA was comparable between summer and winter (O/C = 0.62 vs. 0.63). Positive matrix factorization analysis showed that SOA contributed dominantly to WSOA (72%) indicating that WSOA was mainly from secondary formation. The two water-soluble SOA factors that are associated with regional processing (OOA-1) and photochemical production (OOA-2), respectively, showed very different behaviors throughout the study. OOA-2 showed much enhanced contribution during polluted periods with low relative humidity (RH), while OOA-1 played a more important role during high RH periods. Molecular composition analysis of WSOA revealed a high diversity of CHO (compounds only containing carbon, hydrogen and oxygen) and CHOS (sulfur-containing organics) in WSOA in summer. Particularly, the relative intensity fraction of CHOS- compounds was increased by 42% from clean to polluted days which was associated with large increases (20%) in organosulfates (OSs) with lower O∗/C (0.1–0.4), and OOA-1. These results suggest the formation of more unsaturated OSs in OOA-1 during polluted days in summer. Comparatively, the biogenic-derived OSs remained relatively stable (24–31%) for the entire study highlighting the ubiquitous importance of biogenic SOA in summer.

Modeling organic aerosol over Europe in summer conditions with the VBS-GECKO parameterization: sensitivity to secondary organic compound properties and IVOC (intermediate-volatility organic compound) emissions

Abstract. The VBS-GECKO (volatility basis set – Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) parameterization for secondary organic aerosol (SOA) formation was integrated into the chemistry-transport model CHIMERE. Concentrations of organic aerosol (OA) and SOA were simulated over Europe for the July–August 2013 period. Simulated concentrations with VBS-GECKO were compared to results obtained with the former H2O parameterization implemented in CHIMERE and to observations from EMEP, ACTRIS and other observations available in the EBAS database. The model configuration using the VBS-GECKO parameterization slightly improves the performances compared to the model configuration using the former H2O parameterization. The VBS-GECKO model configuration performs well for stations showing a large SOA concentration from biogenic sources, especially in northern Europe, but underestimates OA concentrations over stations close to urban areas. Simulated OA was found to be mainly secondary (∼85 %) and from terpene oxidation. Simulations show negligible contribution of the oxidation of mono-aromatic compounds to SOA production. Tests performed to examine the sensitivity of simulated OA concentrations to hydro-solubility, volatility, aging rates and NOx regime have shown that the VBS-GECKO parameterization provides consistent results, with a weak sensitivity to changes in the parameters provided by the gas-phase mechanism included in CHIMERE (e.g., HOx or NOx concentrations). Different scenarios considering intermediate-volatility organic compound (IVOC) emissions were tested to examine the contribution of IVOC oxidation to SOA production. At the continental scale, these simulations show a weak sensitivity of OA concentrations to IVOC emission variations. At the local scale, accounting for IVOC emissions was found to lead to a substantial increase in OA concentrations in the plume from urban areas. This additional OA source remains too small to explain the gap between simulated and measured values at stations where anthropogenic sources are dominant.

Characterization of organic aerosol across the global remote troposphere: a comparison of ATom measurements and global chemistry models

