Search

Biomass burning activities are ubiquitous in China, especially in northern China, where there is a large rural population and winter heating custom. Biomass burning tracers (i.e., levoglucosan, mannosan and potassium (K + )), as well as other chemical components, were quantified at a rural site (Gucheng, GC) in northern China from 15 October to 30 November, during a transition heating season, when the field burning of agricultural residue was becoming intense. The measured daily average concentrations of levoglucosan, mannosan and K + in PM 2.5 (particulate matter with aerodynamic diameters less than 2.5 µ m) during this study were 0.79 ± 0.75, 0.03 ± 0.03 and 1.52 ± 0.62 µ g m −3 , respectively. Carbonaceous components and biomass burning tracers showed higher levels during nighttime than daytime, while secondary inorganic ions were enhanced during daytime. An episode with high levels of biomass burning tracers was encountered at the end of October 2016, with high levoglucosan at 4.37 µ g m −3 . Based on the comparison of chemical components during different biomass burning pollution periods, it appeared that biomass combustion can obviously elevate carbonaceous component levels, whereas there was essentially no effect on secondary inorganic aerosols in the ambient air. Moreover, the levoglucosan / mannosan ratios during different biomass burning pollution periods remained at high values (in the range of 18.3–24.9); however, the levoglucosan / K + ratio was significantly elevated during the intensive biomass burning pollution period (1.67) when air temperatures were decreasing, which was substantially higher than in other biomass burning periods (averaged at 0.47).

Peroxyacetyl nitrate (PAN) is an important indicator for photochemical pollution, formed similar to ozone in the photochemistry of certain volatile organic compounds (VOCs) in the presence of nitrogen oxides, and has displayed surprisingly high concentrations during wintertime that were better correlated to particulate rather than ozone concentrations, for which the reasons remained unknown. In this study, wintertime observations of PAN, VOCs, PM2.5, HONO, and various trace gases were investigated to find the relationship between aerosols and wintertime PAN formation. Wintertime photochemical pollution was affirmed by the high PAN concentrations (average: 1.2 ± 1.1 ppb, maximum: 7.1 ppb), despite low ozone concentrations. PAN concentrations were determined by its oxygenated VOC (OVOC) precursor concentrations and the NO/NO2 ratios and can be well parameterized based on the understanding of their chemical relationship. Data analysis and box modeling results suggest that PAN formation was mostly contributed by VOC aging processes involving OH oxidation or photolysis rather than ozonolysis pathways. Heterogeneous reactions on aerosols have supplied key photochemical oxidants such as HONO, which produced OH radicals upon photolysis, promoting OVOC formation and thereby enhancing PAN production, explaining the observed PM2.5-OVOC-PAN intercorrelation. In turn, parts of these OVOCs might participate in the formation of secondary organic aerosol, further aggravating haze pollution as a feedback. Low wintertime temperatures enable the long-range transport of PAN to downwind regions, and how that will impact their oxidation capacity and photochemical pollution requires further assessment in future studies.

Fine-particle pollution associated with winter haze threatens the health of more than 400 million people in the North China Plain. The Multiphase chemistry experiment in Fogs and Aerosols in the North China Plain (McFAN) investigated the physicochemical mechanisms leading to haze formation with a focus on the contributions of multiphase processes in aerosols and fogs. We integrated observations on multiple platforms with regional and box model simulations to identify and characterize the key oxidation processes producing sulfate, nitrate and secondary organic aerosols. An outdoor twin-chamber system was deployed to conduct kinetic experiments under real atmospheric conditions in comparison to literature kinetic data from laboratory studies. The experiments were spanning multiple years since 2017 and an intensive field campaign was performed in the winter of 2018. The location of the site minimizes fast transition between clean and polluted air masses, and regimes representative for the North China Plain were observed at the measurement location in Gucheng near Beijing. The consecutive multi-year experiments document recent trends of PM2.5 pollution and corresponding changes of aerosol physical and chemical properties, enabling in-depth investigations of established and newly proposed chemical mechanisms of haze formation. This study is mainly focusing on the data obtained from the winter campaign 2018. To investigate multiphase chemistry, the results are presented and discussed by means of three characteristic cases: low humidity, high humidity and fog. We find a strong relative humidity dependence of aerosol chemical compositions, suggesting an important role of multiphase chemistry. Compared with the low humidity period, both PM1 and PM2.5 show higher mass fraction of secondary inorganic aerosols (SIA, mainly as nitrate, sulfate and ammonium) and secondary organic aerosols (SOA) during high humidity and fog episodes. The changes in aerosol composition further influence aerosol physical properties, e.g., with higher aerosol hygroscopicity parameter κ and single scattering albedo SSA under high humidity and fog cases. The campaign-averaged aerosol pH is 5.1 ± 0.9, of which the variation is mainly driven by the aerosol water content (AWC) concentrations. Overall, the McFAN experiment provides new evidence of the key role of multiphase reactions in regulating aerosol chemical composition and physical properties in polluted regions.

Higher alkanes are a major class of intermediate-volatility organic compounds (IVOCs), which have been proposed to be important precursors of secondary organic aerosols (SOA) in the atmosphere. Accurate estimation of SOA from higher alkanes and their oxidation processes in the atmosphere is limited, partially due to the difficulty of their measurement. High-time-resolution (10 s) measurements of higher alkanes were performed using NO+ chemical ionization in proton transfer reaction time-of-flight mass spectrometry (NO+ PTR-ToF-MS) at an urban site in Guangzhou in the Pearl River Delta (PRD) and at a rural site in the North China Plain (NCP). High concentrations were observed in both environments, with significant diurnal variations. At both sites, SOA production from higher alkanes is estimated from their photochemical losses and SOA yields. Higher alkanes account for significant fractions of SOA formation at the two sites, with average contributions of 7.0 % ± 8.0 % in Guangzhou and 9.4 % ± 9.1 % in NCP, which are comparable to or even higher than both single-ring aromatics and naphthalenes. The significant contributions of higher alkanes to SOA formation suggests that they should be explicitly included in current models for SOA formation. Our work also highlights the importance of NO+ PTR-ToF-MS in measuring higher alkanes and quantifying their contributions to SOA formation.

The NO–NO2 cycle determines the formation of O3 and hence plays a critical role in the oxidizing capacity of troposphere. Traditional view concluded that the heterogeneous oxidation of NO to NO2 wa...

