利用气相色谱-质谱仪/火焰离子检测器（Online-GC-MS/FID）对2017年冬季山东德州大气中99种挥发性有机物（VOCs）进行连续测量，研究了VOCs浓度和组分特征、日变化趋势、来源及其对臭氧(O3)、二次有机气溶胶（SOA）生成的贡献。结果表明，德州大气VOCs平均体积分数为（47.74±33.11）×10-9，烷烃占比最大，为40.66%。总VOCs及其组分表现出早晚体积分数高、中午体积分数低的日变化规律。德州大气中丙烷、丙烯、苯及甲苯和二氯甲烷分别受到液化石油气挥发、生物质燃烧、机动车排放和溶剂使用等人为源的影响。反向轨迹模型分析发现，北方内陆气团对德州VOCs体积分数具有一定贡献。烷烃、烯烃、芳香烃的臭氧生成潜势分别为（34.87±33.60）、（120.48±118.76）和（59.77±94.14）μg/m3，乙烯、丙烯、甲苯和间/对二甲苯的贡献较大。芳香烃氧化主导了SOA生成，其贡献率为93.7%，甲苯、间/对二甲苯、苯对SOA生成的贡献最大。为解决大气复合污染问题、实现臭氧和PM2.5协同控制，德州应重点控制甲苯、间/对二甲苯等芳香烃的排放。

Nitro-aromatic compounds (NACs) were measured hourly at a rural site in China during wintertime to monitor the changes due to local and regional impacts of biomass burning (BB). Concurrent and continuous measurements of the concentrations of 16 NACs in the gas and particle phases were performed with a time-of-flight chemical ionization mass spectrometer (CIMS) equipped with a Filter Inlet for Gas and Aerosol (FIGAERO) unit using iodide as the reagent ion. NACs accounted for < 2 % of the mass concentration of organic matter (OM) and total particulate matter (PM), but the total particle mass concentrations of these compounds can reach as high as 1000 ng m−3 (299 ng m−3ave.), suggesting that they may contribute significantly to the radiative forcing effects of atmospheric particles. Levels of gas-phase NACs were highest during the daytime (15:00–16:00 local time, L.T.), with a smaller night-time peak around 20:00 L.T. Box-model simulations showed that this occurred because the rate of NAC production from gas-phase sources exceeded the rate of loss, which occurred mainly via the OH reaction and to a lesser degree via photolysis. Data gathered during extended periods with high contributions from primary BB sources (resulting in 40–60 % increases in NAC concentrations) were used to characterize individual NACs with respect to gas-particle partitioning and the contributions of regional secondary processes (i.e. photochemical smog). On days without extensive BB, secondary formation was the dominant source of NACs and NAC levels correlated strongly with the ambient ozone concentration. Analyses of individual NACs in the regionally aged plumes sampled on these days allowed precursors such as phenol and catechol to be linked to their NAC derivatives (i.e. nitrophenol and nitrocatechol). Correlation analysis using the high time resolution data and box-model simulation results constrained the relationships between these compounds and demonstrated the contribution of secondary formation processes. Furthermore, 13 of 16 NACS were classified according to primary or secondary formation process. Primary emission was the dominant source (accounting for 60–70 % of the measured concentrations) of 5 of the 16 studied NACs, but secondary formation was also a significant source. Photochemical smog thus has important effects on brown carbon levels even during wintertime periods dominated by primary air pollution in rural China.