Abstract. The spatial distribution and properties of submicron organic aerosol (OA) are among the key sources of uncertainty in our understanding of aerosol effects on climate. Uncertainties are particularly large over remote regions of the free troposphere and Southern Ocean, where very few data have been available and where OA predictions from AeroCom Phase II global models span 2 to 3 orders of magnitude, greatly exceeding the model spread over source regions. The (nearly) pole-to-pole vertical distribution of non-refractory aerosols was measured with an aerosol mass spectrometer onboard the NASA DC-8 aircraft as part of the Atmospheric Tomography (ATom) mission during the Northern Hemisphere summer (August 2016) and winter (February 2017). This study presents the first extensive characterization of OA mass concentrations and their level of oxidation in the remote atmosphere. OA and sulfate are the major contributors by mass to submicron aerosols in the remote troposphere, together with sea salt in the marine boundary layer. Sulfate was dominant in the lower stratosphere. OA concentrations have a strong seasonal and zonal variability, with the highest levels measured in the lower troposphere in the summer and over the regions influenced by biomass burning from Africa (up to 10 µg sm−3). Lower concentrations (∼0.1–0.3 µg sm−3) are observed in the northern middle and high latitudes and very low concentrations (&lt;0.1 µg sm−3) in the southern middle and high latitudes. The ATom dataset is used to evaluate predictions of eight current global chemistry models that implement a variety of commonly used representations of OA sources and chemistry, as well as of the AeroCom-II ensemble. The current model ensemble captures the average vertical and spatial distribution of measured OA concentrations, and the spread of the individual models remains within a factor of 5. These results are significantly improved over the AeroCom-II model ensemble, which shows large overestimations over these regions. However, some of the improved agreement with observations occurs for the wrong reasons, as models have the tendency to greatly overestimate the primary OA fraction and underestimate the secondary fraction. Measured OA in the remote free troposphere is highly oxygenated, with organic aerosol to organic carbon (OA ∕ OC) ratios of ∼2.2–2.8, and is 30 %–60 % more oxygenated than in current models, which can lead to significant errors in OA concentrations. The model–measurement comparisons presented here support the concept of a more dynamic OA system as proposed by Hodzic et al. (2016), with enhanced removal of primary OA and a stronger production of secondary OA in global models needed to provide better agreement with observations.

Chemical characteristics and sources of water-soluble organic aerosol in southwest suburb of Beijing

PM2.5 filter sampling and components measurement were conducted in autumn and winter from 2014 to 2015 at a suburban site (referred herein as “LLH site”) located in the southwest of Beijing. The offline aerosol mass spectrometry (offline-AMS) analysis and positive matrix factorization (PMF) were applied for measurement and source apportionment of water-soluble organic aerosol (WSOA). Organic aerosol (OA) always dominated PM2.5 during the sampling period, especially in winter. WSOA pollution was serious during the polluted period both in autumn (31.1 µg/m3) and winter (31.9 µg/m3), while WSOA accounted for 54.4% of OA during the polluted period in autumn, much more than that (21.3%) in winter. The oxidation degree of WSOA at LLH site was at a high level (oxygen-to-carbon ratio, O/C=0.91) and secondary organic aerosol (SOA) contributed more mass ratio of WSOA than primary organic aerosol (POA) during the whole observation period. In winter, coal combustion OA (CCOA) was a stable source of OA and on average accounted for 25.1% of WSOA. In autumn, biomass burning OA (BBOA) from household combustion contributed 38.3% of WSOA during polluted period. In addition to oxygenated OA (OOA), aqueous-oxygenated OA (aq-OOA) was identified as an important factor of SOA. During heavy pollution period, the mass proportion of aq-OOA to WSOA increased significantly, implying the significant SOA formation through aqueous-phase process. The result of this study highlights the concentration on controlling the residential coal and biomass burning, as well as the research needs on aqueous chemistry in OA formation.

Online Chemical Characterization and Source Identification of Summer and Winter Aerosols in Măgurele, Romania

Aerosols and organic source apportionment were characterized using data collected during two measurement campaigns. These campaigns were conducted during the summer and winter seasons at Măgurele, a site located southwest of Bucharest, the capital of Romania and one of the largest cities in southeastern Europe (raking seven in Europe based on population). The summer campaign was conducted between 7 June–18 July 2012, and the winter campaign from 14 January–6 February 2013. Approximately 50% of the organic fraction contribution to the total submicron particulate matter sampled by aerosol mass spectrometer was evidenced during both seasons. Submicronic organic aerosol sources were quantified using the positive matrix factorization approach. For warm (summer) and cold (winter) seasons, more than 50% from total organics was represented by oxidized factors. For the summer season, separate analyses were conducted on data influenced by urban and non-urban sources. The influence of pollution from Bucharest on the measurement site was observed in aerosol concentration and composition. The primary organic aerosols have different contribution percentage during summer, depending on their main origin. The influence of Bucharest, during summer, included cooking contribution of 13%. The periods with more regional influence were characterized by lower contribution from traffic and biomass burning in a total proportion of 28%. In winter, the influence of local non-traffic sources was dominant. For more than 99% of the measurements, the biomass burning indicator, f 60 , exceeded the background value, with residential heating being an important source in this area. Fossil fuel contribution was confirmed for one week during the winter campaign, when 14 C analysis of total and elemental carbon revealed the presence of 17% fossil contributions to total carbon. Mass spectrometry, 14 C and absorption data suggest biomass burning as the predominant primary source of organic aerosols for the winter season.