Stringent emission controls effectively brought down particulate mass concentrations by >30% in the North China Plain (NCP) and Pearl River Delta (PRD) regions. However, the low-visibility (

Secondary organic aerosol (SOA) constitutes a large fraction of organic aerosol worldwide, however, the formation mechanisms in polluted environments remain poorly understood. Here we observed fast daytime growth of oxygenated organic aerosol (OOA) (with formation rates up to 10 μg m-3 h-1) during low relative humidity (RH, daytime average 38 ± 19%), high RH (53 ± 19%), and fog periods (77 ± 13%, fog occurring during nighttime with RH reaching 100%). Evidence showed that photochemical aqueous-phase SOA (aqSOA) formation dominantly contributed to daytime OOA formation during the periods with nighttime fog, while both photochemical aqSOA and gas-phase SOA (gasSOA) formation were important during other periods with the former contributing more under high RH and the latter under low RH conditions, respectively. Compared to daytime photochemical aqSOA production, dark aqSOA formation was only observed during the fog period and contributed negligibly to the increase in OOA concentrations due to fog scavenging processes. The rapid daytime aging, as indicated by the rapid decrease in m,p-xylene/ethylbenzene ratios, promoted the daytime formation of precursors for aqSOA formation, e.g., carbonyls such as methylglyoxal. Photooxidants related to aqSOA formation such as OH radical and H2O2 also bear fast daytime growth features even under low solar radiative conditions. The simultaneous increases in ultraviolet radiation, photooxidant, and aqSOA precursor levels worked together to promote the daytime photochemical aqSOA formation. We also found that biomass burning emissions can promote photochemical aqSOA formation by adding to the levels of aqueous-phase photooxidants and aqSOA precursors. Therefore, future mitigation of air pollution in a polluted environment would benefit from stricter control on biomass burning especially under high RH conditions.

The hygroscopicity of organic aerosol (OA) is important for investigation of its climatic and environmental impacts. However, the hygroscopicity parameter κOA remains poorly characterized, especially in the relatively polluted environment on the North China Plain (NCP). Here we conducted simultaneous wintertime measurements of bulk aerosol chemical compositions of PM2.5 and PM1 and bulk aerosol hygroscopicity of PM10 and PM1 on the NCP using a capture-vaporizer time-of-flight aerosol chemical speciation monitor (CV-ToF-ACSM) and a humidified nephelometer system which measures the aerosol light-scattering enhancement factor f(RH). A method for calculating κOA based on f(RH) and bulk aerosol chemical-composition measurements was developed. We found that κOA varied in a wide range with significant diurnal variations. The derived κOA ranged from almost 0.0 to 0.25, with an average (±1σ) of 0.08 (±0.06) for the entire study. The derived κOA was highly correlated with f44 (fraction of m∕z 44 in OA measured by CV-ToF-ACSM), an indicator of the oxidation degree of OA (R=0.79), and the relationship can be parameterized as κOA=1.04×f44-0.02 (κOA=0.3×O:C-0.02, based on the relationship between the f44 and O∕C ratio for CV-ToF-ACSM). On average, κOA reached the minimum (0.02) in the morning near 07:30 local time (LT) and then increased rapidly, reaching the peak value of 0.16 near 14:30 LT. The diurnal variations in κOA were highly and positively correlated with those of mass fractions of oxygenated OA (R=0.95), indicating that photochemical processing played a dominant role in the increase in κOA in winter on the NCP. Results in this study demonstrate the potential wide applications of a humidified nephelometer system together with aerosol composition measurements for investigating the hygroscopicity of OA in various environments and highlight that the parameterization of κOA as a function of OA aging processes needs to be considered in chemical transport models for better evaluating the impacts of OA on cloud formation, atmospheric chemistry, and radiative forcing.

To investigate the impacts of relative humidity (RH) on secondary organic aerosol (SOA) concentrations and chemical reactions, the carbonaceous aerosol components [i.e., organic carbon (OC) and element carbon (EC)] were quantified in daily PM2.5 samples collected at a background site in East China during summer 2015. Based on the method of EC-tracer, the concentration of secondary organic carbon (SOC) demonstrated an obvious negative relationship with RH higher than 60%. Moreover, the ratio of SOC/EC also exhibited obvious decreasing trends with increasing RH, indicating negative effects for chemical production of SOA under high RH conditions. Due to high RH, photochemistry was weakened, gaseous oxidant concentrations was lowered (e.g., significantly decreased O3 levels), and the production rates of SOA were relatively low. On the other hand, because of more water uptake under higher RH conditions, the aerosol droplet acidity was reduced and enhancement of SOA formation by acidity was accordingly absent. In addition, high RH also plays an important role in changing viscosity of pre-existing aerosol coatings, which can affect reactive uptake yield of SOA. Overall, the results from this study imply that SOA production may be more associated with photochemical processes, while aqueous-phase chemistry is not very important for some SOA formation in a moist ambient environment. In the ambient atmosphere, oxidant concentrations, reaction rates, airborne species, etc., are highly variable. How do these factors affect SOA yields under given ambient environment warrants further detailed investigations.

The study of atmospheric nitrous acid (HONO), which is the primary source of OH radicals, is crucial with respect to understanding atmospheric photochemistry and heterogeneous chemical processes. Heterogeneous NO2 chemistry under haze conditions has been identified as one of the missing sources of HONO on the North China Plain, and also produces sulfate and nitrate. However, controversy exists regarding the various proposed HONO production mechanisms, mainly regarding whether SO2 directly takes part in the HONO production process and what roles NH3 and the pH value play. In this paper, never before seen explosive HONO production was reported and evidence was found – for the first time in field measurements during fog (usually with 4

Laboratory experiments were conducted to investigate femtosecond filamentation induced particle formation and growth in particle-free air as well as in the presence of pre-existing ammonium sulfate aerosols. The ability of laser induced particles to act as cloud condensation nuclei (CCN) was explored. The influence of water vapor and the pulse energy on the production efficiency and activation properties of particles were also examined. In particle-free air, laser filaments could lead to a significant production of new particles, the number concentration of which was comparable to or larger than that in polluted ambient air, depending upon the pulse energy and humidity. Total particle number and mass concentrations within 20–708 nm were predominantly contributed by particles with a diameter smaller than 100 nm. Remarkably high NOx up to an order of ∼101 ppm was generated in the chamber, allowing sufficient production of HNO3 and probably subsequent HNO3-H2O binary nucleation. In the presence of pre-existing particles, the yield of particle number was largely enhanced in laser filaments, especially in humid air. Particle number size distribution shifted towards smaller particle size, leading to a slight increase in particle mass. It was found that a considerable portion of laser induced particles, no matter generated with or without pre-existing particles, could act as CCN. The amount of CCN at 0.80% supersaturation was in the magnitude of 104∼105 cm−3 in all experiments, nearly one order larger than the average ambient level even in severely polluted regions. Overall, increasing the pulse energy and water vapor would favor particle formation and growth as well as the production of CCN. Raising the pulse energy also resulted in a decline of the hygroscopic parameter κ, implying the modification of aerosol chemical composition. Though more investigative studies are still needed to explore mechanisms underlying some of these experimental results, laser filaments are undoubtedly capable of inducing substantial particle formation and modifying microphysical/chemical properties of pre-existing particles. By influencing these crucial properties and thereby aerosol direct/indirect climatic and environmental effects, laser filamentation would provide a promising potential for related atmospheric applications.

