ALBERT

Description: Severe winter haze accompanied by high concentrations of fine particulate matter (PM2.5) occurs frequently in the North China Plain and threatens public health. Organic matter (OM) and sulfate are recognized as major components of PM2.5, while atmospheric models often fail to predict their high concentrations during severe winter haze due to incomplete understanding of secondary aerosol formation mechanisms. By using a novel combination of single-particle mass spectrometry and an optimized ion chromatography method, here we show that hydroxymethanesulfonate (HMS), formed by the reaction between formaldehyde (HCHO) and dissolved SO2 in aerosol water, is ubiquitous in Beijing during winter. The HMS concentration and the molar ratio of HMS to sulfate increased with the deterioration of winter haze. High concentrations of precursors (SO2 and HCHO) coupled with low oxidant levels, low temperature, high relative humidity, and moderately acidic pH facilitate the heterogeneous formation of HMS, which could account for up to 15 % of OM in winter haze and lead to up to 36 % overestimates of sulfate when using traditional ion chromatography. Despite the clean air actions having substantially reduced SO2 emissions, the HMS concentration and molar ratio of HMS to sulfate during severe winter haze increased from 2015 to 2016 with the growth in HCHO concentration. Our findings illustrate the significant contribution of heterogeneous HMS chemistry to severe winter haze in Beijing, which helps to improve the prediction of OM and sulfate and suggests that the reduction in HCHO can help to mitigate haze pollution.

Description: The chemical mechanisms responsible for rapid sulfate production, an important driver of winter haze formation in northern China, remain unclear. Here, we propose a potentially important heterogeneous hydroxymethanesulfonate (HMS) chemical mechanism. Through analyzing field measurements with aerosol mass spectrometry, we show evidence for a possible significant existence in haze aerosols of organosulfur primarily as HMS, misidentified as sulfate in previous observations. We estimate that HMS can account for up to about one-third of the sulfate concentrations unexplained by current air quality models. Heterogeneous production of HMS by SO2 and formaldehyde is favored under northern China winter haze conditions due to high aerosol water content, moderately acidic pH values, high gaseous precursor levels, and low temperature. These analyses identify an unappreciated importance of formaldehyde in secondary aerosol formation and call for more research on sources and on the chemistry of formaldehyde in northern China winter.

Description: The North China Plain (NCP) has become one of the most polluted regions in China, with the rapidly increasing economic growth in the past decades. High concentrations of ambient O3 and aerosol have been observed at urban as well as rural sites in the NCP. Most of the in situ observations of air pollutants have been conducted near the ground so that current knowledge about the vertical distributions of tropospheric O3 and aerosol over the NCP region is still limited. In this study, vertical profiles of O3 and size-resolved aerosol concentrations below 2.5 km were measured in summer 2014 over a rural site in the NCP, using an unmanned aerial vehicle (UAV) equipped with miniature analyzers. In addition, vertical profiles of aerosol scattering property in the lower troposphere and vertical profiles of O3 below 1 km were also observed at the site using a lidar and tethered balloon, respectively. The depths of the mixed layer and residual layer were determined according to the vertical gradients of lidar particle extinction and aerosol number concentration. Average O3 and size-resolved aerosol number concentration in both the mixed and residual layer were obtained from the data observed in seven UAV flights. The results show that during most of the flights the O3 levels above the top of mixed layer were higher than those below. Such a positive gradient in the vertical distribution of O3 makes the residual layer an important source of O3 in the mixed layer, particularly during the morning when the top of mixed layer is rapidly elevated. In contrast to O3, aerosol number concentration was normally higher in the mixed layer than in the residual layer, particularly in the early morning. Aerosol particles were overwhelmingly distributed in the size range  

Description: Both peroxyacetyl nitrate (PAN) and ozone (O3) are key photochemical products in the atmosphere. Most of the previous in situ observations of both gases have been made in polluted regions and at low-altitude sites. Here we present the first simultaneous measurements of PAN and O3 at Nam Co (NMC; 30°46′ N, 90°57′ E, 4745 m a.s.l.), a remote site in the central Tibetan Plateau (TP). The observations were made during summer periods in 2011 and 2012. The PAN levels averaged 0.36 ppb (range: 0.11–0.76 ppb) and 0.44 ppb (range: 0.21–0.99 ppb) during 17–24 August 2011 and 15 May to 13 July 2012, respectively. The O3 level varied from 27.9 to 96.4 ppb, with an average of 60.0 ppb. Profound diurnal cycles of PAN and O3 were observed with minimum values around 05:00 LT, steep rises in the early morning, and broader platforms of high values during 09:00–20:00 LT. The evolution of the planetary boundary layer (PBL) played a key role in shaping the diurnal patterns of both gases, particularly the rapid increases of PAN and O3 in the early morning. Air entrainment from the free troposphere into the PBL seemed to cause the early-morning increase and be a key factor for sustaining the daytime high concentrations of both gases. The days with higher daytime PBL (about 3 km) showed stronger diurnal variations in both gases and were mainly distributed in the drier pre-monsoon period, while those with shallower daytime PBL (about 2 km) showed minor diurnal variations and were mainly distributed in the humid monsoon period. Episodes of higher PAN levels were occasionally observed at NMC. These PAN episodes were caused either by rapid downward transport of air masses from the middle/upper troposphere or by long-range transport of PAN plumes from north India, north Pakistan, and Nepal. The maximum PAN level in the downward transport cases ranged from 0.5 to 0.7 ppb. In the long-range transport case, the PAN level varied in the range of 0.3–1.0 ppb, with an average of 0.6 ppb. This long-range transport process influenced most of the western and central TP region for about a week in early June 2012. Our results suggest that polluted air masses from South Asia can significantly enhance the PAN level over the TP. As PAN acts as a reservoir of NOx, the impacts of pollution transport from South Asia on tropospheric photochemistry over the TP region deserve further studies.