To clarify the aerosol optical properties under different pollution levels and their impacting factors, hourly organic carbon (OC), elemental carbon (EC), and water-soluble ion (WSI) concentrations in PM2.5 were observed by using monitoring for aerosols and gases (MARGA) and a semicontinuous OC/EC analyzer (Model RT-4) in Wuhan from 9 to 26 January 2018. The aerosol extinction coefficient (bext) was reconstructed using the original Interagency Monitoring of Protected Visual Environment (IMPROVE) formula with a modification to include sea salt aerosols. A good correlation was obtained between the reconstructed bext and measured bext converted from visibility. bext presented a unimodal distribution on polluted days (PM2.5 mass concentrations &gt; 75 μg•m-3), peaking at 19:00. bext on clean days (PM2.5 mass concentrations &lt; 75 μg•m-3) did not change much during the day, while on polluted days, it increased rapidly starting at 12:00 due to the decrease of wind speed and increase of relative humidity (RH). PM2.5 mass concentrations, the aerosol scattering coefficient (bscat), and the aerosol extinction coefficient increased with pollution levels. The value of bext was 854.72 Mm-1 on bad days, which was 4.86, 3.1, 2.29, and 1.28 times of that obtained on excellent, good, acceptable, and poor days, respectively. When RH &lt; 95%, bext exhibited an increasing trend with RH under all pollution levels, and the higher the pollution level, the bigger the growth rate was. However, when RH &gt; 95%, bext on acceptable, poor and bad days decreased, while bext on excellent and good days still increased. The overall bext inWuhan in January was mainly contributed by NH4NO3 (25.2%) and organic matter (20.1%). The contributions of NH4NO3 and (NH4)2SO4 to bext increased significantly with pollution levels. On bad days, NH4NO3 and (NH4)2SO4 contributed the most to bext, accounting for 38.2% and 27.0%, respectively. © 2019 by the authors.

Spectral light-absorption properties measured with an Aethalometer (AE; Model AE33; Magee Scientific) are widely used in radiative forcing studies and source appointment in China. However, considerable uncertainty regarding the measured absorption coefficient (σabs) exists because of the multiple-scattering effects, loading effects, and differences in filter tape. This study evaluated σabs by comparing the values measured with an AE33 using Tape 8050, an AE33 using Tape 8060 (which differs from Tape 8050 in material), and a three-wavelength photoacoustic soot spectrometer (PASS-3) during two field campaigns in eastern China. The results indicated that the AE33-measured σabs using either tape exceeded the PASS-3-measured value by approximately three times, mainly owing to the multiple-scattering effect. A wavelength-independent multiple-scattering compensation factor (2.90), which varies slightly (± 0.04) for eastern China, is recommended for these regions. When σabs was measured with the AE33 using Tape 8050, the value highly depended on the loading on the tape, which led to significant uncertainty and discontinuity in the absorption Å ngström exponent compared to using Tape 8060. A method was proposed to effectively correct the historical datasets of σabs and the absorption Å ngström exponent by using the AE33 with Tape 8050. This work provides insight into the quality of measured absorption data when filter-based measurement technology is applied. © The Author(s).

Secondary organic aerosol (SOA) is a major component of aerosols in the atmosphere, which plays a crucial role in climate change, regional pollution and human health. Laboratory simulations are usually used to mimic SOA formation. The most commonly used simulation facilities are environmental chambers and potential aerosol mass (PAM) reactors. Here in this work, we review the studies about influencing factors and mechanisms of SOA formation, as well as the evolution of SOA aging. We summarize the influencing factors on SOA yields, i.e. OH exposure, NOx level, and the loading and chemical composition of seed particles. The effects of NOx level (i.e. VOCs/NOx) and OH exposure are nonmonotonic. The NOx level influences the fate of RO2 radicals, so SOA yields will increase and then decrease with the addition of NOx. Similarly, the increase of OH exposure affects the major oxidation mechanism from functionalization to fragmentation, leading to the up and down trend of SOA yields. The higher seed particle loading provides more surface area for condensable products and then increases the SOA yields. The particle acidity favors the uptake process for gas-phase products and promote the SOA formation via further reactions in the condense phase. Trace components e.g. transition metals and minerals can be involved in the SOA formation and aging by catalysis or affecting the uptake of oxidants and their products. Chambers and PAM reactors are usually used to explore SOA formation potential of different sources. SOA formation potential from vehicles will be influenced by engine types, engine loading and composition of fuel. The highest SOA enhancement ratio (SOA/POA) from gasoline engines is about 4~14, when the equivalent photochemical days are 2~3 d. The SOA production mass from gasoline vehicles is from about 10~40 to 400~500 mg/kg fuel. The SOA formation potential is about 400~500 mg/kg fuel. The largest SOA enhancement ratio for biomass burning is 1.4~7.6, which occurs at 3~4 photochemical days. The SOA enhancement ratio from ambient air differs from region to region. However, the highest ratios all occur at the photochemical age of about 2~4 d. We summarize the SOA characteristics evolution with aging. Oxidation state of particles will increase with OH exposure. Changes of H/C and O/C with increasing OH exposure can be plotted in the Van Krevelen diagrams. The slopes of fitted curve range from -1 to 0, indicating OA evolution chemistry involving addition of carboxylic acids or addition of alcohols/peroxides. In addition, the volatility and hygroscopicity of oxidized OA will be higher than primary organic aerosols. In the future, more studies should be focused on developing new technologies to measuring the oxidized intermediate products at a molecular level. Also the researches on the mechanism of SOA formation from complex precursors are also crucial to understand the SOA formation at real atmosphere. © 2020 Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences.

