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The lockdown due to COVID-19 created a rare opportunity to examine the nonlinear responses of secondary aerosols, which are formed through atmospheric oxidation of gaseous precursors, to intensive precursor emission reductions. Based on unique observational data sets from six supersites in eastern China during 2019-2021, we found that the lockdown caused considerable decreases (32-61%) in different secondary aerosol components in the study region because of similar-degree precursor reductions. However, due to insufficient combustion-related volatile organic compound (VOC) reduction, odd oxygen (Ox = O3 + NO2) concentration, an indicator of the extent of photochemical processing, showed little change and did not promote more decreases in secondary aerosols. We also found that the Chinese provinces and international cities that experienced reduced Ox during the lockdown usually gained a greater simultaneous PM2.5 decrease than other provinces and cities with an increased Ox. Therefore, we argue that strict VOC control in winter, which has been largely ignored so far, is critical in future policies to mitigate winter haze more efficiently by reducing Ox simultaneously.

The North China Plain (NCP) is a region that experiences serious aerosol pollution. A number of studies have focused on aerosol pollution in urban areas in the NCP region; however, research on characterizing aerosols in rural NCP areas is comparatively limited. In this study, we deployed a TD-HR-AMS (thermodenuder high-resolution aerosol mass spectrometer) system at a rural site in the NCP region in summer 2013 to characterize the chemical compositions and volatility of submicron aerosols (PM1). The average PM1 mass concentration was 51.2 ± 48.0 µg m−3 and organic aerosol (OA) contributed most (35.4%) to PM1. Positive matrix factorization (PMF) analysis of OA measurements identified four OA factors, including hydrocarbon-like OA (HOA, accounting for 18.4%), biomass burning OA (BBOA, 29.4%), less-oxidized oxygenated OA (LO-OOA, 30.8%) and more-oxidized oxygenated OA (MO-OOA, 21.4%). The volatility sequence of the OA factors was HOA > BBOA > LO-OOA > MO-OOA, consistent with their oxygen-to-carbon (O:C) ratios. Additionally, the mean concentration of organonitrates (ON) was 1.48–3.39 µg m−3, contributing 8.1%–19% of OA based on cross validation of two estimation methods with the high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) measurement. Correlation analysis shows that ON were more correlated with BBOA and black carbon emitted from biomass burning but poorly correlated with LO-OOA. Also, volatility analysis for ON further confirmed that particulate ON formation might be closely associated with primary emissions in rural NCP areas.

An in-depth analysis of the specific evolution of air pollution in a given city can provide a better understanding of the chronic effects of air pollution on human health. In this study, we reported trends in ambient concentrations of particulate matter (PM) and gaseous pollutants [sulfur dioxide (SO2), nitrogen dioxide (NO2), and ozone (O3)] from 1995 to 2017 and PM2.5 composition for the period of 2000-2017 in Guangzhou, Wuhan, Chongqing, and Lanzhou. We provided socio-economic indicators to help explain the pollution trends. SO2 and PM (including PM10 and PM2.5) concentrations showed a downward trend in recent years with the most notable reduction in SO2 in Chongqing and PM2.5 in Guangzhou. There was an overall flat trend for NO2, while O3 showed an upward trend in recent years except in Lanzhou. The majority of PM2.5 mass was SO4 2- (6.0-30 µg/m3) and organic carbon (6.0-38 µg/m3), followed by NO3 - (2.0-12 µg/m3), elemental carbon (2.1-12 µg/m3), NH4 + (1.0-10 µg/m3), K+ (0.2-2.0 µg/m3), and Cl- (0.2-1.9 µg/m3). Except for secondary inorganic aerosols in Wuhan, annual average concentrations of all PM2.5 constituents showed a declining trend after 2013, corresponding to the trend of PM2.5. The secondary sources in PM2.5 were found to be most prominent in Wuhan, while the most abundant EC and Cl- in Lanzhou was attributed to the use of coal. Despite temporal and spatial variabilities across the four cities, coal combustion, traffic emissions, and secondary pollution have been the major sources of PM2.5 pollution. These trends in ambient air pollution levels and PM2.5 composition may help understand changes in health outcomes measured at different times within the time period of 1995-2017 in the four cities.

Refractory black carbon (rBC) aerosols emitted from incomplete combustion are important climate forcers. Understanding the chemical characteristics and evolution of rBC-related components is particularly crucial to assess rBC environmental impacts. Here, we explored the chemical components of rBC in Shenzhen, China, using a soot-particle aerosol mass spectrometer (SP-AMS). The observations showed that the rBC coating was mainly composed of secondary aerosols with an average mass contribution of 84.7 %. Among them, secondary organic coating occupied ∼57.7 % of the total coating mass. Exploration of the relationship between secondary organic aerosol (SOA) coating and Ox (=NO

Atmospheric particles are important reaction vessels for multiphase chemistry. We conducted a meta-analysis of previous field observations in various environments (includes ocean, urban and rural regions), showing that particle hygroscopicity inhomogeneity (PHI) is ubiquitous for the continental atmospheric particles, in which a considerable part of the particulate matters is hydrophobic (10%–33% on average). However, the effects of PHI in quantifying the uptake process of reactive gases are still unclear. Here, taking N2O5 uptake as an example, we showed that using a laboratory-based parameterization scheme without considering the PHI might result in a misestimation of uptake rate coefficient, especially under low ambient relative humidity (RH). Such misestimation may be caused by the differences of the uptake coefficients, as well as the proportion of surface area concentration (SA) between hydrophilic and hydrophobic particles. We suggested that the PHI should be well-considered in establishing the reactive traces gases heterogeneous uptake parameterizations.

Oxygenated volatile organic compounds (OVOCs) are important precursors and products of atmospheric secondary pollution. The sources of OVOCs, however, are still quite uncertain, especially in the atmosphere with much pollution in China. To study the sources of OVOCs in rural atmospheres, a proton transfer reaction mass spectrometry (PTR-MS) was deployed at a northern rural site (WD) and a southern rural site (YMK) in China during the summer of 2014 and 2016, respectively. The continuous observation showed that the mean concentration of TVOCs (totally 17 VOCs) measured at WD (52.4 ppbv) was far higher than that at YMK (11.1 ppbv), and the OVOCs were the most abundant at both the two sites. The diurnal variations showed that local sources of OVOCs were still prominent at WD, while regional transport influenced YMK much. The photochemical age-based parameterization method was then used to quantitatively apportion the sources of ambient OVOCs. The anthropogenic primary sources at WD and YMK contributed less (2%–16%) to each OVOC species. At both the sites, the atmospheric background had a dominant contribution (~ 50%) to acetone and formic acid, while the anthropogenic secondary formation was the main source (~ 40%) of methanol and MEK. For acetaldehyde and acetic acid, the biogenic sources were their largest source (~ 40%) at WD, while the background (39%) and anthropogenic secondary formation (42%) were their largest sources at YMK, respectively. This study reveals the complexity of sources of OVOCs in China, which urgently needs explored further.

Particle phase state plays a key role in gas-particle partitioning, heterogeneous and multiphase reactions, and secondary aerosol formation. In this work, the rebound fraction and chemical composition of submicron particles were simultaneously measured to investigate the particle phase state and its link to chemical composition in a subtropical coastal urban city (Shenzhen, China). Submicron particles were found to be in the liquid state for most of the measurement period in spring. During the sampling time, both high relative humidity (RH, ranged from 40% to 93%) and inorganic mass fraction in particles (62.6 ± 12.4% of dry particles, on average) resulted in abundant aerosol liquid water (43 ± 6% in the wet PM

Size-resolved particulate matter (PM) was collected at the Heshan Super-Station in the Pearl River Delta (PRD) region, China, to evaluate their chemical characteristics and potential health risks. The chemical mass closures illustrate that the dominant fraction in coarse (2.5 μm

Volatile organic compounds (VOCs) are important precursors of photochemical pollution. However, a substantial fraction of VOCs, namely, oxygenated VOCs (OVOCs), have not been sufficiently characterized to evaluate their sources in air pollution in China. In this study, a total of 119 VOCs, including 60 OVOCs in particular, were monitored to provide a more comprehensive picture based on different online measurement techniques, proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) and online gas chromatography/mass spectrometry (GC/MS), at a receptor site in southeastern China during a photochemically active period. Positive matrix factorization (PMF) and photochemical age-based parameterization were combined to identify and quantify different sources of major VOCs during daytime hours, with the advantage of including VOC decay processes. The results revealed the unexpected role of biomass burning (21%) in terms of ozone (O3) formation potential (OFP) when including the contributions of OVOCs and large contributions (30–32%) of biomass burning to aldehydes, as more OVOCs were measured in this study. We argue that biomass burning could significantly enhance the continental atmospheric oxidizing capacity, in addition to the well-recognized contributions of primary pollutants, which should be seriously considered in photochemical models and air pollution control strategies.