Summertime and wintertime atmospheric processes of secondary aerosol in Beijing

Abstract. Secondary aerosol constitutes a large fraction of fine particles in urban air of China. However, its formation mechanisms and atmospheric processes remain largely uncertain despite considerable study in recent years. To elucidate the seasonal variations in fine-particle composition and secondary aerosol formation, an Aerodyne quadrupole aerosol chemical speciation monitor (Q-ACSM), combined with other online instruments, was used to characterize the sub-micrometer particulate matter (diameter &lt; 1 µm, PM1) in Beijing during summer and winter 2015. Our results suggest that photochemical oxidation was the major pathway for sulfate formation during summer, whereas aqueous-phase reaction became an important process for sulfate formation during winter. High concentrations of nitrate (17 % of the PM1 mass) were found during winter, explained by enhanced gas-to-particle partitioning at low temperature, while high nitrate concentrations (19 %) were also observed under the conditions of high relative humidity (RH) during summer, likely due to the hydrophilic property of NH4NO3 and hydrolysis of N2O5. As for organic aerosol (OA) sources, secondary OA (SOA) dominated the OA mass (74 %) during summer, while the SOA contribution decreased to 39 % during winter due to enhanced primary emissions in the heating season. In terms of the SOA formation, photochemical oxidation perhaps played an important role for summertime oxygenated OA (OOA) formation and less-oxidized wintertime OOA (LO-OOA) formation. The wintertime more-oxidized OOA (MO-OOA) showed a good correlation with aerosol liquid water content (ALWC), indicating a more important contribution of aqueous-phase processing over photochemical production to MO-OOA. Meanwhile, the dependence of LO-OOA and the mass ratio of LO-OOA to MO-OOA on atmospheric oxidative tracer (i.e., Ox) both degraded when RH was greater than 60 %, suggesting that RH or aerosol liquid water may also affect LO-OOA formation.

Efficient Nighttime Biogenic SOA Formation in a Polluted Residual Layer

AbstractOrganic nitrates formed from nighttime reaction between anthropogenic nitrate radicals (NO3) and biogenic volatile organic compounds (BVOCs) are an important but highly uncertain source of secondary organic aerosol (SOA). Here we report on the enhanced nighttime biogenic SOA formation observed in a polluted residual layer over Sacramento, California, the morning of 15 June 2010 during the Carbonaceous Aerosols and Radiative Effects Study (CARES). Trajectory analysis showed that the residual layer air, containing isoprene and trace amounts of monoterpenes left over after nighttime oxidation, was influenced by the San Francisco Bay Area emissions the previous evening. The residual layer aerosol was also enriched in nitrate, with about 64% of it estimated to be in the form of organic nitrates. The nitrate:organic mass ratio of the SOA was about 0.47 ± 0.044, which corresponds to the range typically found in isoprene mononitrates. Assuming the SOA was composed of organic mononitrates, its nominal molecular weight was estimated at 186 ± 11 g mol−1, consistent with the highly functionalized isoprene hydroxynitrates that have been observed in the particle phase in the southeast United States. Overall, our findings show that the efficiency of nighttime biogenic SOA formation, expressed as the change in organic aerosol mass relative to carbon monoxide (∆OA/∆CO), equals ~100 μg m−3 ppmv and is comparable to the range previously estimated for enhanced daytime SOA formation from mixed anthropogenic and biogenic emissions during CARES. Assuming the SOA was formed from isoprene oxidation by NO3, we estimated mass yields of up to 0.55, consistent with previous field estimates.

