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The high concentration of fine particles and gaseous pollutants makes polluted areas, such as the urban setting of North China Plain (NCP) of China, a different environment for new particle formation (NPF) compared to many clean regions. Such conditions also hold for other polluted environments in this region (for instance, the rural area of NCP), yet the underlying mechanisms for NPF remain less understood, owing to the limited observations of particles in the sub−3 nm range. Comprehensive measurements, particularly covering the particle number size distribution down to 1.3 nm, were conducted at a rural background site of Gucheng (GC) in the North China Plain (NCP) from 12 November to 24 December 2018. In total, five NPF events during the 39 effective days of measurements for the campaign were identified, with the mean particle nucleation rate (J1.3) and growth rate (GR1.3–2.4) being 22.0 cm−3 s−1 and 3.9 nm h−1, respectively. During these 5 d, NPF concurrently occurred at an urban site in Beijing. Sharing similar sources and transport paths of air masses arriving at our site to that of urban Beijing, we hypothesize that NPF events during these days in this region might be a regional phenomenon. The simultaneous occurrence of NPF in both places implies that H2SO4-amine nucleation, concluded for urban Beijing there, could probably be the dominating mechanism for NPF at our rural site. The higher concentration of sulfuric acid during many non-event days compared to that of event days indicates that the content of sulfuric acid may not necessarily lead to NPF events under current atmosphere. Only when the condensation sink or coagulation sink was significantly lowered, atmospheric NPF occurred, implying that condensation sinks (CSs) and coagulation sinks (CoagSs) are the dominating factors controlling the occurrence of NPF for the present rural environment of the NCP, which is quite similar to the feature seen in urban Beijing.

Secondary organic aerosols (SOAs) account for a large fraction of atmospheric aerosol mass and play significant roles in visibility impairment by scattering solar radiation. However, comprehensive evaluations of SOA scattering abilities under ambient relative humidity (RH) conditions on the basis of field measurements are still lacking due to the difficulty of simultaneously direct quantifications of SOA scattering efficiency in dry state and SOA water uptake abilities. In this study, field measurements of aerosol chemical and physical properties were conducted in winter in Guangzhou (lasting about 3 months) using a humidified nephelometer system and aerosol chemical speciation monitor. A modified multilinear regression model was proposed to retrieve dry-state mass scattering efficiencies (MSEs, defined as scattering coefficient per unit aerosol mass) of aerosol components. The more oxidized oxygenated organic aerosol (MOOA) with an O/C ratio of 1.17 was identified as the most efficient light scattering aerosol component. On average, 34 % mass contribution of MOOA to total submicron organic aerosol mass contributed 51 % of dry-state organic aerosol scattering. The overall organic aerosol hygroscopicity parameter κOA was quantified directly through hygroscopicity closure, and hygroscopicity parameters of SOA components were further retrieved using a multilinear regression model by assuming hydrophobic properties of primary organic aerosols. The highest water uptake ability of MOOA among organic aerosol factors was revealed with κMOOA reaching 0.23, thus further enhancing the fractional contribution of MOOA in ambient organic aerosol scattering. In particular, the scattering abilities of MOOA were found to be even higher than those of ammonium nitrate under RH of %, which was identified as the most efficient inorganic scattering aerosol component, demonstrating that MOOA had the strongest scattering abilities in ambient air (average RH of 57 %) during winter in Guangzhou. During the observation period, secondary aerosols contributed dominantly to visibility degradation (∼70 %), with substantial contributions from MOOA (16 % on average), demonstrating significant impacts of MOOA on visibility degradation. The findings of this study demonstrate that more attention needs to be paid to SOA property changes in future visibility improvement investigations. Also, more comprehensive studies on MOOA physical properties and chemical formation are needed to better parameterize its radiative effects in models and implement targeted control strategies on MOOA precursors for visibility improvement.

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).

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 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.

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 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.

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.