Description: China is a highly polluted region, particularly the North China Plain (NCP). However, emission reductions have been occurring in China for about the last 10 years; these reduction measures have been in effect since 2006 for SO2 emissions and since 2010 for NOx emissions. Recent studies have shown a decrease in the NO2 tropospheric column since 2013 that has been attributed to the reduction in NOx emissions. Quantifying how these emission reductions translate regarding ozone concentrations remains unclear due to apparent inconsistencies between surface and satellite observations. In this study, we use the lower tropospheric (LT) columns (surface – 6 km a.s.l. – above sea level) derived from the IASI-A satellite instrument to describe the variability and trend in LT ozone over the NCP for the 2008–2016 period. First, we investigate the IASI retrieval stability and robustness based on the influence of atmospheric conditions (thermal conditions and aerosol loading) and retrieval sensitivity changes. We compare IASI-A observations with the independent IASI-B instrument aboard the Metop-B satellite as well as comparing them with surface and ozonesonde measurements. The conclusion from this evaluation is that the LT ozone columns retrieved from IASI-A are reliable for deriving a trend representative of the lower/free troposphere (3–5 km). Deseasonalized monthly time series of LT ozone show two distinct periods: the first period (2008–2012) with no significant trend (

Description: The real-time measurements of NH3 and trace gases were conducted, in conjunction with semi-continuous measurements of water-soluble ions in PM2.5 at a rural site in the North China Plain (NCP) from May to September 2013 in order to better understand chemical characteristics of ammonia and the impact of secondary ammonium aerosols on formation in the NCP. Extremely high NH3 and NH4+ concentrations were observed after a precipitation event within 7–10 days following urea application. Elevated NH3 levels coincided with elevated NH4+, indicating that NH3 likely influenced particulate ammonium mass. For the sampling period, the average conversion ∕ oxidation ratios for NH4+ (NHR), SO42- (SOR), and NO3- (NOR) were estimated to be 0.30, 0.64, and 0.24, respectively. The increased NH3 concentrations, mainly from agricultural activities and regional transport, coincided with the prevailing meteorological conditions. The high NH3 level with NHR of about 0.30 indicates that the emission of NH3 in the NCP is much higher than needed for aerosol acid neutralisation, and NH3 plays an important role in the formation of secondary aerosols as a key neutraliser. The hourly data obtained were used to investigate gas–aerosol partitioning characteristics using the thermodynamic equilibrium model ISORROPIA-II. Modelled SO42-, NO3-, and NH3 values agree well with the measurements, while the modelled NH4+ values largely underestimate the measurements. Our observation and modelling results indicate that strong acids in aerosol are completely neutralised. Additional NH4+ exists in aerosol, probably a result of the presence of a substantial amount of oxalic and other diacids.

Description: 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.

Description: Ozone pollution in eastern China has become one of the top environmental issues. Quantifying the temporal trend of surface ozone helps to assess the impacts of the anthropogenic precursor reductions and the likely effects of emission control strategies implemented. In this paper, ozone data collected at the Shangdianzi (SDZ) regional atmospheric background station from 2003 to 2015 are presented and analyzed to obtain the variation in the trend of surface ozone in the most polluted region of China, north of eastern China or the North China Plain. A modified Kolmogorov–Zurbenko (KZ) filter method was performed on the maximum daily average 8 h (MDA8) concentrations of ozone to separate the contributions of different factors from the variation of surface ozone and remove the influence of meteorological fluctuations on surface ozone. Results reveal that the short-term, seasonal and long-term components of ozone account for 36.4, 57.6 and 2.2 % of the total variance, respectively. The long-term trend indicates that the MDA8 has undergone a significant increase in the period of 2003–2015, with an average rate of 1.13 ± 0.01 ppb year−1 (R2 = 0.92). It is found that meteorological factors did not significantly influence the long-term variation of ozone and the increase may be completely attributed to changes in emissions. Furthermore, there is no significant correlation between the long-term O3 and NO2 trends. This study suggests that emission changes in VOCs might have played a more important role in the observed increase of surface ozone at SDZ.

Description: 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

Description: 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.