In this study, the black carbon (BC) measurements in the atmosphere of Nanjing, China were continuously conducted from 2015 to 2018 using a Model AE-33 aethalometer. By combining dataset of PM2.5, PM10, CO, NO2, SO2, O3 and meteorological parameters, the temporal variations and the source apportionment of BC were given in this study. The results showed that the PM2.5 mass concentrations decreased in Nanjing, with an average annual rate of variation of 6.50 μg/(m3⋅year). Differently, the annual average concentrations of BC increased with an average annual variation rate of 214.71 ng/(m3⋅year). The seasonal variations showed the pattern of BC mass concentrations in winter &gt; autumn &gt; spring &gt; summer. The diurnal variations of BC mass concentrations showed a double-peak in all four seasons. The first peak occurred at approximately 7:00 in spring, summer and autumn and around 8:00 in winter. The second peak took place after 18:00. The average AAE (absorption Ångström exponent) was 1.26 with a maximum of 1.35 during wintertime and the lowest (1.12) during summertime. In addition, the AAE was smaller in the daytime than that at night, with a minimum occurring between 13:00 and 14:00. BC and visibility show a good power-function relationship at different humidity levels. The average values of the visibility thresholds of the BC mass concentrations in spring, summer, autumn and winter were 1.326, 5.522, 1.340 and 0.708 μg/m3, respectively. The greater the relative humidity, the smaller the visibility threshold for the BC mass concentrations was. © 2020

Gaseous dicarboxylic acids (diacids) are suggested to participate in atmospheric new particle formation via bonding with sulfuric acid (SA), ammonia (NH3), amines, and other molecules. However, there is a lack of observational evidence for the involvement of diacids in particle nucleation. Comprehensive measurements were conducted at a rural site of the North China Plain in winter, and unexpectedly high nucleation rates (JOBS, 30.5-839.7 cm-3 s-1) were observed under low SA levels (0.7 × 106 to 4.4 × 106 cm-3). Neither SA-NH3 nor SA-dimethylamine (DMA) mechanisms could fully explain the JOBS. Gaseous diacid monomers and dimers and diacid-SA-DMA clusters were identified in this study. The JOBS values were enhanced by a factor of 5 to 10 as the signal intensities of diacids increased 4-fold. Products of diacid signals and SA concentrations showed a positive correlation with the JOBS (Pearson's correlation coefficient = 0.72). Experimental evidence was found that succinic acid competes with the second SA molecule for addition to the SA·DMA cluster. The concentrations of diacids were estimated to be 1-3 orders of magnitude higher than those of SA. We propose that diacids could actively participate in particle nucleation and may dominate the initial steps under high [diacids]/[SA] ratios. Copyright © 2020 American Chemical Society.