Atmospheric nitrogen deposition is of great concern to both air quality and the ecosystem, particularly in northern China, which covers one-quarter of China&rsquo, s cultivated land and has many heavily air polluted cities. To understand the characteristics of wet N deposition at rural sites in northern China, one-year wet deposition samples were collected in the Daheitin reservoir region. Due to the intense emissions of gaseous nitrogen compounds from heating activities during cold seasons and distinct dilution effects under different rainfall intensities and frequencies, the volume weighted mean concentrations of wet N deposition showed higher levels in dry seasons but lower levels in wet seasons. In contrast, the wet N deposition rates varied consistently with precipitation, i.e., high during the wet season and lower during the dry season. The annual wet deposition rate of total inorganic ions (the sum of NO3&minus, &ndash, N and NH4+&ndash, N) at the rural site in North China from July 2019 to June 2020 was observed at 18.9 kg N ha&minus, 1 yr&minus, 1, still remained at a relatively high level. In addition, biomass burning activities are ubiquitous in China, especially in northern China, however, studies on its impact on wet N deposition are limited. Non-sea salt potassium ion (nss-K+) was employed as a molecular tracer to investigate the characteristics of biomass burning activities as well as their impact on the chemical properties of wet N deposition. Three precipitation events with high nss-K+ levels were captured during the harvest season (June to July). The variations in the patterns of nss-K+, deposited N species, and ratios of nss-K+ to nitrogen species as well as their relationships all indicated that biomass burning emissions contributed remarkably to NO3&minus, N but had a minor influence on NH4+&ndash, N.

Atmospheric peroxyacetyl nitrate (PAN) and ozone (O3) are two typical indicators for photochemical pollution that have adverse effects on the ecosystem and human health. Observation networks for these pollutants have been expanding in developed regions of China, such as North China Plain (NCP) and Pearl River Delta (PRD), but are sparse in Yangtze River Delta (YRD), meaning their concentration and influencing factors remain poorly understood. Here, we performed a one-year measurement of atmospheric PAN, O3, particulate matter with aerodynamic diameter smaller than 2.5 μm (PM2.5), nitrogen oxides (NOx), carbon monoxide (CO), and meteorological parameters from December 2016 to November 2017 in Shanghai. Overall, high hourly maximum PAN and O3 were found to be 7.0 and 185 ppbv in summer, 6.2 and 146 ppbv in autumn, 5.8 and 137 ppbv in spring, and 6.0 and 76.7 ppbv in winter, respectively. Continental air masses probably carried atmospheric pollutants to the sampling site, while frequent maritime winds brought in less polluted air masses. Furthermore, positive correlations (R: 0.72–0.85) between PAN and O3 were found in summer, indicating a predominant role of photochemistry in their formation. Unlike in summer, weak or no correlations between PAN and O3 were featured during the other seasons, especially in winter, due to their different loss pathways. Unexpectedly, positive correlations between PAN and PM2.5 were found in all seasons. During summer, moderate correlation could be attributed to the strong photochemistry acting as a common driver in the formation of secondary aerosols and PAN. During winter, high PM2.5 might promote PAN production through HONO production, hence resulting in a good positive correlation. Additionally, the loss of PAN by thermal decomposition (TPAN) only accounted for a small fraction (ca. 1%) of the total (PAN + TPAN) during a typical winter episode, while it significantly reached 14.4 ppbv (71.1% of the total) in summer.

Biomass burning (BB) activities are ubiquitous in China, especially in North China, where there is an enormous rural population and winter heating custom. In order to better understand their impacts on aerosol chemical characteristics in rural and agricultural areas of the North China Plain, BB tracers (i.e., levoglucosan (LG), mannosan (MN) and potassium (K+)), as well as other chemical components were quantified at a rural site (Gucheng, GC) from 15 October to 30 November, during a transition heating season, when the field burning of agricultural residues was becoming intense. The measured daily average PM2.5 concentrations of LG, MN and K+ during this study were 0.79 ± 0.75 μg m−3, 0.03 ± 0.03 μg m−3 and 1.52 ± 0.62 μg m−3. Due to the planetary boundary layer development, carbonaceous components and BB tracers showed higher levels at nighttime than daytime, while OM and secondary inorganic ions were enhanced during daytime, likely due to enhanced photochemical activity. An episode with high levels of BB tracers was encountered at the end of October, 2016, with high LG at 4.37 μg m−3. Based on the comparison of chemical components during different BB periods, it appeared that biomass combustion can obviously elevate carbonaceous components levels, whereas there seems to be essentially no effect on secondary inorganic ions in the ambient air. Moreover, the LG / MN ratios in different BB periods were consistent, while the LG / K+ ratio during intensive BB periods was significantly elevated at times, with K+ not increasing as much as LG during intensive BB episodes. This indicated that there were other sources of K+ in the study region, such as fireworks, fertilizer use, or soil resuspension, which don't have variable contributions of K+ during the intensive BB periods; however, local soft wood and vegetation combustion can't be excluded, which have efficient formation of levoglucosan during flaming fires.

The light scattering enhancement factor f (RH), defined as the ratio of the light scattering coefficient ( σ S P ) observed under an elevated relative humidity (RH) conditions to that under dry conditions, is a crucial parameter for estimating aerosol direct radiative effects and atmospheric visibility. In this paper, a new f (RH) parameterization scheme considering both the influence of aerosol chemical compositions and that of particle number size distribution (PNSD) is proposed based on in situ measurements in the North China Plain. The development of this parameterization scheme includes three steps. First, aerosol hygroscopicity parameter κ is parameterized with aerosol chemical compositions. Then, the ratio between f (RH) fitted parameter κ s c a ( f ( R H ) = 1 + κ s c a R H 100 − R H ) and κ is introduced to correlate f (RH) with κ . The ratio, influenced mostly by PNSD, is described as a function of scattering Angstrom exponent (SAE) because the SAE can represent the predominant size of aerosol particles to some extent. Finally, f (RH) cycle is parameterized with κ s c a . Validation results show that a good consistency between the parameterized and measured f (RH = 80%) is achieved and the correlation coefficient is 0.80. This parameterization scheme between aerosol chemistry and f (RH) can be used in chemical transport models for reducing uncertainties in estimations of direct aerosol radiative forcing and air quality assessments.