Oxygenated volatile organic compounds (OVOCs) are key intermediates in the atmospheric photooxidation process. To further study the primary and secondary sources of OVOCs, their ambient levels were monitored using a proton-transfer reaction mass spectrometer (PTR-MS) at an urban site in the Pearl River Delta of China. Continuous monitoring campaigns were conducted in the spring, summer, fall, and winter of 2016. Among the six types of OVOC species, the mean concentrations of methanol were the highest in each season (up to 13–20 ppbv), followed by those of acetone, acetaldehyde and acetic acid (approximately 2–4 ppbv), while those of formic acid and methyl ethyl ketone (MEK) were the lowest (approximately 1–2 ppbv). As observed from a diurnal variation chart, the OVOCs observed in Shenzhen may have been affected by numerous factors such as their primary and secondary sources and photochemical consumption. The photochemical age-based parameterization method was used to apportion the sources of ambient OVOCs. Methanol had significant anthropogenic primary sources but negligible anthropogenic secondary sources during all of the seasons. Acetone, MEK and acetic acid were mostly attributed to anthropogenic primary sources during each season with smaller contributions from anthropogenic secondary sources. Acetaldehyde had similar contributions from both anthropogenic secondary and anthropogenic primary sources throughout the year. Meanwhile, anthropogenic primary sources contributed the most to formic acid.

Atmospheric sub-micrometer particles (PM1, particles with an aerodynamic diameter ≤ 1.0 μm) monitoring in Qingdao, a coastal city in Northern China, was conducted for two consecutive years from November 1, 2018 to January 31, 2019 (hereafter referred to as OP2018–2019) and from October 28, 2019 to January 20, 2020 (hereafter referred to as OP2019–2020). The results showed that compared with OP2018–2019, the concentrations of V, Ni, As, Pb, and Cd in PM1 in OP2019–2020 decreased by 61.9%, 31.4%, 49.2%, 25.4%, and 27.1%, respectively. For the indicators of ship emission sources, a significant reduction in V (73.3%) and Ni (22.1%) concentrations were observed after the implementation of the updated Domestic Emission Control Area (DECA 2.0) policy for ships since January 1, 2019 proposed by the Ministry of Transportation. This result demonstrated that the implementation of the DECA 2.0 policy had a significant effect on reducing ship emissions. The Field Emission Scanning Electron Microscope analysis identified the impact of ship emission sources, while the inconsistent distribution of V and Ni revealed other potential sources of Ni. The V/Ni ratios during the pre-policy and post-policy periods decreased by 40.7%. Along with the further implementation of the domestic coastal ship pollution control zone policy, V/Ni ratio should be cautiously used as a parameter for ship emission sources. The positive matrix factorization method identified five source factors: coal combustion/biomass burning (47.8%), crustal sources (21.2%), vehicle exhaust/road dust (15.1%), industrial emissions (11.1%), and ship emissions (4.9%). The contribution rates of ship emission sources before and after the DECA 2.0 policy were analyzed and found to be 5.6% and 3.4%. The potential source contribution factor analysis of As showed that the potential emission source areas were significantly reduced in OP2019–2020, which might be related to the coal fired cleanup operations conducted in Beijing-Tianjin-Hebei and surrounding areas.

Water-soluble organic matter (WSOM) represents a critical fraction of fine particles (PM2.5) in the air, but its changing behaviors and formation mechanisms are not well understood yet, partly due to the lack of fast techniques for the ambient measurements. In this study, a novel system for the on-line measurement of water-soluble components in PM2.5, the particle-into-liquid sampler (PILS)-Nebulizer-aerosol chemical speciation monitor (ACSM), was developed by combining a PILS, a nebulizer, and an ACSM. High time resolution concentrations of WSOM, sulfate, nitrate, ammonium, and chloride, as well as mass spectra, can be obtained with satisfied quality control results. The system was firstly applied in China for field measurement of WSOM. The mass spectrum of WSOM was found to resemble that of oxygenated organic aerosol, and WSOM agreed well with secondary inorganic ions. All evidence collected in the field campaign demonstrated that WSOM could be a good surrogate of secondary organic aerosol (SOA). The PILS-Nebulizer-ACSM system can thus be a useful tool for intensive study of WSOM and SOA in PM2.5.

Organic aerosols (OAs), which consist of thousands of complex compounds emitted from various sources, constitute one of the major components of fine particulate matter. The traditional positive matrix factorization (PMF) method often apportions aerosol mass spectrometer (AMS) organic datasets into less meaningful or mixed factors, especially in complex urban cases. In this study, an improved source apportionment method using a bilinear model of the multilinear engine (ME-2) was applied to OAs collected during the heavily polluted season from two Chinese megacities located in the north and south with an Aerodyne high-resolution aerosol mass spectrometer (HR-ToF-AMS). We applied a rather novel procedure for utilization of prior information and selecting optimal solutions, which does not necessarily depend on other studies. Ultimately, six reasonable factors were clearly resolved and quantified for both sites by constraining one or more factors: hydrocarbon-like OA (HOA), cooking-related OA (COA), biomass burning OA (BBOA), coal combustion (CCOA), less-oxidized oxygenated OA (LO-OOA) and more-oxidized oxygenated OA (MO-OOA). In comparison, the traditional PMF method could not effectively resolve the appropriate factors, e.g., BBOA and CCOA, in the solutions. Moreover, coal combustion and traffic emissions were determined to be primarily responsible for the concentrations of PAHs and BC, respectively, through the regression analyses of the ME-2 results.

With the rapid economic development and urbanization of China, haze and photochemical smog events have been frequently observed during the last decade. To explore the temporal and spatial pollution characteristics in Ningbo, a medium-sized coastal city located in the Yangtze River Delta (YRD) in southeast China, 24-h PM2.5 (particulate matter with aerodynamic diameter ≤ 2.5 µm) samples were simultaneously collected at five sites (two urban residential sites, two urban coastal sites, and one suburban site) from winter 2012 to autumn 2013. The average PM2.5 concentration was 53.2 ± 30.4 µg m–3. Furthermore, the concentration exhibited a seasonal variation: It was highest in winter and lowest in summer. The urban residential sites had the highest PM2.5 concentrations, followed by the urban coastal sites, and the suburban site had the lowest concentration. OM (Organic Matters) and secondary inorganic ions (sulfate, nitrate, and ammonium) were the dominant components of the PM2.5. As a coastal city with industrial zones, sources are more complex in Ningbo than in inland cities due to ship emissions and the interactions between land and sea, and the marine and atmospheric environments. Positive matrix factorization (PMF) was used to apportion the particle sources. Nine factors were resolved in this study: secondary nitrate, vehicle exhaust, secondary sulfate, coal combustion, industrial emission, ship emission, dust, biomass burning, and aged sea salt, with average contributions of 26%, 21%, 13%, 12%, 9%, 7%, 5%, 4%, and 3%, respectively. Secondary nitrate and vehicle exhaust were the major sources of PM2.5 pollution in Ningbo. Coal combustion contributed significantly in winter and autumn, whereas sea salt formed a considerable contribution in summer. This study suggests that decreasing the PM2.5 pollution in Ningbo requires not only strategies for reducing local primary sources but also joint inter-regional prevention and the control of air pollution in the YRD.

