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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.

Organic aerosol (OA), a large fraction of fine particles, has a large impact on climate radiative forcing and human health, and the impact depends strongly on size distributions. Here we conducted size-resolved OA measurements using a high-resolution aerosol mass spectrometer at urban and rural sites in the North China Plain (NCP) in summer and winter. Our results showed substantially different size distributions of OA with the diameters peaking at ∼550 nm in summer, and 420 nm and 350 nm at urban and rural sites, respectively, during wintertime. Positive matrix factorization (PMF) of size-resolved high-resolution mass spectra of OA resolved various OA factors at urban and rural sites. In particular, we found that the mass spectra of the same type of secondary OA (SOA) from bulk PMF analysis can be largely different across different sizes. Biomass burning OA (BBOA) and fossil-fuel-related OA (FFOA) showed broad size distributions peaking at 350 nm in winter at the rural site, where primary OA (POA = BBOA + FFOA) dominated OA across different sizes. Comparatively, secondary OA (SOA) in the NCP peaked at ∼400–500 nm during wintertime, and ∼500–650 nm in summer. SOA played an enhanced role during more severely polluted days with peak diameters shifting to larger sizes, while the changes in POA size distributions were small. The size-resolved oxygen-to-carbon (O/C) ratios were also determined and linked with the hygroscopicity parameter of OA (κOA). The results showed that κOA increased substantially with particle size, with higher values in summer in Beijing (0.28 ± 0.021) than those during wintertime (0.17 ± 0.019 and 0.12 ± 0.018). The size-resolved κOA would benefit a better prediction of cloud condensation nuclei than bulk κOA in future studies.

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.

Significant upward trends in surface ozone (O

The radiative forcing of black carbon (BC) depends strongly on its mixing state in different chemical environments. Here, we analyzed the chemical composition and mixing state of BC-containing particles by using a single particle aerosol mass spectrometer and investigated their impacts on light absorption enhancement (Eabs) at an urban (Beijing) and a rural site (Gucheng) in North China Plain. While the BC was dominantly mixed with organic carbon (OC), nitrate and sulfate at both urban and rural sites, the rural site showed much higher fraction of BC coated with OC and nitrate (36 % vs. 15 – 20 %). Moreover, the BC mixing state evolved significantly as a function of relative humidity with largely increased coatings of OC-nitrate and nitrate at high RH levels. By linking with the bulk composition of organic aerosol (OA), we found that the OC coated on BC comprised dominantly secondary OA in Beijing, while primary and secondary OA were similarly important in Gucheng. Furthermore, Eabs was highly dependent on the secondary inorganic aerosol coated on BC at both sites, while the coated primary OC also resulted in an Eabs of ~1.2 for relatively fresh BC particles at the rural site. Positive matrix factorization analysis was performed to quantify the impact of different mixing state on Eabs. Our results showed the small Eabs (1.06 ~ 1.11) for BC particles from fresh primary emissions, while the Eabs increased significantly above 1.3 when BC was aged rapidly with increased coatings of OC-nitrate or nitrate, and it can reach above 1.4 as sulfate was involved in BC aging.

China's "Blue Sky Action Plan" aimed at tremendous improvements in atmospheric visibility. While stringent emission control policies have substantially brought down PM

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

The characteristics of wintertime volatile organic compounds (VOCs) in the North China Plain (NCP) region are complicated and remain obscure. VOC measurements were conducted by a proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS) at a rural site in the NCP from November to December 2018. Uncalibrated ions measured by PTR-ToF-MS were quantified and the overall VOC compositions were investigated by combining the measurements of PTR-ToF-MS and gas chromatography-mass spectrometer/flame ionization detector (GC-MS/FID). The measurement showed that although atmospheric VOCs concentrations are often dominated by primary emissions, the secondary formation of oxygenated VOCs (OVOCs) is non-negligible in the wintertime, i.e., OVOCs accounts for 42% ± 7% in the total VOCs (151.3 ± 75.6 ppbV). We demonstrated that PTR-MS measurements for isoprene are substantially overestimated due to the interferences of cycloalkanes. The chemical changes of organic carbon in a pollution accumulation period were investigated, which suggests an essential role of fragmentation reactions for large, chemically reduced compounds during the heavy-polluted stage in wintertime pollution. The changes of emission ratios of VOCs between winter 2011 and winter 2018 in the NCP support the positive effect of "coal to gas" strategies in curbing air pollutants. The high abundances of some key species (e.g. oxygenated aromatics) indicate the strong emissions of coal combustion in wintertime of NCP. The ratio of naphthalene to C8 aromatics was proposed as a potential indicator of the influence of coal combustion on VOCs.

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.

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 are limited, partially due to difficulty in their measurements. High-time resolution (10 s) measurements of higher alkanes were performed using a novel online mass spectrometry method at an urban site of Guangzhou in Pearl River Delta (PRD) and at a rural site in North China Plain (NCP), respectively. 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 7.1 ± 9.5 % in NCP, which are comparable or even higher than both single-ring aromatics and naphthalenes. The significant contributions of higher alkanes in 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.

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.

Laboratory experiments suggest acid-catalyzed aqueous-phase production can promote the formation of isoprene SOA, i.e., 2-methyltetrols. In this study we use ambient observations of the 2-methyltetrols along with other chemical measurements, as well as meteorological factors to investigate the relative importance of environmental influence for isoprene epoxydiols (IEPOX) SOA formation under atmospheric humidity conditions. The 2-Methyltetrols revealed good relationships with temperature and total solar radiation, but were weakly correlated with aerosol acidity and SO

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.

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.

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.

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.

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.

From July 2009–April 2011, 304 whole-air samples were collected at urban and suburban sites in four Chinese cities. The results indicated that recent chlorofluorocarbon (CFC) concentrations in all four cities are approaching Northern Hemispheric (NH) background levels, suggesting that the phase-out of CFCs in China is underway. However, hydrochlorofluorocarbon (HCFC) and 1,1,1,2-tetrafluoroethane (HFC-134a, CH2FCF3) concentrations have risen far above the NH background levels. Their concentration variability is evident, suggesting significant regional emissions. One-way analysis of variance (ANOVA) and independent-sample t-tests were applied to analyze the spatial distributions and emissions. Monochlorodifluoromethane (HCFC-22, CHClF2) levels at the urban sites were 30% higher than those observed at the suburban sites (P

Measurements of ozone and its precursors conducted within the HaChi (Haze in China) project in summer 2009 were analyzed to characterize volatile organic compounds (VOCs) and their effects on ozone photochemical production at a suburban site in the North China Plain (NCP). Ozone episodes, during which running 8-h average ozone concentrations exceeding 80 ppbv lasted for more than 4 h, occurred on about two thirds of the observational days during the 5-week field campaign. This suggests continuous ozone exposure risks in this region in the summer. Average concentrations of nitrogen oxides (NOx) and VOCs are about 20 ppbv and 650 ppbC, respectively. On average, total VOC reactivity is dominated by anthropogenic VOCs. The contribution of biogenic VOCs to total ozone-forming potential, however, is also considerable in the daytime. Key species associated with ozone photochemical production are 2-butenes (18 %), isoprene (15 %), trimethylbenzenes (11 %), xylenes (8.5 %), 3-methylhexane (6 %), n-hexane (5 %) and toluene (4.5 %). Formation of ozone is found to be NOx-limited as indicated by measured VOCs/NOx ratios and further confirmed by a sensitivity study using a photochemical box model NCAR_MM. The Model simulation suggests that ozone production is also sensitive to changes in VOC reactivity under the NOx-limited regime, although this sensitivity depends strongly on how much NOx is present.