Mixing layer height (MLH) is a key parameter for evaluating the transport and diffusion of atmospheric pollutants in both air quality forecasting and satellite data retrieval. However, there is a lack of methods for obtaining the nocturnal MLH. In this study, a novel instrument named the charge-coupled device-laser aerosol detection system (CCD-LADS) was developed to study the nocturnal MLH and boundary layer structure from the surface. The system mainly includes a continuous laser and a charge-coupled device camera with a fisheye lens. Structures of atmospheric layers characterized by the CCD-LADS were compared with those measured by a ceilometer. The heights of two atmospheric layers quantified by measurements with the CCD-LADS and the ceilometer show good agreement, with a relative difference of 5%. The results of this comparison demonstrated that the CCD-LADS is capable of distinctly identifying the nocturnal vertical structure of the atmosphere. The advantage of the CCD-LADS in retrieving the nocturnal MLH is that the CCD-LADS can provide the boundary layer structures under 100 m, while the ceilometer and other lidar measurements cannot retrieve the atmospheric structures below that altitude. CCD-LADS was deployed in a comprehensive field campaign measuring air pollution in the University of Chinese Academy of Sciences, located at the border between the North China Plain and Yanshan Mountain, during January 2016. The fine characteristics and patterns of the nocturnal boundary layer structures were derived with the CCD-LADS measurements.

Water condensed on ambient aerosol particles plays significant roles in atmospheric environment, atmospheric chemistry and climate. Before now, no instruments were available for real-time monitoring of ambient aerosol liquid water contents (ALWCs). In this paper, a novel method is proposed to calculate ambient ALWC based on measurements of a three-wavelength humidified nephelometer system, which measures aerosol light scattering coefficients and backscattering coefficients at three wavelengths under dry state and different relative humidity (RH) conditions, providing measurements of light scattering enhancement factor f(RH). The proposed ALWC calculation method includes two steps: the first step is the estimation of the dry state total volume concentration of ambient aerosol particles, Va(dry), with a machine learning method called random forest model based on measurements of the “dry” nephelometer. The estimated Va(dry) agrees well with the measured one. The second step is the estimation of the volume growth factor Vg(RH) of ambient aerosol particles due to water uptake, using f(RH) and the Ångström exponent. The ALWC is calculated from the estimated Va(dry) and Vg(RH). To validate the new method, the ambient ALWC calculated from measurements of the humidified nephelometer system during the Gucheng campaign was compared with ambient ALWC calculated from ISORROPIA thermodynamic model using aerosol chemistry data. A good agreement was achieved, with a slope and intercept of 1.14 and −8.6 µm3 cm−3 (r2 = 0.92), respectively. The advantage of this new method is that the ambient ALWC can be obtained solely based on measurements of a three-wavelength humidified nephelometer system, facilitating the real-time monitoring of the ambient ALWC and promoting the study of aerosol liquid water and its role in atmospheric chemistry, secondary aerosol formation and climate change.

The Yangtze River Delta (YRD) is one of the most densely populated regions in China with severe air quality issues that have not been fully understood. Thus, in this study, based on 1-year (2013) continuous measurement at a National Reference Climatological Station (NRCS, 30.22° N, 120.17° E; 41.7 m a.s.l.) in the center of Hangzhou in the YRD, we investigated the seasonal characteristics, interspecies relationships, and the local emissions and the regional potential source contributions of trace gases (including O3, NOx, NOy, SO2, and CO) and particulate matter (PM2.5 and PM10). Results revealed that severe two-tier air pollution (photochemical and haze pollution) occurred in this region, with frequent exceedances in O3 (38 days) and PM2.5 (62 days). O3 and PM2.5 both exhibited distinct seasonal variations with reversed patterns: O3 reaching a maximum in warm seasons (May and July) but PM2.5 reaching a maximum in cold seasons (November to January). The overall results from interspecies correlation indicated a strong local photochemistry favoring the O3 production under a volatile organic compound (VOC)-limited regime, whereas it moved towards an optimum O3 production zone during warm seasons, accompanied by the formation of secondary fine particulates under high O3. The emission maps of PM2.5, CO, NOx, and SO2 demonstrated that local emissions were significant for these species on a seasonal scale. The contributions from the regional transport among inland cities (Zhejiang, Jiangsu, Anhui, and Jiangxi Province) on a seasonal scale were further confirmed to be crucial to air pollution at the NRCS site by using backward trajectory simulations. Air masses transported from the offshore areas of the Yellow Sea, East Sea, and South Sea were also found to be highly relevant to the elevated O3 at the NRCS site through the analysis of potential source contribution function (PSCF). Case studies of photochemical pollution (O3) and haze (PM2.5) episodes both suggested the combined importance of local atmospheric photochemistry and synoptic conditions during the accumulation (related with anticyclones) and dilution process (related with cyclones). Apart from supplementing a general picture of the air pollution state in the city of Hangzhou in the YRD region, this study specifically elucidates the role of local emission and regional transport, and it interprets the physical and photochemical processes during haze and photochemical pollution episodes. Moreover, this work suggests that cross-regional control measures are crucial to improve air quality in the YRD region, and it further emphasizes the importance of local thermally induced circulation for air quality.

Inter-annual variability and long-term trends in tropospheric ozone are both environmental and climate concerns. Ozone measured at Mt Waliguan Observatory (WLG, 3816 m a.s.l.) on the Tibetan Plateau over the period of 1994–2013 has increased significantly by 0.2–0.3 ppbv yr−1 during spring and autumn but shows a much smaller trend in winter and no significant trend in summer. Here we explore the factors driving the observed ozone changes at WLG using backward trajectory analysis, chemistry–climate model hindcast simulations (GFDL AM3), a trajectory-mapped ozonesonde data set, and several climate indices. A stratospheric ozone tracer implemented in GFDL AM3 indicates that stratosphere-to-troposphere transport (STT) can explain ∼ 60 % of the simulated springtime ozone increase at WLG, consistent with an increase in the NW air-mass frequency inferred from the trajectory analysis. Enhanced STT associated with the strengthening of the mid-latitude jet stream contributes to the observed high ozone anomalies at WLG during the springs of 1999 and 2012. During autumn, observations at WLG are more heavily influenced by polluted air masses originating from South East Asia than in the other seasons. Rising Asian anthropogenic emissions of ozone precursors are the key driver of increasing autumnal ozone observed at WLG, as supported by the GFDL AM3 model with time-varying emissions, which captures the observed ozone increase (0.26 ± 0.11 ppbv yr−1). AM3 simulates a greater ozone increase of 0.38 ± 0.11 ppbv yr−1 at WLG in autumn under conditions with strong transport from South East Asia and shows no significant ozone trend in autumn when anthropogenic emissions are held constant in time. During summer, WLG is mostly influenced by easterly air masses, but these trajectories do not extend to the polluted regions of eastern China and have decreased significantly over the last 2 decades, which likely explains why summertime ozone measured at WLG shows no significant trend despite ozone increases in eastern China. Analysis of the Trajectory-mapped Ozonesonde data set for the Stratosphere and Troposphere (TOST) and trajectory residence time reveals increases in direct ozone transport from the eastern sector during autumn, which adds to the autumnal ozone increase. We further examine the links of ozone variability at WLG to the quasi-biennial oscillation (QBO), the East Asian summer monsoon (EASM), and the sunspot cycle. Our results suggest that the 2–3-, 3–7-, and 11-year periodicities are linked to the QBO, EASM index, and sunspot cycle, respectively. A multivariate regression analysis is performed to quantify the relative contributions of various factors to surface ozone concentrations at WLG. Through an observational and modelling analysis, this study demonstrates the complex relationships between surface ozone at remote locations and its dynamical and chemical influencing factors.