Haze in China is primarily caused by high pollution of atmospheric fine particulates (PM 2.5 ). However, the detailed source structures of PM 2.5 light extinction have not been well established, especially for the roles of various organic aerosols, which makes haze management lack specified targets. This study obtained the mass concentrations of the chemical compositions and the light extinction coefficients of fine particles in the winter in Dongguan, Guangdong Province, using high time resolution aerosol observation instruments. We combined the positive matrix factor (PMF) analysis model of organic aerosols and the multiple linear regression method to establish a quantitative relationship model between the main chemical components, in particular the different sources of organic aerosols and the extinction coefficients of fine particles with a high goodness of fit ( R 2 = 0.953). The results show that the contribution rates of ammonium sulphate, ammonium nitrate, biomass burning organic aerosol (BBOA), secondary organic aerosol (SOA) and black carbon (BC) were 48.1%, 20.7%, 15.0%, 10.6%, and 5.6%, respectively. It can be seen that the contribution of the secondary aerosols is much higher than that of the primary aerosols (79.4% versus 20.6%) and are a major factor in the visibility decline. BBOA is found to have a high visibility destroying potential, with a high mass extinction coefficient, and was the largest contributor during some high pollution periods. A more detailed analysis indicates that the contribution of the enhanced absorption caused by BC mixing state was approximately 37.7% of the total particle absorption and should not be neglected.

The phase state of biomass burning aerosols (BBA) remains largely unclear, impeding our understanding of their effects on air quality, climate and human health, due to its profound roles in mass transfer between gaseous and particulate phase. In this study, the phase state of BBA was investigated by measuring the particle rebound fraction ƒ combining field observations and laboratory experiments. We found that both ambient and laboratory-generated BBA had unexpectedly lower rebound fraction ƒ (0.6) under the dry conditions (RH = 20-50%), indicating that BBA were in non-solid state at such low RH. This was obviously different from the secondary organic aerosols (SOA) derived from the oxidation of both anthropogenic and biogenic volatile organic compounds, typically with a rebound fraction ƒ larger than 0.8 at RH below 50%. Therefore, we proposed that the diffusion coefficient of gaseous molecular in the bulk of BBA might be much higher than SOA under the dry conditions.

Rapid economic development and urbanization in China has been concentrated in coastal cities, resulting in haze and photochemical smog issues, especially in the densely-populated Yangtze River Delta. In this study, we explore particulate matter (specifically PM 2.5 ) pollution in a city in Zhejiang Province (Ningbo), chosen to represent a typical, densely-populated urban city with residential and industrial sections. PM 2.5 samples were collected at five sites in four seasons from Dec. 2012 to Nov. 2013. The annual average PM 2.5 mass concentration was 53.2 ± 30.4 μg/m 3 , with the highest concentration in winter and lowest in summer. Among the five sites, PM 2.5 concentration was highest in an urban residential site and lowest in a suburban site, due to effects of urbanization and the anthropogenic influences. The chemical components of PM 2.5 show significant seasonal variation. In addition, secondary transformation was high in Ningbo, with the highest proportion of secondary components found at a suburban site and the lowest at the industrial sites. Ningbo is controlled by five major air masses originating from inland China, from the Bohai Sea, offshore from the southeast, the Yellow Sea, and off the east coast of Korea. The relative contributions of these air masses differ, by season, with the Bohai Sea air mass dominating in winter and spring, the maritime southeast air mass in summer, and the Yellow Sea and coastal Korean air masses dominating in autumn. The continental air mass is associated with a high PM 2.5 concentration, indicating that it is primarily transports primary emissions. In contrast, the concentration ratios among secondary formed pollutants were higher in the maritime air masses, which suggests that sea breezes control temporal and spatial variations of air pollution over coastal cities.

Taiwan Strait is a special channel for subtropical East Asian Monsoon and its western coast is an important economic zone in China. In this study, a suburban site in the city of Xiamen on the western coast of Taiwan Strait was selected for fine aerosol study to improve the understanding of air pollution sources in this region. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and an Aethalometer were deployed to measure fine aerosol composition with a time resolution of 5 min from May 1 to 18, 2015. The average mass concentration of PM1 was 46.2 ± 26.3 μg/m3 for the entire campaign. Organics (28.3%), sulfate (24.9%), and nitrate (20.6%) were the major components in the fine particles, followed by ammonium, black carbon (BC), and chloride. Evolution of nitrate concentration and size distribution indicated that local NOx emissions played a key role in high fine particle pollution in Xiamen. In addition, organic nitrate was found to account for 9.0%-13.8% of the total measured nitrate. Positive Matrix Factorization (PMF) conducted with high-resolution organic mass spectra dataset differentiated the organic aerosol into three components, including a hydrocarbon-like organic aerosol (HOA) and two oxygenated organic aerosols (SV-OOA and LV-OOA), which on average accounted for 27.6%, 28.8%, and 43.6% of the total organic mass, respectively. The relationship between the mass concentration of submicron particle species and wind further confirmed that all major fine particle species were influenced by both strong local emissions in the southeastern area of Xiamen and regional transport through the Taiwan Strait.

To investigate the regional transport and formation mechanisms of submicron aerosols in the North China Plan (NCP), for the first time, we conducted simultaneous combined observations of the non-refractory submicron aerosols (NR-PM1) chemical compositions using aerosol mass spectrometer at urban Beijing (BJ) and at regional background area of the NCP (XL), from November 2018 to January 2019. During the observation period, average mass concentrations of PM1 in BJ and XL were 26.6 +/- 31.7 and 16.0 +/- 18.7 mu g m(-3) respectively. The aerosol composition in XL showed a lower contribution of organic aerosol (33% vs. 43%) and higher fractions of nitrate (35% vs. 30%), ammonium (16% vs. 13%), and chlorine (2% vs. 1%) than in BJ. Additionally, a higher contribution of secondary organic aerosol (SOA) was also observed in XL, suggesting low primary emissions and highly oxidized OA in the background area. Nitrate displayed a significantly enhanced contribution with the aggravation of aerosol pollution in both BJ and XL, which was completely neutralized by excess ammonium at both sites, that the abundant ammonia emissions in the NCP favor nitrate formation on a regional scale. In addition, a higher proportion of nitrate in XL can be attributed to the more neutral and higher oxidation capacity of the background atmosphere. Heterogeneous aqueous reaction plays an important role in sulfate and SOA formation, and is more efficient in BJ which can be attributed to the higher aerosol surface areas at urban site. Regional transport from the southwestern regions of NCP showed a significant impact on the formation of haze episodes. Beside the invasion of transported pollutants, the abundant water vapor associated with the air mass to the downwind background area further enhanced local secondary transformation and expanded the regional scope of the haze pollution in the NCP. (C) 2019 Elsevier B.V. All rights reserved.

To elucidate the influence of long-range transported biomass burning organic aerosols (BBOA) on the Tibetan Plateau, the molecular compositions and light absorption of HUmic-Like Substances (HULIS), major fractions of brown carbon, were characterized during the premonsoon season. Under the significant influence of biomass burning, HULIS concentrations increased to as high as 26 times of the background levels, accounting for 54% of water-soluble organic carbon (WSOC) and 50% of organic carbon (OC). The light absorption of HULIS also enhanced up to 42 times of the background levels, contributing 61% of the WSOC absorption and 50% of OC absorption. Meanwhile, elevated nitrogen-containing compounds (NOCs) among HULIS were observed. The NOCs from fresh and aged BBOA were unambiguously identified on the molecular level, through comparing with the molecular compositions of NOCs from lab-controlled and field burning experiments. N-Heterocyclic bases represent major fractions in the reduced nitrogen compounds from fresh BBOA, and nitroaromatic compounds are important groups among the oxidized nitrogen compounds from aged BBOA. The nitrogen-containing compounds, including nitroaromatics and N-heterocyclic compounds, were also important chromophores, which contributed to the enhanced light absorption of extracted HULIS during biomass burning-influenced periods.

The volatility of atmospheric aerosols greatly influences the gas-particle partitioning, chemical mechanisms and lifetime of aerosols. Due to the complex composition, the volatility of organic aerosol is one of the major sources of uncertainty in measuring and modeling ambient aerosols. Despite high aerosol loading in the atmosphere in China, especially in winter, few field measurements were conducted targeting the volatility of ambient organic aerosol (OA). With the deployment of a thermodenuder-aerosol mass spectrometer (TD-AMS) system, the volatility of non-refractory submicron aerosols (NR-PM1) were measured on an island near the coastal line for the regional air in wintertime in southern China. NO3− and Cl− showed the highest volatility in the NR-PM1 chemical species, while SO42− showed the least volatility. Organic aerosol showed a moderate volatility, evaporating at a stable rate (0.57% °C−1) at temperatures lower than 150 °C and keeping a stable volatility when its loading increases, which could be an advantage for parameterization of OA in air quality models. Based on both positive matrix factorization and chemical mass balance modeling of OA composition, biomass burning OA was found to be the most volatile factor, followed by hydrocarbon-like OA and more-oxidized oxygenated OA. By summarizing the OA volatility measured in this study and in the literature, we found that the volatilities of different OA factors at different locations do not have a clear relationship with the OA oxidation state, possibly due to the vague understanding of local OA aging mechanisms and mixing states.