Most previous studies treat regional transport of aerosols as a whole, without distinguishing the transport of secondary aerosols and that of their precursors. A new method of quantifying the transport forms of secondary inorganic aerosols (SIA) using the Nested Air Quality Prediction Modeling System was proposed. The contribution of nonlocal emissions to SIA in the receptor region was divided into three parts: (1) SIA chemically formed by nonlocal emissions in their source regions; (2) SIA chemically formed by nonlocal emissions during transport; and (3) SIA chemically formed by nonlocal emissions in the receptor region, representing transport of precursors. In the North China Plain, the transport of precursors and SIA produced during transport are the two main transport forms. Furthermore, the contribution from transport of precursors increased under polluted conditions in most cities. The results indicate that joint control of precursors is paramount for mitigating air pollution. ©2020. The Authors.

Formaldehyde (HCHO) is one of the most important intermediate products of atmospheric photochemical reactions and is also a radical source that promotes ozone formation. Given its high solubility, HCHO is likely to exist in particulate form. In this work, gaseous HCHO (HCHOg) and particulate HCHO (HCHOp) were separated and collected by a rotating wet annular denude (RWAD) and an aerosol growth chamber-coil aerosol cooler (AC). The collected HCHO from the RWAD and AC are measured by two online Hantzsch method-based formaldehyde analyzers. The comprehensive campaign was held in the Yangtze River Delta of China from 15 May to 18 June 2018, which is during the harvest season. Several biomass burning events were identified by using acetonitrile as a tracer. During the period influenced by biomass burning, the mixing ratios of HCHOg and HCHOp were respectively 122% and 231% higher than those during other time periods. The enhancement ratio of HCHOg to acetonitrile obtained from this work generally agrees with those from the existing literature. Biomass burning contributed 14.8% to HCHOg, but the abundant freshly discharged precursors it emitted greatly promoted the secondary production of HCHOg. We suggest that the high concentration of HCHOp during the biomass burning period was from uptake of HCHOg by aerosols during their transportation; the liquid state particles are conducive to HCHOg uptake. High relative humidity, a low particle rebound fraction f, as well as low temperatures may result in higher uptake coefficient values.

Particle size distribution, water soluble ions, and black carbon (BC) concentration in a long-term haze-fog episode were measured using a wide-range particle spectrometer (WPS), a monitor for aerosols and gases (MARGA), and an aethalometer (AE33) in Nanjing from 16 to 27 November, 2018. The observation included five processes of clean, mist, mix, haze, and fog. Combined with meteorological elements, the HYSPLIT model, and the IMPROVE model, we analyzed the particle size distribution, chemical composition, and optical properties of aerosols in different processes. The particle number size distribution (PNSD) in five processes differed: It was bimodal in mist and fog and unimodal in clean, mix, and haze. The particle surface area size distribution (PSSD) in different processes showed a bimodal distribution, and the second peak of the mix and fog processes shifted to a larger particle size at 480 nm. The dominant air masses in five processes differed and primarily originated in the northeast direction in the clean process and the southeast direction in the haze process. In the mist, mix, and fog processes local air masses dominated. NO3- was the primary component of water soluble ions, with the lowest proportion of 45.6% in the clean process and the highest proportion of 53.0% in the mix process. The ratio of NH4+ in the different processes was stable at approximately 23%. The ratio of SO42- in the clean process was 26.2%, and the ratio of other processes was approximately 20%. The average concentration of BC in the fog processes was 10,119 ngm(-3), which was 3.55, 1.80, 1.60, and 1.46 times that in the processes of clean, mist, mix, and haze, respectively. In the different processes, BC was primarily based on liquid fuel combustion. NO3-, SO42-, and BC were the main contributors to the atmospheric extinction coefficient and contributed more than 90% in different processes. NO3- contributed 398.43 Mm(-1) in the mix process, and SO42- and BC contributed 167.90 Mm(-1) and 101.19 Mm(-1), respectively, during the fog process.