With rapid economic development and urbanization, particular attention has been paid to atmospheric chemical studies in the Yangtze River Delta in China. PM2.5 samples were collected by a MiniVol™ air sampler in summer time at a background site of the Yangtze River Delta in China. Carbonaceous components, i.e., OC and EC, levoglucosan and water-soluble inorganic ions, including sulfate, nitrate, ammonium, etc., were quantified. The average concentration of PM2.5 in summer at Lin'an was 30.19 ± 8.86 μg m−3, lower than previous studies reported, confirming that air pollution in China is improving, e.g., by emission control measures and subsequent reduction in PM emissions in China. Investigating the relationship among sulfate, nitrate and ammonium showed that SO42− existed as (NH4)2SO4, while NO3− may have been present as NaNO3 and KNO3. Based on molecular tracers, synoptic data as well as air mass back trajectory analysis, it was revealed that regional transport and stable synoptic conditions both play an important role in controlling the variations of aerosol chemical components. The comparison of chemical species between clean and hazy days showed that secondary organic and inorganic aerosols have different production processes. Secondary organic carbon (SOC) was much more important during clean days, while secondary inorganic aerosol species were readily produced and consequently became more important during polluted periods in Lin'an during summer time.

The first Tropospheric Ozone Assessment Report (TOAR) provides information on present-day distributions and long-term trends of ozone metrics relevant for climate change, human health, and vegetation. However, only few results are available in TOAR for China due to limited long-term ozone observations. Here, we present an integrated analysis of long-term measurements of surface ozone from eight sites distributed in the North China Plain (NCP) and Yangtze River Delta (YRD), the relatively underdeveloped region Northeast China, and the remote regions in Northwest and Southwest China. Trends and present-day values for seven annual and five seasonal ozone metrics were calculated following the TOAR methodologies. We compare the seasonal and diurnal cycles of ozone concentrations as well as the present-day values of ozone among sites and discuss the long-term trends in the ozone metrics. Large and significant increases of ozone are detected at the background site in the NCP, moderate increases at the global baseline site in western China, significant decreases at the northwestern edge of China, and nearly no trend at other sites. Extremely high values of ozone occurred in the NCP and YRD, particularly in warmer seasons. The present-day levels of summer ozone metrics in the NCP are much higher than the thresholds set in TOAR for the highest value groups of ozone metrics. The summer ozone metrics at the Shangdianzi background site in the NCP indicate increases at rates of more than 2%/yr during 2004–2016. In contrast, ozone at the Lin’an background site in the YRD was constant over the period 2006–2016. Our results fill some knowledge gaps in spatiotemporal changes of ozone in China and may be of useful in the assessment of ozone impacts on human health and vegetation.

Isocyanic acid (HNCO) is a potentially toxic atmospheric pollutant, whose atmospheric concentrations are hypothesized to be linked to adverse health effects. An earlier model study estimated that concentrations of isocyanic acid in China are highest around the world. However, measurements of isocyanic acid in ambient air have not been available in China. Two field campaigns were conducted to measure isocyanic acid in ambient air using a high-resolution time-of-flight chemical ionization mass spectrometer (ToF-CIMS) in two different environments in China. The ranges of mixing ratios of isocyanic acid are from below the detection limit (18 pptv) to 2.8 ppbv (5 min average) with the average value of 0.46 ppbv at an urban site of Guangzhou in the Pearl River Delta (PRD) region in fall and from 0.02 to 2.2 ppbv with the average value of 0.37 ppbv at a rural site in the North China Plain (NCP) during wintertime, respectively. These concentrations are significantly higher than previous measurements in North America. The diurnal variations of isocyanic acid are very similar to secondary pollutants (e.g., ozone, formic acid, and nitric acid) in PRD, indicating that isocyanic acid is mainly produced by secondary formation. Both primary emissions and secondary formation account for isocyanic acid in the NCP. The lifetime of isocyanic acid in a lower atmosphere was estimated to be less than 1 day due to the high apparent loss rate caused by deposition at night in PRD. Based on the steady state analysis of isocyanic acid during the daytime, we show that amides are unlikely enough to explain the formation of isocyanic acid in Guangzhou, calling for additional precursors for isocyanic acid. Our measurements of isocyanic acid in two environments of China provide important constraints on the concentrations, sources, and sinks of this pollutant in the atmosphere.

The characteristics of benzene, toluene, ethylbenzene, and xylene (BTEX) concentrations, their temporal and spatial variations, and their source origins from September–December 2017 at an urban and a background site in Beijing, China were investigated. The averaged (±σ) total mixing ratios of benzene, toluene, ethylbenzene, m, p-xylenes, and o-xylene were 0.40 ± 0.39 ppbv, 0.31 ± 0.34 ppbv, 0.08 ± 0.07 ppbv, 0.08 ± 0.08 ppbv, and 0.05 ± 0.05 ppbv at the SDZ site, which were 63%, 79%, 83%, 85%, and 89% lower than those at the Chinese Academy of Meteorological Sciences site (CMA). It is worth noting that the average mixing ratios of BTEX at SDZ and CMA were 0.86 ± 1.03 ppbv and 3.38 ± 2.80 ppbv during the heating period (HP), which were 2.3% and 21.9% lower than those before the HP, a decrease that was mainly related to the frequent occurrence of strong northerly and northwesterly winds and low relative humidity (RH) during the HP. Obvious differences were also observed between the BTEX composition proportions at the SDZ and CMA sites. On average, benzene comprised 44% of the total BTEX at SDZ, whereas toluene was the largest contributor to the total BTEX at CMA, accounting for 37%. In addition, the contributions of C8 aromatics (the sum of ethylbenzene, m, p-xylenes, and o-xylene) at CMA (36%) were also higher than those at SDZ (21%), reflecting the different emission sources of the two sites. In addition, the BTEX species showed similar and pronounced diurnal profiles at SDZ and CMA, all characterized by much higher values at night than during the day. Diagnostic ratios and source implications suggested that SDZ was affected mainly by biomass/biofuel/coal burning, with substantially elevated benzene levels during the winter HP, whereas CMA was affected both by traffic-related emissions and biomass/biofuel/coal burning emissions. These findings suggest the necessity of regionally-tailored control strategies both to reduce BTEX levels and to mitigate their environmental impact. Further analysis of the backward trajectories revealed that the BTEX compounds varied greatly in terms of air mass origins, but generally exhibited high values for slow air masses passing over areas south of Beijing, with dominant contributions from benzene, toluene, and m, p-xylenes.