Although China's severe air pollution has become a focus in the field of atmospheric chemistry and the mechanisms of urban air pollution there have been researched extensively, few field sampling campaigns have been conducted at remote background sites in China, where air pollution characteristics on a larger scale are highlighted. In this study, an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), together with an Aethalometer, was deployed at two of China's national background sites in northern (Lake Hongze site; 33.23° N, 118.33° E; altitude 21 m) and southern (Mount Wuzhi site; 18.84° N, 109.49° E; altitude 958 m) China in the spring seasons in 2011 and 2015, respectively, in order to characterize submicron aerosol composition and sources. The campaign-average PM1 concentration was 36.8 ± 19.8 µg m−3 at the northern China background (NCB) site, which was far higher than that at the southern China background (SCB) site (10.9 ± 7.8 µg m−3). Organic aerosol (OA) (27.2 %), nitrate (26.7 %), and sulfate (22.0 %) contributed the most to the PM1 mass at NCB, while OA (43.5 %) and sulfate (30.5 %) were the most abundant components of the PM1 mass at SCB, where nitrate only constituted a small fraction (4.7 %) and might have contained a significant amount of organic nitrates (5–11 %). The aerosol size distributions and organic aerosol elemental compositions all indicated very aged aerosol particles at both sites. The OA at SCB was more oxidized with a higher average oxygen to carbon (O ∕ C) ratio (0.98) than that at NCB (0.67). Positive matrix factorization (PMF) analysis was used to classify OA into three components, including a hydrocarbon-like component (HOA, attributed to fossil fuel combustion) and two oxygenated components (OOA1 and OOA2, attributed to secondary organic aerosols from different source areas) at NCB. PMF analysis at SCB identified a semi-volatile oxygenated component (SV-OOA) and a low-volatility oxygenated component (LV-OOA), both of which were found to be secondary species and could be formed from precursors co-emitted with BC. Using the total potential source contribution function model, the likely source areas of the major PM1 components at both sites were a on large regional scale in East Asia. The possible sources may include not only emissions from the Chinese mainland but also emissions from ocean-going cargo ships and biomass burning in neighboring countries.

Cross-regional transport potentially contributes to PM2.5 nitrate (pNO3), and this can occur as indirect transport, through which pNO3 precursors are transported to targeted regions, wherein they subsequently react with locally emitted ones to produce pNO3. However, the process has been rarely studied, which limits its comprehensive understanding. We applied the CMAQ model to study the contributions and mechanisms of pNO3 transport during autumn in the Pearl River Delta (PRD), a metropolitan region under the growing influence of cross-regional transport on PM2.5 pollution. Results showed that cross-regional transport contributed to 58% pNO3 monthly in the PRD, and this mostly occurred as indirect transport contributions (accounting for 43% among all contributions). For the first time, we identified the mechanism of indirect pNO3 transport in the PRD, which mainly involves transported O3 and locally emitted NOx reacting to produce pNO3 through N2O5 heterogeneous hydrolysis. pNO3 contributions in different periods and regions indicated differences in the indirect transport contributions to N2O5 heterogeneous hydrolysis under varying O3 availability conditions, which are determined by wind fields and the intensity of NOx emissions. On the regional scale, the pNO3 level is controlled by both transported O3 and local NOx emissions, but pNO3 sensitivity to these two precursors varies among cities. This study demonstrates the notable effect and complex process of cross-regional pNO3 transport in the PRD. Considering the important role of transported O3 for pNO3, O3 reduction within a larger scale is required to achieve PM2.5 pollution control target.

Oxygenated volatile organic compounds (OVOCs) are critical atmospheric ozone and secondary organic aerosol (SOA) precursors and radical sources, while understanding of OVOC sources in the atmosphere, especially with large anthropogenic emissions, still has large uncertainties. A high-sensitivity proton transfer reaction mass spectrometer (PTR-MS) was deployed in vastly different atmospheres in southern China, including an urban site (SZ-U), a regional site (NA-R), and a background site (NL-B). Four critical OVOCs, i.e., methanol, acetone, methyl ethyl ketone (MEK) and acetaldehyde, five groups of aromatic hydrocarbons, isoprene and acetonitrile were measured with a high time resolution. The featured relative abundance and diurnal variations of the OVOCs indicated that methanol, acetone and MEK had prominent contributions from urban industrial activities, while acetaldehyde was closely related to the photochemical formation at all three sites. The photochemical age-based parameterization method was improved locally and then applied to quantify different sources of daytime OVOCs: anthropogenic secondary and biogenic sources (together 60–73%) were always the dominant source for acetaldehyde in various atmospheres; in addition to a significant background for methanol, acetone and MEK, anthropogenic primary emissions (mostly industrial) were their dominant source at SZ-U (38–73%), while biogenic sources played the key role for them at NL-B (30–43%); biomass burning contributed a small fraction of 5–17% for the four OVOCs at the three sites.

To investigate the atmospheric oxidizing capacity in certain polluted isoprene-rich environments, such as the forests surrounding megacities. Here we present online observations of isoprene and its first-stage oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) in summer 2016 at a remote, high-altitude mountain forest site (1690 m a.s.l.) to the north of the air-polluted Pearl River Delta (PRD) region in southern China. The observed isoprene level was found to be significantly lower in comparison with other forest sites either in China or around the world, although the sampling site was surrounded with subtropical evergreen broad-leaved trees which are strong isoprene emitters. Also, high (MVK+MACR)/isoprene ratio was observed. Based on the observations, we hypothesized that the lower isoprene levels in the study forest might be attributable to a strong atmospheric oxidative capacity in relation to the elevated regional complex air pollution. High daytime OH and nighttime NO3 radical concentrations estimated by using a photochemical box model incorporating Master Chemical Mechanism (PBM-MCM), as well as calculated short atmospheric reaction times of isoprene and long photochemical age, indicated that the isoprene was rapidly and fully oxidized at this aged atmospheric environment, which confirmed our hypothesis. The study suggests that the complex air pollution in the PRD region has significantly elevated the background atmospheric oxidative capacity of the adjacent forests, and most likely does would probably affect the regional air quality and ecological environment in the long term. The feedback of forest ecosystems to the increasing atmospheric oxidation capacity warrants further studies.

In recent years, fine particulate matter (PM) pollution and visibility degradation have become severe air quality issues in China. In this study, PM 2.5 pollution over the Pearl River Delta (PRD) region during January, April, August, and November 2009 was simulated using the Community Multiscale Air Quality (CMAQ) model. An in-depth diagnostic analysis, focused on November 2009, was also conducted to reveal the patterns of sulfate and nitrate distribution, and to identify the main factors that influence the formation of sulfate and nitrate under typical meteorological conditions. The CMAQ model reasonably reproduced the observed concentrations, but showed better performance for January and November than it did for April and August, for which there was light-moderate underestimation of SO 2 , NO x , O 3 , PM 10 , and PM 2.5 concentrations, and slight overestimation of daily 8-h maximum concentrations of O 3 . Utilizing a sulfate tracking technique, it was found that on nearly 20 days in November 2009, characterized by northeasterly winds, cross-boundary transport contributed to >75% of the total sulfate budget, while local gas phase oxidation and primary emissions averaged 10% and 8%, respectively. Aqueous sulfate typically contributed less than 1% of the total sulfate budget, except when the winds were directed from the sea and high humidity favored aqueous oxidation, and the percentage contribution reached up to 46%. NH 3 was generally sufficient to fully neutralize H 2 SO 4 ; however, the formation of nitrate over the PRD was limited by the availability of NH 3 .