A phenomenon of frequent noontime SO2 concentration peaks was discovered in a detailed analysis of the SO2 concentrations in the North China Plain (NCP). The possible causes and their contributions are analyzed. The impacts of such a phenomenon on the sulphur cycle were studied and the implications of the phenomenon for atmospheric chemistry, cloud physics, and climate were discussed. Different from the more common SO2 diurnal patterns with high nighttime concentrations, NCP witnessed high frequencies of noontime SO2 peaks, with an occurrence frequency of 50 to 72% at four stations. Down mixing of elevated pollution layers, plume transport processes, mountain-valley winds, and fog/high RH haze events were the possible causes. The contribution of each process varies from day to day and from station to station, however, none of those four processes can be neglected. SO2 peaks occurring during noontime instead of nighttime will lead to a 13 to 35% increase in sulphur dry deposition, a 9 to 23% increase in gas phase oxidation, and an 8 to 33% increase in aqueous phase conversions, which will increase the hygroscopicity and the light scattering of aerosols, thus having important impacts on atmospheric chemistry, cloud physics, and climate.

Water can be a major component of an aerosol particle. Also water serves as a medium for aqueous-phase reactions in aerosols. In this study, a novel method is presented to calculate the aerosol liquid water content at high relative humidity based on measurements of aerosol hygroscopic growth factor, particle number size distribution and relative humidity in the Haze in China (HaChi) summer field campaign (July–August 2009) in the North China Plain. The aerosol liquid water content calculated using this method agreed well with that calculated using a thermodynamic equilibrium model (ISORROPIA II) at high relative humidity (>60 %) with a correlation coefficient of 0.9658. At low relative humidity (

This work analyses optical properties of the dry tropospheric aerosol measured at the regional Global Atmosphere Watch (GAW) observation site Melpitz in East Germany. For a continuous observation period between 2007 and 2010, we provide representative values of the dry-state scattering coefficient, hemispheric backscattering coefficient, absorption coefficient, single scattering albedo, and scattering Ångström exponent. Besides the direct measurement, the aerosol scattering coefficient was alternatively computed from experimental particle number size distributions using a Mie model. Within pre-defined limits, a closure could be achieved with the direct measurement. The achievement of closure implies that such calculations can be used as a high-level quality control measure for data sets involving multiple instrumentation. All dry-state optical properties show pronounced annual and diurnal variations, which are attributed to the corresponding variations in the regional emission fluxes, the intensity of secondary particle formation, and the mixing layer height. Air mass classification shows that atmospheric stability is a major factor influencing the dry aerosol properties at the GAW station. In the cold season, temperature inversions limit the volume available for atmospheric mixing, so that the dry-state aerosol optical properties near the ground proved quite sensitive to the geographical origin of the air mass. In the warm season, when the atmosphere is usually well-mixed during daytime, considerably less variability was observed for the optical properties between different air masses. This work provides, on the basis of quality-checked in situ measurements, a first step towards a climatological assessment of direct aerosol radiative forcing in the region under study.

Rapid economic growth has given rise to a significant increase in ozone precursor emissions in many regions of China, especially in the densely populated North China Plain (NCP) and Yangtze River Delta (YRD). Improved understanding of ozone formation in response to different precursor emissions is imperative to address the highly nonlinear ozone problem and to provide a solid scientific basis for efficient ozone abatement in these regions. A comparative study on ozone photochemical production in summer has thus been carried out in the megacities of Tianjin (NCP) and Shanghai (YRD). Two intensive field campaigns were carried out respectively at an urban and a suburban site of Tianjin, in addition to routine monitoring of trace gases in Shanghai, providing data sets of surface ozone and its precursors including nitrogen oxides (NOx) and various non-methane hydrocarbons (NMHCs). Ozone pollution in summer was found to be more severe in the Tianjin region than in the Shanghai region, based on either the frequency or the duration of high ozone events. Such differences might be attributed to the large amount of highly reactive NMHCs in Tianjin. Industry related species like light alkenes were of particular importance in both urban and suburban Tianjin, while in Shanghai aromatics dominated. In general, the ozone problem in Shanghai is on an urban scale. Stringent control policies on local emissions would help reduce the occurrence of high ozone concentrations. By contrast, ozone pollution in Tianjin is probably a regional problem. Combined efforts to reduce ozone precursor emissions on a regional scale must be undertaken to bring the ozone problem under control.