To clarify the aerosol optical properties under different pollution levels and their impacting factors, hourly organic carbon (OC), elemental carbon (EC), and water-soluble ion (WSI) concentrations in PM2.5 were observed by using monitoring for aerosols and gases (MARGA) and a semicontinuous OC/EC analyzer (Model RT-4) in Wuhan from 9 to 26 January 2018. The aerosol extinction coefficient (b(ext)) was reconstructed using the original Interagency Monitoring of Protected Visual Environment (IMPROVE) formula with a modification to include sea salt aerosols. A good correlation was obtained between the reconstructed b(ext) and measured b(ext) converted from visibility. b(ext) presented a unimodal distribution on polluted days (PM2.5 mass concentrations > 75 mu g.m(-3)), peaking at 19:00. b(ext) on clean days (PM2.5 mass concentrations < 75 mu g.m(-3)) did not change much during the day, while on polluted days, it increased rapidly starting at 12:00 due to the decrease of wind speed and increase of relative humidity (RH). PM2.5 mass concentrations, the aerosol scattering coefficient (b(scat)), and the aerosol extinction coefficient increased with pollution levels. The value of b(ext) was 854.72 Mm(-1) on bad days, which was 4.86, 3.1, 2.29, and 1.28 times of that obtained on excellent, good, acceptable, and poor days, respectively. When RH < 95%, b(ext) exhibited an increasing trend with RH under all pollution levels, and the higher the pollution level, the bigger the growth rate was. However, when RH > 95%, b(ext) on acceptable, poor and bad days decreased, while b(ext) on excellent and good days still increased. The overall b(ext) in Wuhan in January was mainly contributed by NH4NO3 (25.2%) and organic matter (20.1%). The contributions of NH4NO3 and (NH4)(2)SO4 to b(ext) increased significantly with pollution levels. On bad days, NH4NO3 and (NH4)(2)SO4 contributed the most to b(ext), accounting for 38.2% and 27.0%, respectively.

High concentrations of ultrafine particles (UFPs), approaching 1 million/cm3, are frequently produced from new particle formation under urban environments, but the fundamental mechanisms regulating nucleation and growth for UFPs are poorly understood. From simultaneous ambient and environmental chamber measurements, we demonstrate remarkable formation of UFPs from urban traffic emissions. By replicating ambient conditions using an environmental chamber method, we elucidate the roles of existing particles, photochemistry, and synergy of multipollutant photooxidation in nucleation and growth of UFPs. Our results reveal that synergetic oxidation of vehicular exhaust leads to efficient formation of UFPs under urban conditions. Recognition of this large urban source for UFPs is essential to accurately assessing their impacts and to effectively developing mitigation policies.High levels of ultrafine particles (UFPs; diameter of less than 50 nm) are frequently produced from new particle formation under urban conditions, with profound implications on human health, weather, and climate. However, the fundamental mechanisms of new particle formation remain elusive, and few experimental studies have realistically replicated the relevant atmospheric conditions. Previous experimental studies simulated oxidation of one compound or a mixture of a few compounds, and extrapolation of the laboratory results to chemically complex air was uncertain. Here, we show striking formation of UFPs in urban air from combining ambient and chamber measurements. By capturing the ambient conditions (i.e., temperature, relative humidity, sunlight, and the types and abundances of chemical species), we elucidate the roles of existing particles, photochemistry, and synergy of multipollutants in new particle formation. Aerosol nucleation in urban air is limited by existing particles but negligibly by nitrogen oxides. Photooxidation of vehicular exhaust yields abundant precursors, and organics, rather than sulfuric acid or base species, dominate formation of UFPs under urban conditions. Recognition of this source of UFPs is essential to assessing their impacts and developing mitigation policies. Our results imply that reduction of primary particles or removal of existing particles without simultaneously limiting organics from automobile emissions is ineffective and can even exacerbate this problem.