Aerosol pollution has been a very serious environmental problem in China for many years. The volatility of aerosols can affect the distribution of compounds in the gas and aerosol phases, the atmospheric fates of the corresponding components, and the measurement of the concentration of aerosols. Compared to the characterization of chemical composition, few studies have focused on the volatility of aerosols in China. In this study, a thermodenuder aerosol mass spectrometer (TD-AMS) system was deployed to study the volatility of non-refractory submicron particulate matter ( PM1 ) species during winter in Shenzhen. To our knowledge, this paper is the first report of the volatilities of aerosol chemical components based on a TD-AMS system in China. The average PM1 mass concentration during the experiment was 42.7±20.1 µg m−3 , with organic aerosol (OA) being the most abundant component (43.2 % of the total mass). The volatility of chemical species measured by the AMS varied, with nitrate showing the highest volatility, with a mass fraction remaining (MFR) of 0.57 at 50 ∘ C. Organics showed semi-volatile characteristics (the MFR was 0.88 at 50 ∘ C), and the volatility had a relatively linear correlation with the TD temperature (from the ambient temperature to 200 ∘ C), with an evaporation rate of 0.45 % ∘ C - 1 . Five subtypes of OA were resolved from total OA using positive matrix factorization (PMF) for data obtained under both ambient temperature and high temperatures through the TD, including a hydrocarbon-like OA (HOA, accounting for 13.5 %), a cooking OA (COA, 20.6 %), a biomass-burning OA (BBOA, 8.9 %), and two oxygenated OAs (OOAs): a less-oxidized OOA (LO-OOA, 39.1 %) and a more-oxidized OOA (MO-OOA, 17.9 %). Different OA factors presented different volatilities, and the volatility sequence of the OA factors at 50 ∘ C was HOA (MFR of 0.56) > LO-OOA (0.70) > COA (0.85) ≈ BBOA (0.87) > MO-OOA (0.99), which was not completely consistent with the sequence of their O ∕ C ratios. The high volatility of HOA implied that it had a high potential to be oxidized to secondary species in the gas phase. The aerosol volatility measurement results in this study provide useful parameters for the modeling work of aerosol evolution in China and are also helpful in understanding the formation mechanisms of secondary aerosols.

The molecular composition of humic-like substances (HULIS) in different aerosol samples was analyzed using an ultrahigh-resolution mass spectrometer to investigate the influence of biomass burning on ambient aerosol composition. HULIS in background aerosols were characterized with numerous molecular formulas similar to biogenic secondary organic aerosols. The abundance of nitrogen-containing organic compounds (NOC), including nitrogen-containing bases (N-bases) and nitroaromatics, increased dramatically in ambient aerosols affected by crop residue burning in the farm field. The molecular distribution of N-bases in these samples exhibited similar patterns to those observed in smoke particles freshly emitted from lab-controlled burning of straw residues but were significantly different with those observed from wood burning. Signal intensity of the major N-bases correlated well with the atmospheric concentrations of potassium and levoglucosan. These N-bases can serve as molecular markers distinguishing HULIS from crop residue burning with from wood burning. More nitroaromatics were detected in ambient aerosols affected by straw burning than in fresh smoke aerosols, indicating that many of them are formed in secondary oxidation processes as smoke plumes evolve in the atmosphere. This study highlights the significant contribution of crop residue burning to atmospheric NOC. Further study is warranted to evaluate the roles of NOC on climate and human health.

In order to understand the aging and processing of organic aerosols (OA), an intensive field campaign (Campaign of Air Pollution at Typical Coastal Areas IN Eastern China, CAPTAIN) was conducted March–April at a receptor site (a Changdao island) in central eastern China. Multiple fast aerosol and gas measurement instruments were used during the campaign, including a high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) that was applied to measure mass concentrations and non-refractory chemical components of submicron particles (PM1nr). The average mass concentration of PM1(PM1nr+black carbon) was 47 ± 36 μg m−3 during the campaign and showed distinct variation, depending on back trajectories and their overlap with source regions. Organic aerosol (OA) is the largest component of PM1 (30%), followed by nitrate (28%), sulfate (19%), ammonium (15%), black carbon (6%), and chloride (3%). Four OA components were resolved by positive matrix factorization (PMF) of the high-resolution spectra, including low-volatility oxygenated organic aerosol (LV-OOA), semi-volatile oxygenated OA (SV-OOA), hydrocarbon-like OA (HOA) and a coal combustion OA (CCOA). The mass spectrum of CCOA had high abundance of fragments from polycyclic aromatic hydrocarbons (PAHs) (m/z 128, 152, 178, etc.). The average atomic ratio of oxygen to carbon in OA (O / C) at Changdao was 0.59, which is comparable to other field studies reported at locations downwind of large pollution sources, indicating the oxidized nature of most OA during the campaign. The evolution of OA elemental composition in the van Krevelen diagram (H / C vs. O / C) showed a slope of −0.63; however, the OA influenced by coal combustion exhibits a completely different evolution that appears dominated by physical mixing. The aging of organic aerosols vs. photochemical age was investigated. It was shown that OA / ΔCO, as well as LV-OOA / ΔCO and SV-OOA / ΔCO, positively correlated with photochemical age. LV-OOA accounted for 73% of the OA secondary formation (SOA) in the oldest plumes (photochemical age of 25 h). The kOH at Changdao, by assuming SOA formation and aging as a first-order process proportional to OH, was calculated to be 5.2 × 10−12 cm3 molec.−1 s−1, which is similar to those determined in recent studies of polluted air in other continents.

We used the regional air quality model CMAQ to simulate organic aerosol (OA) concentrations over the Pearl River Delta region (PRD) and compared model results to measurements. Our goals were (1) to evaluate the potential contribution of the aqueous reactive uptake of dicarbonyls (glyoxal and methylglyoxal) as a source of secondary organic aerosol (SOA) in an urban environment, and (2) to quantify the sources of SOA in the PRD in fall. We improved the representation of dicarbonyl gas phase chemistry in CMAQ, as well as added SOA formation via the irreversible uptake of dicarbonyls by aqueous aerosols and cloud droplets, characterized by a reactive uptake coefficient γ = 2.9 × 10 −3 based on laboratory studies. Our model results were compared to aerosol mass spectrometry (AMS) measurements in Shenzhen during a photochemical smog event in fall 2009. Including the new dicarbonyl SOA source in CMAQ led to an increase in the simulated mean SOA concentration at the sampling site from 4.1 μg m −3 to 9.0 μg m −3 during the smog event, in better agreement with the mean observed oxygenated OA (OOA) concentration (8.0 μg m −3 ). The simulated SOA reproduced the variability of observed OOA ( r = 0.89). Moreover, simulated dicarbonyl SOA was highly correlated with simulated sulfate ( r = 0.72), consistent with the observed high correlation between OOA and sulfate ( r = 0.84). Including the dicarbonyl SOA source also increased the mean simulated concentrations of total OA from 8.2 μg m −3 to 13.1 μg m −3 , closer to the mean observed OA concentration (16.5 μg m −3 ). The remaining difference between the observed and simulated OA was largely due to impacts from episodic biomass burning emissions, but the model did not capture this variability. We concluded that, for the PRD in fall and outside of major biomass burning events, 75% of the total SOA was biogenic. Isoprene was the most important precursor, accounting for 41% of the total SOA. Aromatics accounted for 13% of the total SOA. Our results show that the aqueous chemistry of dicarbonyls can be an important SOA source, potentially accounting for 53% of the total surface SOA in the PRD in fall.

In 2014, a large, comprehensive field campaign was conducted in the densely populated North China Plain. The measurement site was located in a botanic garden close to the small town Wangdu, without major industry but influenced by regional transportation of air pollution. The loss rate coefficient of atmospheric hydroxyl radicals (OH) was quantified by direct measurements of the OH reactivity. Values ranged between 10 and 20 s−1 for most of the daytime. Highest values were reached in the late night with maximum values of around 40 s−1. OH reactants mainly originated from anthropogenic activities as indicated (1) by a good correlation between measured OH reactivity and carbon monoxide (linear correlation coefficient R2 = 0.33) and (2) by a high contribution of nitrogen oxide species to the OH reactivity (up to 30 % in the morning). Total OH reactivity was measured by a laser flash photolysis–laser-induced fluorescence instrument (LP-LIF). Measured values can be explained well by measured trace gas concentrations including organic compounds, oxygenated organic compounds, CO and nitrogen oxides. Significant, unexplained OH reactivity was only observed during nights, when biomass burning of agricultural waste occurred on surrounding fields. OH reactivity measurements also allow investigating the chemical OH budget. During this campaign, the OH destruction rate calculated from measured OH reactivity and measured OH concentration was balanced by the sum of OH production from ozone and nitrous acid photolysis and OH regeneration from hydroperoxy radicals within the uncertainty of measurements. However, a tendency for higher OH destruction compared to OH production at lower concentrations of nitric oxide is also observed, consistent with previous findings in field campaigns in China.