In this paper, the mixing state of light absorbing carbonaceous (LAC) was investigated with a two-parameter aerosol optical model and in situ aerosol measurements at a regional site in the North China Plain (NCP). A closure study between the hemispheric backscattering fraction (HBF) measured by an integrating nephelometer and that calculated with a modified Mie model was conducted. A new method was proposed to retrieve the ratio of the externally mixed LAC mass to the total mass of LAC (rext-LAC) based on the assumption that the ambient aerosol particles were externally mixed and consisted of a pure LAC material and a core-shell morphology in which the core is LAC and the shell is a less absorbing material. A Monte Carlo simulation was applied to estimate the overall influences of input parameters of the algorithm to the retrieved rext-LAC. The diurnal variation of rext-LAC was analyzed and the PartMC-MOSAIC model was used to simulate the variation of the aerosol mixing state. Results show that, for internally mixed particles, the assumption of core-shell mixture is more appropriate than that of homogenous mixture which has been widely used in aerosol optical calculations. A significant diurnal pattern of the retrieved rext-LAC was found, with high values during the daytime and low values at night. The consistency between the retrieved rext-LAC and the model results indicates that the diurnal variation of LAC mixing state is mainly caused by the diurnal evolution of the mixing layer.

North China Plain (NCP) is one of the most densely populated regions in China and has experienced enormous economic growth in the past decades. Its regional trace gas pollution has also become one of the top environmental concerns in China. Measurements of surface trace gases, including O3, NOx, SO2 and CO were carried out within the HaChi (Haze in China) project at Wuqing Meteorology Station, located between 2 mega-cities (Beijing and Tianjin) in the NCP, from 9 July 2009 to 21 January 2010. Detailed statistical analyses were made in order to provide information on the levels of the measured air pollutants and their characteristics. Gaseous air pollutant concentrations were also studied together with meteorological data and satellite data to help us better understand the causes of the observed variations in the trace gases during the field campaign. In comparison to measurements from other rural and background stations in the NCP, relatively high concentrations were detected in Wuqing, presumably due to regional mixing and transport of pollutants. Local meteorology had deterministic impacts on air pollution levels, which have to be accounted for when evaluating other effects on pollutant concentrations. Trace gas concentrations showed strong dependence on wind, providing information on regional pollution characteristics. O3 mixing ratio also showed clear dependencies on temperature and relative humidity.

Size-resolved and bulk activation properties of aerosols were measured at a regional/suburban site in the North China Plain (NCP), which is occasionally heavily polluted by anthropogenic aerosol particles and gases. A Cloud Condensation Nuclei (CCN) closure study is conducted with bulk CCN number concentration (NCCN) and calculated CCN number concentration based on the aerosol number size distribution and size-resolved activation properties. The observed CCN number concentration (NCCN-obs) are higher than those observed in other locations than China, with average NCCN-obs of roughly 2000, 3000, 6000, 10 000 and 13 000 cm−3 at supersaturations of 0.056, 0.083, 0.17, 0.35 and 0.70%, respectively. An inferred critical dry diameter (Dm) is calculated based on the NCCN-obs and aerosol number size distribution assuming homogeneous chemical composition. The inferred cut-off diameters are in the ranges of 190–280, 160–260, 95–180, 65–120 and 50–100 nm at supersaturations of 0.056, 0.083, 0.17, 0.35 and 0.7%, with their mean values 230.1, 198.4, 128.4, 86.4 and 69.2 nm, respectively. Size-resolved activation measurements show that most of the 300 nm particles are activated at the investigated supersaturations, while almost no particles of 30 nm are activated even at the highest supersaturation of 0.72%. The activation ratio increases with increasing supersaturation and particle size. The slopes of the activation curves for ambient aerosols are not as steep as those observed in calibrations with ammonium sulfate suggesting that the observed aerosols is an external mixture of more hygroscopic and hydrophobic particles. The calculated CCN number concentrations (NCCN-calc) based on the size-resolved activation ratio and aerosol number size distribution correlate well with the NCCN-obs, and show an average overestimation of 19%. Sensitivity studies of the CCN closure show that the NCCN at each supersaturation is well predicted with the campaign average of size-resolved activation curves. These results indicate that the aerosol number size distribution is critical in the prediction of possible CCN. The CCN number concentration can be reliably estimated using time-averaged, size-resolved activation efficiencies without accounting for the temporal variations.