The light absorption black carbon (BC) and brown carbon (BrC) are two important sources of uncertainties in radiative forcing estimate. Here we investigated the light absorption enhancement (Eabs) of BC due to coated materials at an urban (Beijing) and a rural site (Gucheng) in North China Plain (NCP) in winter 2019 by using a photoacoustic extinctiometer coupled with a thermodenuder. Our results showed that the average (±1σ) Eabs was 1.32 (±0.15) at the rural site, which was slightly higher than that at the urban site (1.24 ± 0.15). The dependence of Eabs on coating materials was found to be relatively limited at both sites. However, Eabs presented considerable increases as a function of relative humidity below 70%. Further analysis showed that Eabs during non-heating period in Beijing was mainly caused by secondary components, while it was dominantly contributed by enhanced primary emissions in heating season at both sites. In particular, aerosol particles mixed with coal combustion emissions had a large impact on Eabs (>1.40), while the fresh traffic emissions and freshly oxidized secondary OA (SOA) had limited Eabs (1.00–1.23). Although highly aged or aqueous-phase processed SOA coated on BC showed the largest Eabs, their contributions to the bulk absorption enhancement were generally small. We also quantified the absorption of BrC and source contributions. The results showed the BrC absorption at the rural site was nearly twice that of urban site, yet absorption Angstrom exponents were similar. Multiple linear regression analysis highlighted the major sources of BrC being coal combustion emissions and photochemical SOA at both sites with additional biomass burning at the rural site. Overall, our results demonstrated the relatively limited winter light absorption enhancement of BC in different chemical environments in NCP, which needs be considered in regional climate models to improve BC radiative forcing estimates.

Tropospheric ozone is an important atmospheric oxidant, greenhouse gas and atmospheric pollutant at the same time. The oxidation capacity of the atmosphere, climate, human and vegetation health can be impacted by the increase of the ozone level. Therefore, long-term determination of trends of baseline ozone is highly needed information for environmental and climate change assessment. So far, studies on the long-term trends of ozone at representative sites are mainly available for European and North American sites. Similar studies are lacking for China and many other developing countries. Measurements of surface ozone were carried out at a baseline Global Atmospheric Watch (GAW) station in the north-eastern Tibetan Plateau region (Mt Waliguan, 36°17′ N, 100°54′ E, 3816 m a.s.l.) for the period of 1994 to 2013. To uncover the variation characteristics, long-term trends and influencing factors of surface ozone at this remote site in western China, a two-part study has been carried out, with this part focusing on the overall characteristics of diurnal, seasonal and long-term variations and the trends of surface ozone. To obtain reliable ozone trends, we performed the Mann–Kendall trend test and the Hilbert–Huang transform (HHT) analysis on the ozone data. Our results confirm that the mountain-valley breeze plays an important role in the diurnal cycle of surface ozone at Waliguan, resulting in higher ozone values during the night and lower ones during the day, as was previously reported. Systematic diurnal and seasonal variations were found in mountain-valley breezes at the site, which were used in defining season-dependent daytime and nighttime periods for trend calculations. Significant positive trends in surface ozone were detected for both daytime (0.24 ± 0.16 ppbv year−1) and nighttime (0.28 ± 0.17 ppbv year−1). The largest nighttime increasing rate occurred in autumn (0.29 ± 0.11 ppbv year−1), followed by spring (0.24 ± 0.12 ppbv year−1), summer (0.22 ± 0.20 ppbv year−1) and winter (0.13 ± 0.10 ppbv year−1), respectively. The HHT spectral analysis identified four different stages with different positive trends, with the largest increase occurring around May 2000 and October 2010. The HHT results suggest that there were 2–4a, 7a and 11a periodicities in the time series of surface ozone at Waliguan. The results of this study can be used for assessments of climate and environment change and in the validation of chemistry–climate models.

An observational field campaign was carried out from 20 June to July 31, 2016 at Raoyang, a rural site in the North China Plain (NCP). In-situ measurements of O3 and related gases were obtained and analyzed in this work. Heavy photochemical pollution episodes lasting for a few days were observed in the campaign. The episodes could be divided into two categories, with one being influenced by plume from northeast (NE) via Beijing-Tianjin cities and the other from southeast (SE) via Shandong province. The SE episodes were more frequent with higher O3 concentrations and lagged daily peaks of O3 despite of lower concentrations of precursors. Such episodes could last for several days or even a week. In contrast, the NE episode was associated with relatively lower O3 levels and earlier daily O3 peaks though the levels of precursors were higher. The WRF-Chem model was used to study the differences between typical SE and NE episodes in regional distributions of O3 concentrations, chemical regimes of O3 formation, ozone production efficiency (OPE), photochemical age of plume, and evolution of O3 concentration within the boundary layer. Our results suggest that the O3 production regimes were different for the Raoyang site, with the NE episode being VOCs-sensitive and the SE episode in the VOC-sensitive to NOx-sensitive transition regime. In both episodes, a major part of the NCP was under the VOCs-sensitive regime. Plumes in the SE episodes were more aged than those in the NE episode. The OPE values were higher in more aged SE plumes, resulting in higher O3 concentrations despite of lower precursor concentrations. Our results also indicate that downward mixing of O3 in the nocturnal residual layer played an important role in rapid buildup of surface O3 in the next morning in both NE and SE episodes. The formation of photochemical smog seems to be particularly effective in the SE episode since O3 is rapidly produced during daytime, stored aloft at night, and mixed downward to the ground-level, and the process can circulate for several consecutive days. Our study highlights the complicated role of chemical reaction, transport and boundary layer processes in the formation of severe photochemical smog in the region.