Synchronized online measurements of gas- and particle- phase organics including non-methane hydrocarbons (NMHCs), oxygenated volatile organic compounds (OVOCs) and submicron organic matters (OM) were conducted in November 2010 at Heshan, Guangdong provincial supersite, China. Several biomass burning events were identified by using acetonitrile as a tracer, and enhancement ratios (EnRs) of organics to carbon monoxide (CO) obtained from this work generally agree with those from rice straw burning in previous studies. The influences of biomass burning on NMHCs, OVOCs and OM were explored by comparing biomass burning impacted plumes (BB plumes) and non-biomass burning plumes (non-BB plumes). A photochemical age-based parameterization method was used to characterize primary emission and chemical behavior of those three organic groups. The emission ratios (EmRs) of NMHCs, OVOCs and OM to CO increased by 27-71%, 34-55% and 67% in BB plumes, respectively, in comparison with non-BB plumes. The estimated formation rate of secondary organic aerosol (SOA) in BB plumes was found to be 24% faster than non-BB plumes. By applying the above emission ratios to the whole PRD, the annual emissions of VOCs and OM from open burning of crop residues would be 56.4 and 3.8Gg in 2010 in PRD, respectively.

The 16th Universiade, an international multi-sport event, was hosted in Shenzhen, China from 12 to 23 August 2011. During this time, officials instituted the Pearl River Delta action plan in order to enhance the air quality of Shenzhen. To determine the effect of these controls, the current study examined the trace elements, water-soluble ions, and stable lead isotopic ratios in atmospheric particulate matter (PM) collected during the controlled (when the restrictions were in place) and uncontrolled periods. Fine particles (PM2.5) were collected at two sampling sites in Shenzhen: “LG”—a residential building in the Longgang District, with significant point sources around it and “PU”—Peking University Shenzhen Graduate School in the Nanshan District, with no significant point sources. Results from this study showed a significant increase in the concentrations of elements during the uncontrolled periods. For instance, samples at the LG site showed (controlled to uncontrolled periods) concentrations (in ng·m−3) of: Fe (152 to 290), As (3.65 to 8.38), Pb (9.52 to 70.8), and Zn (98.6 to 286). Similarly, samples at the PU site showed elemental concentrations (in ng·m−3) of: Fe (114 to 301), As (0.634 to 8.36), Pb (4.86 to 58.1), and Zn (29.5 to 259). Soluble Fe ranged from 7%–15% for the total measured Fe, indicating an urban source of Fe. Ambient PM2.5 collected at the PU site has an average 206Pb/204Pb ratio of 18.257 and 18.260 during controlled and uncontrolled periods, respectively. The LG site has an average 206Pb/204Pb ratio of 18.183 and 18.030 during controlled and uncontrolled periods, respectively. The 206Pb/204Pb ratios at the PU and the LG sites during the controlled and uncontrolled periods were similar, indicating a common Pb source. To characterize the sources of trace elements, principal component analysis was applied to the elements and ions. Although the relative importance of each component varied, the major sources for both sites were identified as residual oil combustion, secondary inorganic aerosols, sea spray, and combustion. The PM2.5 levels were severely decreased during the controlled period, but it is unclear if this was a result of the controls or change in meteorology.

A one-year-long observation on major organic compounds in PM 2.5 was performed in a coastal mega-city in South China, Shenzhen, in order to gain information of their ambient concentration levels and the implications for sources. The compounds identified included alkanes, PAHs, hopanes, fatty acids and dicarboxylic acids, whose annual average concentrations during the year were 56.0, 14.8, 2.51, 253, and 25.2 ng m − 3 , respectively. The seasonal molecular distributions of these organic compounds were discussed to explore their contributing sources in Shenzhen. Conclusively, alkanes and PAHs had the dominant source of fossil fuel combustion, although alkanes also had significant contribution from plant wax (~ 16%). The hopane series distributions further indicated that vehicle emissions were the dominant fossil fuel combustion source for PM 2.5 in Shenzhen. Cooking emissions were inferred to be the most possible main source for fatty acids, while both primary and secondary origins were implied for azelaic acid, the dominant one in the dicarboxylic acids identified. Most of the organic compounds analyzed showed a size distribution pattern peaking at 0.32–0.56 or 0.56–1 μm in the accumulation mode, except that the cooking-related organic acids showed implication of a coarse mode-dominated pattern.

Shanghai, with a population of over 20 million, is the largest mega-city in China. Rapidly increasing industrial and metropolitan emissions have deteriorated its air quality in the past decades, with fine particle pollution as one of the major issues. However, systematic characterization of atmospheric fine particles with advanced measurement techniques has been very scarce in Shanghai. During 2010 Shanghai World Expo, we deployed a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a single particle soot photometer (SP2) in urban Shanghai between 15 May and 10 June 2010 to measure fine particles with a high time resolution. The 4-min resolution PM1 mass concentration ranged from 5.5 to 155 μg m−3, with an average of 29.2 μg m−3. On average, sulfate and organic matter (OM) were the most abundant PM1 components, accounting for 33.3 and 28.7% of the total mass, respectively, while the fraction of nitrate showed an increasing trend with the increasing PM1 loading, indicating the photochemical nature of high fine particle pollution in Shanghai. Taking advantage of HR-ToF-AMS and SP2, OM was found to have an average OM/OC ratio (organic matter mass/organic carbon mass) of 1.55 and black carbon (BC) had an average number fraction of internally mixed BC of 41.2%. Positive matrix factorization (PMF) analysis on the high resolution organic mass spectral dataset identified a hydrocarbon-like (HOA), a semi-volatile oxygenated (SV-OOA), and a low-volatility oxygenated (LV-OOA) organic aerosol component, which on average accounted for 24.0, 46.8, and 29.2% of the total organic mass, respectively. The diurnal patterns of them with interesting time delay possibly implied a photochemical oxidizing process from HOA (and/or its concurrently emitted gaseous organic pollutants) to SV-OOA to LV-OOA. Back trajectory analysis indicated that the northwesterly continental air mass represented the most severe pollutant regional transport condition with the highest nitrate and SV-OOA fractions. In addition, the results in Shanghai were compared with similar measurements performed recently in other mega-cities in the world.

As part of the 2008 Campaign of Air Quality Research in Beijing and Surrounding Regions (CAREBeijing 2008), measurements of gaseous sulfuric acid (H2SO4) have been conducted at an urban site in Beijing, China from 7 July to 25 September 2008 using atmospheric pressure ion drift – chemical ionization mass spectrometry (AP-ID-CIMS). This represents the first gaseous H2SO4 measurements in China. Diurnal profile of sulfuric acid is strongly dependent on the actinic flux, reaching a daily maximum around noontime and with an hourly average concentration of 5 × 106 molecules cm−3. Simulation of sulfuric acid on the basis of the measured sulfur dioxide concentration, photolysis rates of ozone and nitrogen dioxide, and aerosol surface areas captures the trend of the measured H2SO4 diurnal variation within the uncertainties, indicating that photochemical production and condensation onto preexisting particle surface dominate the observed diurnal H2SO4 profile. The frequency of the peak H2SO4 concentration exceeding 5 × 106 molecules cm−3 increases by 16 % during the period of the summer Olympic Games (8–24 August 2008), because of the implementation of air quality control regulations. Using a multivariate statistical method, the critical nucleus during nucleation events is inferred, containing two H2SO4 molecules (R2 = 0.85). The calculated condensation rate of H2SO4 can only account for 10–25 % of PM1 sulfate formation, indicating that either much stronger sulfate production exists at the SO2 source region or other sulfate production mechanisms are responsible for the sulfate production.