How emissions uncertainty influences the distribution and radiative impacts of smoke from fires in North America

Abstract. Fires and the aerosols that they emit impact air quality, health, and climate, but the abundance and properties of carbonaceous aerosol (both black carbon and organic carbon) from biomass burning (BB) remain uncertain and poorly constrained. We aim to explore the uncertainties associated with fire emissions and their air quality and radiative impacts from underlying dry matter consumed and emissions factors. To investigate this, we compare model simulations from a global chemical transport model, GEOS-Chem, driven by a variety of fire emission inventories with surface and airborne observations of black carbon (BC) and organic aerosol (OA) concentrations and satellite-derived aerosol optical depth (AOD). We focus on two fire-detection-based and/or burned-area-based (FD-BA) inventories using burned area and active fire counts, respectively, i.e., the Global Fire Emissions Database version 4 (GFED4s) with small fires and the Fire INventory from NCAR version 1.5 (FINN1.5), and two fire radiative power (FRP)-based approaches, i.e., the Quick Fire Emission Dataset version 2.4 (QFED2.4) and the Global Fire Assimilation System version 1.2 (GFAS1.2). We show that, across the inventories, emissions of BB aerosol (BBA) differ by a factor of 4 to 7 over North America and that dry matter differences, not emissions factors, drive this spread. We find that simulations driven by QFED2.4 generally overestimate BC and, to a lesser extent, OA concentrations observations from two fire-influenced aircraft campaigns in North America (ARCTAS and DC3) and from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network, while simulations driven by FINN1.5 substantially underestimate concentrations. The GFED4s and GFAS1.2-driven simulations provide the best agreement with OA and BC mass concentrations at the surface (IMPROVE), BC observed aloft (DC3 and ARCTAS), and AOD observed by MODIS over North America. We also show that a sensitivity simulation including an enhanced source of secondary organic aerosol (SOA) from fires, based on the NOAA Fire Lab 2016 experiments, produces substantial additional OA; however, the spread in the primary emissions estimates implies that this magnitude of SOA can be neither confirmed nor ruled out when comparing the simulations against the observations explored here. Given the substantial uncertainty in fire emissions, as represented by these four emission inventories, we find a sizeable range in 2012 annual BBA PM2.5 population-weighted exposure over Canada and the contiguous US (0.5 to 1.6 µg m−3). We also show that the range in the estimated global direct radiative effect of carbonaceous aerosol from fires (−0.11 to −0.048 W m−2) is large and comparable to the direct radiative forcing of OA (−0.09 W m−2) estimated in the Fifth Assessment Report (AR5) of the Intergovernmental Panel on Climate Change (IPCC). Our analysis suggests that fire emissions uncertainty challenges our ability to accurately characterize the impact of smoke on air quality and climate.

Effect of NOx and SO2 on the photooxidation of methylglyoxal: Implications in secondary aerosol formation

Methylglyoxal (CH3COCHO, MG), which is one of the most abundant α-dicarbonyl compounds in the atmosphere, has been reported as a major source of secondary organic aerosol (SOA). In this work, the reaction of MG with hydroxyl radicals was studied in a 500 L smog chamber at (293 ± 3) K, atmospheric pressure, (18 ± 2)% relative humidity, and under different NOx and SO2. Particle size distribution was measured by using a scanning mobility particle sizer (SMPS) and the results showed that the addition of SO2 can promote SOA formation, while different NOx concentrations have different influences on SOA production. High NOx suppressed the SOA formation, whereas the particle mass concentration, particle number concentration and particle geometric mean diameter increased with the increasing NOx concentration at low NOx concentration in the presence of SO2. In addition, the products of the OH-initiated oxidation of MG and the functional groups of the particle phase in the MG/OH/SO2 and MG/OH/NOx/SO2 reaction systems were detected by gas chromatography mass spectrometry (GC-MS) and attenuated total reflection fourier transformed infrared spectroscopy (ATR-FTIR) analysis. Two products, glyoxylic acid and oxalic acid, were detected by GC-MS. The mechanism of the reaction of MG and OH radicals that follows two main pathways, H atom abstraction and hydration, is proposed. Evidence is provided for the formation of organic nitrates and organic sulfate in particle phase from IR spectra. Incorporation of NOx and SO2 influence suggested that SOA formation from anthropogenic hydrocarbons may be more efficient in polluted environment.

