Likun Xue

Ozone pollution in China: A review of concentrations, meteorological influences, chemical precursors, and effects

High concentrations of ozone in urban and industrial regions worldwide have long been a major air quality issue. With the rapid increase in fossil fuel consumption in China over the past three decades, the emission of chemical precursors to ozone-nitrogen oxides and volatile organic compounds-has increased sharply, surpassing that of North America and Europe and raising concerns about worsening ozone pollution in China. Historically, research and control have prioritized acid rain, particulate matter, and more recently fine particulate matter (PM2.5). In contrast, less is known about ozone pollution, partly due to a lack of monitoring of atmospheric ozone and its precursors until recently. This review summarizes the main findings from published papers on the characteristics and sources and processes of ozone and ozone precursors in the boundary layer of urban and rural areas of China, including concentration levels, seasonal variation, meteorology conducive to photochemistry and pollution transport, key production and loss processes, ozone dependence on nitrogen oxides and volatile organic compounds, and the effects of ozone on crops and human health. Ozone concentrations exceeding the ambient air quality standard by 100-200% have been observed in Chinas major urban centers such as Jing-Jin-Ji, the Yangtze River delta, and the Pearl River delta, and limited studies suggest harmful effect of ozone on human health and agricultural corps; key chemical precursors and meteorological conditions conductive to ozone pollution have been investigated, and inter-city/region transport of ozone is significant. Several recommendations are given for future research and policy development on ground-level ozone.

Transport of north China air pollution by midlatitude cyclones: Case study of aircraft measurements in summer 2007

Warm conveyor belts(WCBs) and frontal activity play important roles in the long-range transport of air pollutants by lifting them from the planetary boundary layer (PBL) into the free troposphere ( FT) in midlatitudes. In summer 2007, an aircraft study was carried out in northeast ( NE) China in order to understand the role of midlatitude cyclones in air pollution transport in north and east China in warm seasons. During a flight on 27 June, high concentrations of ozone and related trace gases were observed, with maximum concentrations (O(3) similar to 140 ppbv, SO(2) similar to 14.6 ppbv, CO similar to 1185 ppbv) recorded at an altitude of 2.6 km. In this paper we present a detailed analysis of this flight. The mesoscale meteorological model Weather Research and Forecasting (WRF) and a Lagrangian dispersion model called FLEXPART were used to aid the diagnostic analysis of the atmospheric dynamic structure and the understanding of the transport characteristics of regional and local air pollution. The flight took place in a region adjacent to a warm front associated with a weak cyclone in north China. The aircraft sampled both the WCB and warm air frontal zone of the cyclone. The simulations show that the observed high air pollution in the FT mostly originated from the North China Plain, especially the megacities Beijing and Tianjin. Their plumes were vented by a stagnant front, probably through, in part, topographic lifting by the mountains in the north, and then were quickly transported in the FT to the study region. Trajectory analysis and satellite data suggest that the observed air masses were further lifted by the WCB into the middle and upper troposphere and were exported from Asia toward North America and the Arctic.

Polluted dust promotes new particle formation and growth

Understanding new particle formation and their subsequent growth in the troposphere has a critical impact on our ability to predict atmospheric composition and global climate change. High pre-existing particle loadings have been thought to suppress the formation of new atmospheric aerosol particles due to high condensation and coagulation sinks. Here, based on field measurements at a mountain site in South China, we report, for the first time, in situ observational evidence on new particle formation and growth in remote ambient atmosphere during heavy dust episodes mixed with anthropogenic pollution. Both the formation and growth rates of particles in the diameter range 15–50 nm were enhanced during the dust episodes, indicating the influence of photo-induced, dust surface-mediated reactions and resulting condensable vapor production. This study provides unique in situ observations of heterogeneous photochemical processes inducing new particle formation and growth in the real atmosphere, and suggests an unexpected impact of mineral dust on climate and atmospheric chemistry.