Cloud condensation nuclei (CCN) play an important role in the formation and evolution of cloud droplets. However, the dataset of global CCN number concentration (NCCN) is still scarce due to the lack of direct CCN measurements, hindering an accurate evaluation of its climate effects. Alternative approaches to determine NCCN have thus been proposed to calculate NCCN based on measurements of other aerosol properties, such as particle number size distribution, bulk aerosol chemical composition and aerosol optical properties. To better understand the interaction between haze pollution and climate, we performed direct CCN measurements in the winter of 2018 at the Gucheng site, a typical polluted suburban site in North China Plain (NCP). The results show that the average CCN concentrations were 3.81 × 103 cm−3, 5.35 × 103 cm−3, 9.74 × 103 cm−3, 1.27 × 104 cm−3, 1.44 × 104 cm−3 at measured supersaturation levels of 0.114%, 0.148%, 0.273%, 0.492% and 0.864%, respectively. Based on these observational data, we have further investigated two methods of calculating NCCN from: (1) bulk aerosol chemical composition and particle number size distribution; (2) bulk aerosol chemical composition and aerosol optical properties. Our results showed that both methods could well reproduce the observed concentration (R2 > 0.88) and variability of NCCN with a 9% to 23% difference in the mean value. Further error analysis shows that the estimated NCCN tends to be underestimated by about 20% during the daytime while overestimated by

Although atmospheric peroxyacetyl nitrate (PAN) and O3 have been extensively measured in Beijing during the summertime, the abundances of PAN, peroxypropionyl nitrate (PPN) and the total odd-reactive nitrogen budget (NOy) and their inter-relationship have been studied comparatively less in the winter. Here we measured atmospheric PAN, PPN, O3, NOx, and NOy in Beijing from Nov. 2012 to Jan. 2013. Compared with our previous results in the summertime, much lower levels were observed in the winter, with the mean and maximum values of 311.8 and 1465 pptv for PAN, 52.8 and 850.6 pptv for PPN, and 11.6 and 36.7 ppbv for O3. In contrast, high levels were found as 94.2 and 374.9 ppbv for NOy, with a major constituent of NOx (75.9%). The source to the west and northwest made the significant contribution to the relatively high O3 concentrations during nighttime. PAN concentrations were highly related with the PAN-rich air mass transported from the southeast during the nighttime, whereas predominated by local photochemical production during the daylight. The distributions of NOx and NOy were dominated by local emission and photochemical production during daylight but also influenced by air masses transported from south direction during nighttime. Significant positive correlation (R2 = 0.9, p 500 pptv) implied a steady state between PAN and PPN achieving rapidly in the polluted air masses. Negative correlation and slopes between PAN and O3 likely resulted from their weak photochemical productions in the winter, coupled with the large NO sources which acted as a local sink for O3, but much less so for PAN due to its enhanced thermal stability under low temperature.

Atmospheric ammonia (NH3) as the most important alkaline gas in the atmosphere has attracted much attention in recent years due to its critical role in haze formation, especially on the North China Plain (NCP). Comprehensive studies are needed for investigating diurnal variations of NH3 and underlying mechanisms in different seasons and their potential impacts on atmospheric chemistry. In this study, continuous long-term observation (Mar. 2016 to May 2017) of NH3 at a rural site in the NCP was used to characterize the diurnal variation of NH3 in different seasons and to unveil its causes and potential impacts on atmospheric chemistry. NH3 concentrations displayed rapid increases during the morning, reaching very prominent peaks mostly between 8:00 to 11:00 LT. Such frequent (55%) morning peaks were mainly caused by the evaporation of dew and guttation water droplets. Average dew and guttation water volume concentrations of 750 mL m−2 was estimated for spring, which resulted in approximate NH3 emissions of 800 ng m−2 s− 1. Such high emission fluxes from dew and guttation water evaporation have never been reported before, suggesting dew and guttation droplets to be significant night-time reservoirs and strong morning sources for NH3. In light of recent studies putting forward that NH3 can promote the heterogeneous formation of HONO and nitrate under high humidity conditions, we investigated the differences in HONO and aerosol chemical composition diurnal variations between days with and without NH3 morning spikes during November. HONO, nitrate and sulfate concentrations were significantly higher for days with NH3 morning spikes, with HONO displaying a morning peak near that of NH3. These results demonstrate that the prevailing NH3 morning spikes on the NCP have significant influences on aerosol formation and atmospheric chemistry. NH3 emission mitigation strategies and regulations are urgently needed.

The number concentration of cloud condensation nuclei (CCN) plays a fundamental role in cloud physics. Instrumentations of direct measurements of CCN number concentration (NCCN) based on chamber technology are complex and costly; thus a simple way for measuring NCCN is needed. In this study, a new method for NCCN calculation based on measurements of a three-wavelength humidified nephelometer system is proposed. A three-wavelength humidified nephelometer system can measure the aerosol light-scattering coefficient (σsp) at three wavelengths and the light-scattering enhancement factor (fRH). The Ångström exponent (Å) inferred from σsp at three wavelengths provides information on mean predominate aerosol size, and hygroscopicity parameter (κ) can be calculated from the combination of fRH and Å. Given this, a lookup table that includes σsp, κ and Å is established to predict NCCN. Due to the precondition for the application, this new method is not suitable for externally mixed particles, large particles (e.g., dust and sea salt) or fresh aerosol particles. This method is validated with direct measurements of NCCN using a CCN counter on the North China Plain. Results show that relative deviations between calculated NCCN and measured NCCN are within 30 % and confirm the robustness of this method. This method enables simplerNCCN measurements because the humidified nephelometer system is easily operated and stable. Compared with the method using a CCN counter, another advantage of this newly proposed method is that it can obtain NCCN at lower supersaturations in the ambient atmosphere.

We investigated the seasonal and spatial ozone variations in China by using three-year surface ozone observation data from the six Chinese Global Atmosphere Watch (GAW) stations and tropospheric column ozone data from satellite retrieval over the period 2010-2012. It is shown that the seasonal ozone variations at these GAW stations are rather different, particularly between the western and eastern locations. Compared with western China, eastern China has lower background ozone levels. However, the Asian summer monsoon (ASM) can transport photochemical pollutants from the southern to the northern areas in eastern China, leading to a northward gradual enhancement of background ozone levels at the eastern GAW stations. Over China, the tropospheric column ozone densities peak during spring and summer in the areas that are directly and/or indirectly affected by the ASM, and the peak time lags from the south to the north in eastern China. We also investigated the regional representativeness of seasonal variations of ozone at the six Chinese GAW stations using the yearly maximum tropospheric column month as indicator. The results show that the seasonal variation characteristics of ozone revealed by the Chinese GAW stations are typical, with each station having a considerable large surrounding area with the ozone maximum occurring at the same month. Ozone variations at the GAW stations are influenced by many complex factors and their regional representativeness needs to be investigated further in a broader sense.

Aerosol optical depth (AOD) is a crucial parameter in describing the atmospheric pollution and analyzing the influences of aerosol on the radiative equilibrium. Currently, no method can precisely and continuously measure the nocturnal AOD. In this study, a novel method was developed to retrieve the nocturnal AOD based on a remote sensing instrument called the charge-coupled device-laser aerosol detective system (CCD-LADS). CCD-LADS consists of a CCD camera, a continuous laser, a fisheye lens, and related filters. The AOD can be calculated by integrating the aerosol extinction coefficient profile retrieved from CCD-LADS measurements. The retrieved AOD was validated with AERONET and MODIS data sets. The comparison shows good agreement.