Pollution Characteristics and Source Apportionment of n-Alkanes and PAHs in Summertime PM2.5 at Background Site of Yangtze River Delta

To investigate the pollution characteristics and sources of organic aerosols at a background site of the Yangtze River Delta, day- and night- PM2.5 samples were collected from May 30th to August 15th, 2018 in Chongming Island, China and measured for their normal alkanes (n-alkanes) and polycyclic aromatic hydrocarbons (PAHs) content employing a GC-MS technique. Concentrations of PM2.5, n-alkanes, and PAHs during the entire sampling period were (33±21) μg·m-3, (26±44) ng·m-3, and (0.76±1.0) ng·m-3, respectively. During the entire campaign, 35% of the collected PM2.5 samples were of a particle loading larger than the first grade of the China National Air Quality Standard (35 μg·m-3), suggesting that further mitigation with respect to air pollution in Chongming Island remains imperative. In the period with a PM2.5 concentration higher than 35 μg·m-3, which was classified as the pollution period, concentrations of n-alkanes and PAHs were one order of magnitude higher than those in the period with PM2.5 less than 15 μg·m-3, which was classified as the clean period. During the entire campaign, OC was higher in the daytime than in the nighttime, mainly due to the daytime photooxidation that enhanced the formation of secondary organic aerosols. During the pollution period, concentrations of EC and other pollutants were higher in the nighttime than in daytime, mainly due to the transport of the inland pollutants by the nighttime land breeze. Such a diurnal difference was not observed for the pollutants in clean periods, mainly due to the relatively clean breeze from East China Sea that diluted the air pollution. Diagnostic ratios showed that 67% of n-alkanes in PM2.5 was derived from fossil fuel combustion. PMF analysis further showed that during the pollution period, vehicle exhausts and industrial emissions were the largest sources of PAHs, both accounting for 51% of the total in PM2.5. In contrast, during the clean periods ship emissions were the largest source, contributing about 45% of the total PAHs, exceeding the sum (38%) of vehicle and industrial emissions.

Large contributions of biogenic and anthropogenic sources to fine organic aerosols in Tianjin, North China

Abstract. In order to better understand the molecular composition and sources of organic aerosols in Tianjin, a coastal megacity in North China, ambient fine aerosol (PM2.5) samples were collected on a day/night basis from November to December 2016 and from May to June 2017. The organic molecular composition of PM2.5 components, including aliphatic lipids (n-alkanes, fatty acids, and fatty alcohols), sugar compounds, and photooxidation products from isoprene, monoterpene, β-caryophyllene, naphthalene, and toluene, was analysed using gas chromatography–mass spectrometry. Fatty acids, fatty alcohols, and saccharides were identified as the most abundant organic compound classes among all of the tracers detected in this study during both seasons. High concentrations of most organics at night in winter may be attributed to intensive residential activities such as house heating as well as the low nocturnal boundary layer height. Based on tracer methods, the contributions of the sum of primary and secondary organic carbon (POC and SOC respectively) to aerosol organic carbon (OC) were 24.8 % (daytime) and 27.6 % (night-time) in winter and 38.9 % (daytime) and 32.5 % (night-time) in summer. In detail, POC derived from fungal spores, plant debris, and biomass burning accounted for 2.78 %–31.6 % (12.4 %; please note that values displayed in parentheses in the following are average values) of OC during the daytime and 4.72 %–45.9 % (16.3 %) at night in winter, and 1.28 %–9.89 % (5.24 %) during the daytime and 2.08 %–47.2 % (10.6 %) at night in summer. Biomass-burning-derived OC was the predominant source of POC in this study, especially at night (16.0±6.88 % in winter and 9.62±8.73 % in summer). Biogenic SOC from isoprene, α-∕β-pinene, and β-caryophyllene exhibited obvious seasonal and diurnal patterns, contributing 2.23±1.27 % (2.30±1.35 % during the daytime and 2.18±1.19 % at night) and 8.60±4.02 % (8.98±3.67 % and 8.21±4.39 %) to OC in winter and summer respectively. Isoprene and α-∕β-pinene SOC were obviously elevated in summer, especially during the daytime, mainly due to strong photooxidation. Anthropogenic SOC from toluene and naphthalene oxidation showed higher contributions to OC in summer (21.0±18.5 %) than in winter (9.58±3.68 %). In summer, toluene SOC was the dominant contributor to aerosol OC, and biomass burning OC also accounted for a high contribution to OC, especially at night-time; this indicates that land/sea breezes also play an important role in the aerosol chemistry of the coastal city of Tianjin in North China.