Source of surface ozone and reactive nitrogen speciation at Mount Waliguan in western China : new insights from the 2006 summer study

measurement period of 2006 (55%) than that of 2003 (25%). The abnormally high values of NOy observed in 2003 were suspected to be due to the positive interference from ammonia (NH3) to the particular catalytic converter used in that study. Varied diurnal patterns were observed for the various NOy components. The ozone production efficiencies (DO3/DNOz), which were estimated from the slope of the O3‐NOz scatterplot, were 7.7–11.3 for the polluted plumes from central and eastern China. The speciation of reactive nitrogen was investigated for the first time in the remote free troposphere in western China. PAN and particulate NO3 − were the most abundant reactive nitrogen species at WLG, with average proportions of 32% and 31%, followed by NOx (24%) and HNO3 (20%). The relatively large contribution of particulate NO3 − to NOy was due to the presence of high concentrations of NH3 and crustal particles, which favor the formation of particulate nitrate. An analysis of backward trajectories for the recent 10 years revealed that air masses from central and eastern China dominated the airflow at WLG in summer, suggesting strong impact of anthropogenic forcing on the surface ozone and other trace constituents on the Plateau.

Increasing external effects negate local efforts to control ozone air pollution : a case study of Hong Kong and implications for other Chinese cities

It is challenging to reduce ground-level ozone (O3) pollution at a given locale, due in part to the contributions of both local and distant sources. We present direct evidence that the increasing regional effects have negated local control efforts for O3 pollution in Hong Kong over the past decade, by analyzing the daily maximum 8 h average O3 and Ox (=O3+NO2) concentrations observed during the high O3 season (September-November) at Air Quality Monitoring Stations. The locally produced Ox showed a statistically significant decreasing trend over 2002-2013 in Hong Kong. Analysis by an observation-based model confirms this decline in in situ Ox production, which is attributable to a reduction in aromatic hydrocarbons. However, the regional background Ox transported into Hong Kong has increased more significantly during the same period, reflecting contributions from southern/eastern China. The combined result is a rise in O3 and a nondecrease in Ox. This study highlights the urgent need for close cross-boundary cooperation to mitigate the O3 problem in Hong Kong. Chinas air pollution control policy applies primarily to its large cities, with little attention to developing areas elsewhere. The experience of Hong Kong suggests that this control policy does not effectively address secondary pollution, and that a coordinated multiregional program is required.

Observations of Nitryl Chloride and Modeling its Source and Effect on Ozone in the Planetary Boundary Layer of Southern China

Nitryl chloride (ClNO2) plays potentially important roles in atmospheric chemistry, but its abundance and effect are not fully understood due to the small number of ambient observations of ClNO2 to date. In late autumn 2013, ClNO2 was measured with a chemical ionization mass spectrometer (CIMS) at a mountain top (957 m above sea level) in Hong Kong. During 12 nights with continuous CIMS data, elevated mixing ratios of ClNO2 (>400 parts per trillion by volume) or its precursor N2O5 (>1000 pptv) were observed on six nights, with the highest ever reported ClNO2 (4.7 ppbv, 1 min average) and N2O5 (7.7 ppbv, 1 min average) in one case. Backward particle dispersion calculations driven by winds simulated with a mesoscale meteorological model show that the ClNO2/N2O5-laden air at the high-elevation site was due to transport of urban/industrial pollution north of the site. The highest ClNO2/N2O5 case was observed in a later period of the night and was characterized with extensively processed air and with the presence of nonoceanic chloride. A chemical box model with detailed chlorine chemistry was used to assess the possible impact of the ClNO2 in the well-processed regional plume on next day ozone, as the air mass continued to downwind locations. The results show that the ClNO2 could enhance ozone by 5–16% at the ozone peak or 11–41% daytime ozone production in the following day. This study highlights varying importance of the ClNO2 chemistry in polluted environments and the need to consider this process in photochemical models for prediction of ground-level ozone and haze.