Size distributions can provide important information about aerosol sources, formation, and growth mechanisms. However, compared to size distributions of inorganic aerosols, size distributions of carbonaceous aerosols have been much less studied and reported in the literature. In this paper, we systematically measured size distributions of elemental carbon (EC), organic carbon (OC), oxalate, polycyclic aromatic hydrocarbons (PAHs), as well as major inorganic ions in urban aerosols in Shenzhen, China. Totally 24 sets of samples were collected using a ten-stage micro orifice uniform deposit impactor (MOUDI) during October 2009 to February 2010. Three lognormal modes contained in the size distributions of species were resolved based on positive matrix factorization (PMF) analysis of the measured dataset, corresponding to the condensation (peak = 0.34 μm), droplet (peak = 0.84 μm), and coarse (peak = 5.4 μm) modes, respectively. The mean concentrations of EC in the condensation, droplet, and coarse modes were 2.20, 1.18, and 0.64 μg m −3 , respectively, and the modal characteristics of EC indicate that fresher local combustion emissions contributed mostly to aerosol EC in the urban atmosphere of Shenzhen. The mean concentrations of OC in the condensation, droplet, and coarse modes were 2.29, 3.34, and 3.51 μg m −3 , respectively, and the modal characteristics of OC indicate that its sources were more primary in the condensation mode while more secondary in the droplet mode. The modal characteristics of aerosol oxalate and PAHs suggest that they were predominantly from in-cloud secondary formation and local emissions, respectively.

The Pearl River Delta (PRD) region in South China is one of the most economically developed regions in China, but it is also noted for its severe air pollution due to industrial/metropolitan emissions. In order to continuously improve the understanding and quantification of air pollution in this region, an intensive campaign was executed in PRD during October–November 2008. Here, we report and analyze Aerodyne High-Resolution Aerosol Mass Spectrometer measurements at Kaiping, a rural site downwind of the highly-polluted central PRD area, to characterize the general features of submicron particulate pollution in the regional air. The mean measured PMsub>1 mass concentration was 33.1±18.1 μg m[superscript −3] during the campaign and composed of organic matter (33.8%), sulfate (33.7%), ammonium (14.0%), nitrate (10.7%), black carbon (6.7%), and chloride (1.1%), which is characterized by high fractions of inorganic ions due to huge emissions of SO[subscript 2] and NO[subscript x] in PRD. The average size distributions of the species (except BC) were all dominated by an accumulation mode peaking at ~450 nm in vacuum aerodynamic diameter. Calculations based on high-resolution organic mass spectra indicate that C, H, O, and N on average contributed 56.6, 7.0, 35.1, and 1.3% to the total organic mass, respectively, corresponding to an organic matter mass to organic carbon mass ratio (OM/OC) of 1.77±0.08. Based on the high-resolution organic mass spectral dataset observed, Positive Matrix Factorization (PMF) analysis differentiated the organic aerosol into three components, i.e., biomass burning (BBOA) and two oxygenated (LV-OOA and SV-OOA) organic aerosols, which on average accounted for 24.5, 39.6 and 35.8% of the total organic mass, respectively. The BBOA showed strong features of biomass burning emissions and has been mainly attributed to the open field burning of crop residues after the harvest in PRD rural areas. The LV-OOA and SV-OOA were found to correspond to more aged (and thus less-volatile) and fresher (and semi-volatile) secondary organic aerosol (SOA), respectively. Analysis of meteorological influence supported that regional transport from the central PRD area was the major origin of the PM[subscript 1] observed at the Kaiping site., National High-Tech R&D (863) Plan of China (2006AA06A308), National Natural Science Funds for Distinguished Young Scholars (21025728), National Natural Science Foundation (China) (40805049), National Natural Science Foundation (China) (20777001)

Aerosol mass spectrometry has proved to be a powerful tool to measure submicron particulate composition with high time resolution. Factor analysis of mass spectra (MS) collected worldwide by aerosol mass spectrometer (AMS) demonstrates that submicron organic aerosol (OA) is usually composed of several major components, such as oxygenated (OOA), hydrocarbon-like (HOA), biomass burning (BBOA), and other primary OA. In order to help interpretation of component MS from factor analysis of ambient OA datasets, AMS measurements of different primary sources is required for comparison. Such work, however, has been very scarce in the literature, especially for high resolution MS (HR-MS) measurements, which performs improved characterization by separating the ions of different elemental composition at each m/z in comparison with unit mass resolution MS (UMR-MS) measurements. In this study, primary emissions from four types of Chinese cooking (CC) and six types of biomass burning (BB) were simulated systematically and measured using an Aerodyne High-Resolution Time-of-Flight AMS (HR-ToF-AMS). The MS of the CC emissions show high similarity, with m/z 41 and m/z 55 being the highest signals; the MS of the BB emissions also show high similarity, with m/z 29 and m/z 43 being the highest signals. The MS difference between the CC and BB emissions is much bigger than that between different CC (or BB) types, especially for the HR-MS. The O/C ratio of OA ranges from 0.08 to 0.13 for the CC emissions and from 0.18 to 0.26 for the BB emissions. The UMR ions of m/z 43, m/z 44, m/z 57, and m/z 60, usually used as tracers in AMS measurements, were examined for their HR-MS characteristics in the CC and BB emissions. In addition, the MS of the CC and BB emissions are also compared with component MS from factor analysis of ambient OA datasets observed in China, as well as with other AMS measurements of primary sources in the literature. The MS signatures of cooking and biomass burning emissions revealed in this study can be used as important reference for factor analysis of ambient OA datasets, especially for the relevant studies in East Asia.

Secondary organic aerosol (SOA) is one of the major components of aerosols in the atmosphere and has not been well understood so far. Due to the complex chemical composition of organic aerosols, the identification of SOA has been a hotspot and difficult issue in the field of aerosol study. This study attempts to quantitatively identify SOA in winter of Shenzhen based on positive matrix factorization (PMF) analysis. Major sources were resolved and SOA was identified subsequently according to the characteristic ion fragments measured by highly time-resolved aerosol mass spectrometer measurement. It showed that in the winter of Shenzhen the average SOA concentration was 9.41 ± 6.33 μg/m3, accounting for 39.9 ± 21.8% of the total organic mass. Compared with primary organic aerosol (POA), the SOA concentrations had no large variation, suggestive of characteristics of regional secondary pollutants. The ratio of SOA/BC had pronounced diurnal variation, similar to that of O x (O3+NO2), indicating SOA formation was significantly controlled by activity of photochemistry in the atmosphere. The most effective period for SOA formation was from 9 am ∼3 pm since the SOA/BC ratio increased by 122% during this period. This study provides a new technical method and a new idea for SOA investigation.

As part of Campaigns of Air Quality Research in Beijing and Surrounding Region–2008 (CAREBeijing-2008), an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed in urban Beijing to characterize submicron aerosol particles during the time of 2008 Beijing Olympic Games and Paralytic Games (24 July to 20 September 2008). The campaign mean PM1 mass concentration was 63.1±39.8 μg m−3; the mean composition consisted of organics (37.9%), sulfate (26.7%), ammonium (15.9%), nitrate (15.8%), black carbon (3.1%), and chloride (0.87%). The average size distributions of the species (except BC) were all dominated by an accumulation mode peaking at about 600 nm in vacuum aerodynamic diameter, and organics was characterized by an additional smaller mode extending below 100 nm. Positive Matrix Factorization (PMF) analysis of the high resolution organic mass spectral dataset differentiated the organic aerosol into four components, i.e., hydrocarbon-like (HOA), cooking-related (COA), and two oxygenated organic aerosols (OOA-1 and OOA-2), which on average accounted for 18.1, 24.4, 33.7 and 23.7% of the total organic mass, respectively. The HOA was identified to be closely associated with primary combustion sources, while the COA mass spectrum showed high similarity to that measured from cooking aerosol emissions. The OOA components correspond to aged secondary organic aerosol. Although the two OOA components have similar elemental (O/C, H/C) compositions, they display differences in mass spectra and time series which appear to correlate with the different source regions sampled during the campaign. Back trajectory clustering analysis indicated that the southerly air flows were associated with the highest PM1 pollution during the campaign. This result is similar to observations made in the summer of 2006, although the average PM1 concentration level for the southerly air flows is 31% lower than for the 2008 campaign. Aerosol particles in southern airmasses were especially rich in inorganic and oxidized organic species. Aerosol particles in northern airmasses contained a large fraction of primary HOA and COA species, probably due to stronger influences from local emissions. The lowest concentration levels for all major species were obtained during the Olympic game days (8–24 August 2008), possibly due to the effects of both strict emission controls and favorable meteorological conditions.