Fossil and Non-fossil Fuel Sources of Organic and Elemental Carbonaceous Aerosol in Beijing, Shanghai, and Guangzhou: Seasonal Carbon Source Variation

ABSTRACT We measured the radiocarbon isotope signals in various fractions of carbonaceous aerosols sampled across four seasons (Oct 2013–Jul 2014) in three megacities of China, viz., Beijing, Shanghai, and Guangzhou. The contributions of fossil fuel (FF) and non-fossil fuel (NF) to the carbonaceous aerosol were estimated based on the radiocarbon content in the organic carbon (OC), water-soluble organic carbon (WSOC), water-insoluble organic carbon (WIOC), and elemental carbon (EC). Although NF generated the primary share (> 55%) during autumn in all of the cities, the seasonal contributions of the sources differed by location during the rest of the year. During winter, FF emissions constituted the majority of the carbonaceous pollution (64%) in Beijing, probably as a result of increased coal combustion for heating. On average, the EC, WSOC, and WIOC generated by FF composed ~10%, 35%, and 19% of the total carbon (TC). Overall, NF was identified as the largest source of carbonaceous aerosol in Guangzhou (63%), whereas FF was the largest source, contributing slightly more than NF, in Shanghai (54%). During spring and summer, FF played a greater role than NF in Beijing (~55%) and Guangzhou (~63%); additionally, based on our limited number of samples, it contributed 71% in Shanghai during the latter season, with a significant portion due to fuel combustion (i.e., industrial, vehicular, fishing-boat, and large-vessel emissions).

Sources of organic aerosols in Europe: a modeling study using CAMx with modified volatility basis set scheme

Abstract. Source apportionment of organic aerosols (OAs) is of great importance to better understand the health impact and climate effects of particulate matter air pollution. Air quality models are used as potential tools to identify OA components and sources at high spatial and temporal resolution; however, they generally underestimate OA concentrations, and comparisons of their outputs with an extended set of measurements are still rare due to the lack of long-term experimental data. In this study, we addressed such challenges at the European level. Using the regional Comprehensive Air Quality Model with Extensions (CAMx) and a volatility basis set (VBS) scheme which was optimized based on recent chamber experiments with wood burning and diesel vehicle emissions, and which contains more source-specific sets compared to previous studies, we calculated the contribution of OA components and defined their sources over a whole-year period (2011). We modeled separately the primary and secondary OA contributions from old and new diesel and gasoline vehicles, biomass burning (mostly residential wood burning and agricultural waste burning excluding wildfires), other anthropogenic sources (mainly shipping, industry and energy production) and biogenic sources. An important feature of this study is that we evaluated the model results with measurements over a longer period than in previous studies, which strengthens our confidence in our modeled source apportionment results. Comparison against positive matrix factorization (PMF) analyses of aerosol mass spectrometric measurements at nine European sites suggested that the modified VBS scheme improved the model performance for total OA as well as the OA components, including hydrocarbon-like (HOA), biomass burning (BBOA) and oxygenated components (OOA). By using the modified VBS scheme, the mean bias of OOA was reduced from −1.3 to −0.4 µg m−3 corresponding to a reduction of mean fractional bias from −45 % to −20 %. The winter OOA simulation, which was largely underestimated in previous studies, was improved by 29 % to 42 % among the evaluated sites compared to the default parameterization. Wood burning was the dominant OA source in winter (61 %), while biogenic emissions contributed ∼ 55 % to OA during summer in Europe on average. In both seasons, other anthropogenic sources comprised the second largest component (9 % in winter and 19 % in summer as domain average), while the average contributions of diesel and gasoline vehicles were rather small (∼ 5 %) except for the metropolitan areas where the highest contribution reached 31 %. The results indicate the need to improve the emission inventory to include currently missing and highly uncertain local emissions, as well as further improvement of VBS parameterization for winter biomass burning. Although this study focused on Europe, it can be applied in any other part of the globe. This study highlights the ability of long-term measurements and source apportionment modeling to validate and improve emission inventories, and identify sources not yet properly included in existing inventories.