Interannual variability and long-term trends of tropospheric ozone are both of environmental and climate concerns. Ozone measured at Mt. Waliguan Observatory (WLG, 3816 m asl) on the Tibetan Plateau over the period 19947ndash;2013 has increased significantly by 0.2–0.3 ppbv year-1 during spring and autumn, but shows a much smaller trend in winter and no significant trend in summer. Here we explore the factors driving the observed ozone changes at WLG using backward trajectory analysis, chemistry-climate model hindcast simulations (GFDL-AM3), a trajectory-mapped ozonesonde dataset and various climate indices. A stratospheric ozone tracer implemented in GFDL-AM3 indicates that stratosphere-to-troposphere transport (STT) can explain ~ 70 % of the observed springtime ozone increase at WLG, consistent with an increase in the NW air mass frequency inferred from the trajectory analysis. Enhanced STT associated with the strengthening of the mid-latitude jet stream contributes to the observed high-ozone anomalies at WLG during the springs of 1999 and 2012. During autumn, observations at WLG are more heavily influenced by polluted air masses originated from Southeast Asia than in the other seasons. Rising Asian anthropogenic emissions of ozone precursors is the key driver of increasing autumnal ozone observed at WLG, as supported by the GFDL-AM3 model with time-varying emissions, which captures the observed ozone increase (0.26 ± 0.11 ppbv year-1). AM3 simulates a greater ozone increase of 0.38 ± 0.11 ppbv year-1 at WLG in autumn under conditions with strong transport from Southeast Asia and shows no significant ozone trend in autumn when anthropogenic emissions are held constant in time. During summer, WLG is mostly influenced by easterly air masses but these trajectories do not extend to the polluted regions of eastern China and have decreased significantly over the last two decades, which likely explains why summertime ozone measured at WLG shows no significant trend despite ozone increases in Eastern China. Analysis of the Trajectory-mapped Ozonesonde dataset for the Stratosphere and Troposphere (TOST) and trajectory residence time reveals increases in direct ozone transport from the eastern sector during autumn, which adds to the autumnal ozone increase. We further examine the links of ozone variability at WLG to the QBO, the North Atlantic Oscillation (NAO), the East Asian summer monsoon (EASM) and the sunspot cycle. Our results suggest that the 2–3 year, 3–7 year and 11 year periodicities are linked to QBO, EASMI and NAO and the sunspot cycle, respectively. A multivariate regression analysis is performed to quantify the relative contributions of various factors to surface ozone concentrations at WLG. Through an observational and modelling analysis, this study demonstrates the complex relationships between surface ozone at remote locations and its dynamical and chemical influencing factors.

Biomass burning activities are ubiquitous in China. In order to better understand the biomass burning sources and their impacts on aerosols components in the background air of East China, biomass burning tracers i.e., levoglucosan (LG), mannosan (MN) and non-sea-salt potassium (nss-K+) were quantified at the Lin'an site. The annual average concentrations of LG, MN and nss-K+ in PM2.5 were 0.13 ± 0.14 μg m−3, 0.009 ± 0.010 μg m−3 and 0.65 ± 0.38 μg m−3, respectively. The yearly variations of anhydrosugar tracers, i.e., LG and MN were fairly consistent, as well as nss-K+. However, due to extensive fireworks activity, nss-K+ was observed during a three-day episode from 7 to 9 February 2016, with abnormally high levels (average at 5.38 ± 3.55 μg m−3). The highest levels of biomass burning tracers were associated with the strong continental outflow from inland China in winter, while lower levels of biomass burning tracers were observed in summer season, influenced by maritime air masses. Combined with the analysis of fire activity data, clear seasonal trends of biomass burning pollution in Lin'an are apparent, ranging from high to low in winter, spring, autumn and summer. By analyzing the ratios of LG/MN and LG/nss-K+, biomass burning aerosols in the East China were identified to be predominately associated with burning of rice crop residues. Moreover, based on the relationship between biomass burning tracers and components in aerosols, biomass burning plays an important role in regulating chemical properties of aerosols in the background site in East China, especially for carbonaceous components.

Aerosol surface area concentration ( S A ) is crucial for studying atmospheric chemical reactions happened in aerosol water or on aerosol surface. However, there is no commercial instrument that can provide direct measurements of ambient S A . In this paper, we propose a method to calculate ambient S A based only on measurements of a three-wavelength humidified nephelometer system, which measures aerosol optical properties at three wavelengths under dry state and different relative humidity (RH) conditions. Two critical steps are required in this method: (1) Calculating surface area concentration of ambient aerosols in dry state, S A ( dry ) , using a trained random forest machine learning model based only on optical properties measured by the “dry” nephelometer. The proposed machine learning method is evaluated with particle number size distributions (PNSD) datasets from eight field campaigns conducted on the North China Plain during different seasons. The square of correlation coefficients between predicted and calculated S A ( dry ) for PNSD is about 0.99, the average ratio between predicted and calculated S A ( dry ) is 1.01 and 70% of data points has a relative difference less than 10%. (2) Calculating the surface area growth factor f S ( RH ) of ambient aerosol particles due to water uptake using the proposed f S ( RH ) parameterization scheme f S ( RH ) = ( 1 + κ S R H 100 − R H ) 2 3 , and the hygroscopicity parameter κ S can be calculated using measured aerosol light scattering enhancement factor and A ngstr o ¨ m exponent. The ambient S A values during two field campaigns which are conducted on the North China Plain (Wangdu campaign and Gucheng campaign, in summer and winter respectively) are calculated using the proposed method. The ambient S A ranges from 42 to 1871 μ m 2 / c m 3 with an average of 319 μ m 2 / c m 3 during Wangdu campaign, and ranges from 19 to 4156 μ m 2 / c m 3 with an average of 788 μ m 2 / c m 3 during Gucheng campaign. Drastic daily variations of ambient S A are observed during these two campaigns. The results demonstrate that aerosol hygroscopic growth impacts significantly on variations in ambient S A especially under high RH conditions. The f S ( RH ) ranges from near 1 to 4 with an average of 1.4 during Wangdu campaign, and ranges from near 1 to 2.7 with an average of 1.3 during Gucheng campaign. The results indicate that the larger RH, the more sensitive f S ( RH ) becomes to variations in κ S which highlights that real-time measurements of aerosol hygroscopicity are required for accurate calculations of ambient S A . The advantage of the proposed method is that the ambient S A can be obtained solely based on measurements of a three-wavelength humidified nephelometer system, facilitating real-time measurements of ambient S A and promoting studies in aerosol heterogeneous reactions.