HUmic-LIke Substances (HULIS) comprise a significant fraction of the water-soluble organic aerosol mass and influence the water uptake properties of aerosols in the atmosphere. In this work, the abundance and size distributions of HULIS in ambient aerosols were measured in a rural location in South China at a time with a visible presence of crop residue burning. PM 2.5 samples of fresh smoke from burning rice straw and sugar cane leaves were also collected and analyzed for HULIS and major aerosol constituents. HULIS were abundant in both ambient samples and in fresh biomass burning emissions, accounting for ∼60% of the water-soluble organic carbon in the ambient aerosols and ∼30% in the fresh biomass burning aerosols. In the particles in the range of 0.32–1.8 μm, the abundance of HULIS was 40–90% of the combined abundance of sulfate and ammonium, suggesting that HULIS should be considered when quantifying the role of sulfate aerosols serving as cloud condensation nuclei. The size distribution of HULIS was characterized by a dominant droplet mode with a mass median aerodynamic diameter (MMAD) in the range of 0.63–0.87 μm, accounting for 81% of the total HULIS mass, a minor condensation mode (12%, MMAD: 0.23–0.28 μm) and a coarse mode (7%, MMAD: 4.0–5.7 μm). The small amount of HULIS in the coarse mode indicated that soil-derived HULIS was a very minor source. On the basis of the size distribution characteristics, HULIS were postulated to have multiple sources, including secondary formation in cloud droplets, secondary formation through heterogeneous reactions or aerosol-phase reactions, and primary emissions from biomass burning.

Size-resolved chemical composition of aerosol was investigated during the PRIDE intensive field campaign in October 2004 at Xinken, at Pearl River Delta (PRD), China. Xinken is a rural/coastal site located south of Guangzhou. Size-segregated particles were sampled using Micro-Orifice Uniform Deposit Impactors (MOUDI) in order to characterize regional aerosol pollution. The meteorological conditions during the measurements were stable with low wind speed, high temperature and high RH, leading to high concentrations of fine particles, especially due to secondary components. The average concentrations of PM 1.8 and PM 10 were 51±19 and 84±27 μg m −3 , respectively, with a ratio of PM 1.8 /PM 10 0.64±0.09, which indicates that fine particles dominated in PM 10 . Sulfate, nitrate and ammonium were major ionic components. Aerosol mass size distributions showed either two or three modes. Land–sea circulation brought back aged aerosols to the sampling site leading to an increase of the concentrations of sodium and chloride in aerosols. The “condensation mode” of sulfate, which was formed by gas-to-particle conversion, was in the size range of 0.32–0.56 μm, and the “droplet mode” of sulfate was observed in the size range of 0.56–1.0 or 1.0–1.8 μm. Nitrate was distributed evenly over fine and coarse particles. The analysis of measured and calculated equilibrium constant of NH 4 NO 3 indicates that dissociation of NH 4 NO 3 in daytime is favored, but that at night ammonium nitrate is stable and constitutes the fine mode nitrate, while the coarse mode nitrate may be formed by the reaction of HNO 3 and sea-salt or soil components. Chemical mass closures showed reasonable agreement.

Little is known about the characteristics of particulate matter emissions from vehicles in China, although such information is critical in source apportionment modeling, emission inventories, and health effect studies. In this paper, we report a comprehensive characterization of PM2.5 emissions in the Zhujiang Tunnel in the Pearl River Delta region of China. The chemical speciation included elemental carbon, organic carbon, inorganic ions, trace elements, and organic compounds. The emission factors of individual species and their relative distributions were obtained for a mixed fleet of heavy-duty vehicles (19.8%) and light-duty vehicles (80.2%). In addition, separate emission factors of PM2.5 mass, elemental carbon, and organic matter for heavy-duty vehicles and light-duty vehicles also were derived. As compared to the results of other tunnel studies previously conducted, we found that the abundances and distributions of the trace elements in PM2.5 emissions were more varied. In contrast, the characteristics of the trace organic compounds in the PM2.5 emissions in our study were consistent with characteristics found in other tunnel studies and dynamometer tests. Our results suggested that vehicular PM2.5 emissions of organic compounds are less influenced by the geographic area and fleet composition and thereby are more suitable for use in aerosol source apportionment modeling implemented across extensive regions.

Knowledge of particle number size distribution (PND) and new particle formation (NPF) events in Southern China is essential for mitigation strategies related to submicron particles and their effects on regional air quality, haze, and human health. In this study, seven field measurement campaigns were conducted from December 2013 to May 2015 using a scanning mobility particle sizer (SMPS) at four sites in Southern China, including three urban sites and one background site. Particles were measured in the size range of 15-615nm, and the median particle number concentrations (PNCs) were found to vary in the range of 0.3×104-2.2×104cm-3 at the urban sites and were approximately 0.2×104cm-3 at the background site. The peak diameters at the different sites varied largely from 22 to 102nm. The PNCs in the Aitken mode (25-100nm) at the urban sites were up to 10 times higher than they were at the background site, indicating large primary emissions from traffic at the urban sites. The diurnal variations of PNCs were significantly influenced by both rush hour traffic at the urban sites and NPF events. The frequencies of NPF events at the different sites were 0%-30%, with the highest frequency occurring at an urban site during autumn. With higher SO2 concentrations and higher ambient temperatures being necessary, NPF at the urban site was found to be more influenced by atmospheric oxidizing capability, while NPF at the background site was limited by the condensation sink. This study provides a unique dataset of particle number and size information in various environments in Southern China, which can help understand the sources, formation, and the climate forcing of aerosols in this quickly developing region, as well as help constrain and validate NPF modeling.

Cereal straw is one of the most abundant biomass burned in China but its contribution to fine particulates is not adequately understood. In this study, three main kinds of cereal straws were collected from five grain producing areas in China. Fine particulate matters (PM2.5) from the cereal straws subjected to control burnings, both under smoldering and flaming status, were sampled by using a custom made dilution chamber and sampling system in the laboratory. Element carbon (EC) and organic carbon (OC) was analyzed. 141 compounds of organic matters were measured by gas chromatography-mass spectrum (GC-MS). Source profiles of particulate organic matters emitted from cereal straw burnings were obtained. The results indicated that organic matters contribute a large fraction in fine particulate matters. Levoglucosan had the highest contributions with averagely 4.5% in mass of fine particulates and can be considered as the tracer of biomass burnings. Methyloxylated phenols from lignin degradation also had high concentrations in PM2.5, and contained approximately equal amounts of guaiacyl and syringyl compounds. β-Sitostrol also made up relatively a large fraction of PM2.5 compared with the other sterols (0.18%-0.63% of the total fine particle mass). Normal alkanes, PAHs, fatty acids, as well as normal alkanols had relatively lower concentrations compared with the compounds mentioned above. Carbon preference index (CPI) of normal alkanes and alkanoic acids showed characteristics of biogenic fuel burnings. Burning status significantly influenced the formations of EC and PAHs. The differences between the emission profiles of straw and wood combustions were displayed by the fingerprint compounds, which may be used to identify the contributions between wood and straw burnings in source apportionment researches.

Solvent extractable organic compounds (SEOC), organic carbon, elemental carbon and water soluble organic carbon (WSOC) in PM2.5 samples collected in Shanghai, China in 2002 and 2003 were measured to determine the composition and sources of the organic matter in atmospheric aerosols. Distinct seasonal variations were detected with higher concentrations of organic matter in winter. The concentration of total carbon of about 20 μg m−3 in winter was about three times the summer value. About 30% of the total carbon was water soluble. Unresolved complex mixture (UCM) and fatty acids were the most abundant components quantified in SEOC, similar to other Chinese cities previously studied. High ratio of UCM to n-alkanes (U:R) and the composition of triterpanes indicated that engine exhaust was a major source of the airborne organic matter. Emissions from coal burning had more impact in the rural areas, according to the U:R value and PAHs composition. Chemical mass balance (CMB) modeling shows that about half of the organic carbon was from engine exhaust and about 15% was from coal burning. No clear spatial variation in the concentration of the organic matter was found between urban and rural areas. Our results showed that due to the rapid urbanization and relocation of industrial plants from urban areas to rural areas in the past 20 years, air pollution in rural areas is becoming a serious problem in Shanghai and the Yangtze River delta.