Organic aerosol source apportionment in Zurich using an extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF-MS) – Part 1: Biogenic influences and day–night chemistry in summer

Abstract. Improving the understanding of the health and climate impacts of aerosols remains challenging and is restricted by the limitations of current measurement techniques. Detailed investigation of secondary organic aerosol (SOA), which is typically the dominating fraction of the organic aerosol (OA), requires instrumentation capable of real-time, in situ measurements of molecular composition. In this study, we present the first ambient measurements by a novel extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF-MS). The EESI-TOF-MS was deployed along with a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) during summer 2016 at an urban location (Zurich, Switzerland). Positive matrix factorization (PMF), implemented within the Multilinear Engine (ME-2), was applied to the data from both instruments to quantify the primary and secondary contributions to OA. From the EESI-TOF-MS analysis, a six-factor solution was selected as the most representative and interpretable solution for the investigated dataset, including two primary and four secondary factors. The primary factors are dominated by cooking and cigarette smoke signatures while the secondary factors are discriminated according to their daytime (two factors) and night-time (two factors) chemistry. All four factors showed strong influence by biogenic emissions but exhibited significant day–night differences. Factors dominating during daytime showed predominantly ions characteristic of monoterpene and sesquiterpene oxidation while the night-time factors included less oxygenated terpene oxidation products, as well as organonitrates which were likely derived from NO3 radical oxidation of monoterpenes. Overall, the signal measured by the EESI-TOF-MS and AMS showed a good correlation. Further, the two instruments were in excellent agreement in terms of both the mass contribution apportioned to the sum of POA and SOA factors and the total SOA signal. However, while the oxygenated organic aerosol (OOA) factors separated by AMS analysis exhibited a flat diurnal pattern, the EESI-TOF-MS factors illustrated significant chemical variation throughout the day. The captured variability, inaccessible from AMS PMF analysis, was shown to be consistent with the variations in the physiochemical processes influencing chemical composition and SOA formation. The improved source separation and interpretability of EESI-TOF-MS results suggest it to be a promising approach to source apportionment and atmospheric composition research.

Understanding the Impact of High-NOx Conditions on the Formation of Secondary Organic Aerosol in the Photooxidation of Oil Sand-Related Precursors.

Oil sands (OS) are an important type of heavy oil deposit, for which operations in Alberta, Canada, were recently found to be a large source of secondary organic aerosol (SOA). However, SOA formation from the OS mining, processing, and subsequent tailings, especially in the presence of NOx, remains unclear. Here, photooxidation experiments for OS-related precursors under high-NOx conditions were performed using an oxidation flow reactor, in which ∼95% of peroxy radicals (RO2) react with NO. The SOA yields under high-NOx conditions were found to be lower than yields under low-NOx conditions for all precursors, which is likely due to the higher volatilities of the products from the RO2 + NO pathway compared with RO2 + HO2. The SOA yields under high-NOx conditions show a strong dependence on pre-existing surface area (not observed in previous low-NOx experiments), again attributed to the higher product volatilities. Comparing the mass spectra of SOA formed from different precursors, we conclude that the fraction of m/z > 80 (F80) can be used as a parameter to separate different types of SOA in the region. In addition, particle-phase organic nitrate was found to be an important component (9-23%) of OS SOA formed under high-NOx conditions. These results have implications for better understanding the atmospheric processing of OS emissions.