Number concentration and size distributions of submicron particles in Jinan urban area: Characteristics in summer and winter

The aerosol number concentration and size distribution were measured with the newly developed Wide-range Particle Spectrometer in summer and winter of 2006 at the urban site of Jinan City. Here reported the characteristics of fine particles of the different observation seasons. Relative high number concentrations for the particles in the diameter range of 10-500 nm were observed in both seasons. It was found that the dominant number distributed in particle diameter smaller than 100 nm and the percentage over the number concentration of all air particles is much higher than what has been measured in other urban sites over the world. The number mean diameter in summer was much smaller than in winter, strongly suggesting the different origin of ultrafine particles in different seasons. That is, particles in ultrafine mode mainly came from nucleation and new particle formation in summer while from traffic emission in winter. The diurnal variation also supported this point. Number concentration in the diameter range of 10-200 nm got their peak values at noontime, well correlated with the mixing ratio of SO2 and the intensity of solar radiation in summer. While in winter, those in the same diameter range showed the main peaks during the traffic hours happened in the morning and evening.

Nighttime chemistry at a high altitude site above Hong Kong

Nighttime reactions of nitrogen oxides influence ozone, volatile organic compounds, and aerosol and are thus important to the understanding of regional air quality. Despite large emissions and rapid recent growth of nitrogen oxide concentrations, there are few studies of nighttime chemistry in China. Here we present measurements of nighttime nitrogen oxides, NO3 and N2O5, from a coastal mountaintop site in Hong Kong adjacent to the megacities of the Pearl River Delta region. This is the first study of nighttime chemistry from a site within the residual layer in China. Key findings include the following. First, highly concentrated urban NOx outflow from the Pearl River Delta region was sampled infrequently at night, with N2O5 mixing ratios up to 8 ppbv (1 min average) or 12 ppbv (1 s average) in nighttime aged air masses. Second, the average N2O5 uptake coefficient was determined from a best fit to the available steady state lifetime data as γ(N2O5) = 0.014 ± 0.007. Although this determination is uncertain due to the difficulty of separating N2O5 losses from those of NO3, this value is in the range of previous residual layer determinations of N2O5 uptake coefficients in polluted air in North America. Third, there was a significant contribution of biogenic hydrocarbons to NO3 loss inferred from canister samples taken during daytime. Finally, daytime N2O5 mixing ratios were in accord with their predicted photochemical steady state. Heterogeneous uptake of N2O5 in fog is determined to be an important production mechanism for soluble nitrate, even during daytime.

Aerosol ionic components at Mt. Heng in central southern China: Abundances, size distribution, and impacts of long-range transport

Water-soluble ions in PM(2.5) were continuously measured, along with the measurements of many other species and collection of size-resolved aerosol samples, at the summit of Mt. Heng in the spring of 2009, to understand the sources of aerosols in rural central southern China. The mean concentrations of SO(4)(2-), NH(4)(+) and NO(3)(-) in PM(2.5) were 8.02, 2.94 and 1.47 μg/m(3), indicating a moderate aerosol pollution level at Mt. Heng. Water-soluble ions composed approximately 40% of the PM(2.5) mass on average. PM(2.5) was weakly acidic with about 66% of the samples being acidic. SO(4)(2-), NO(3)(-) and NH(4)(+) exhibited similar diurnal patterns with a broad afternoon maximum. SO(4)(2-) and NH(4)(+) were mainly present in the fine aerosols with a peak in the droplet mode of 0.56-1 μm, suggesting the important role of cloud processing in the formation of aerosol sulfate. NO(3)(-) was largely distributed in the coarse particles with a predominant peak in the size-bin of 3.2-5.6 μm. Long-distance transport of processed air masses, dust aerosols, and cloud/fog processes were the major factors determining the variations of fine aerosol at Mt. Heng. The results at Mt. Heng were compared with those obtained from our previous study at Mt. Tai in north China. The comparison revealed large differences in the aerosol characteristics and processes between southern and northern China. Backward trajectories indicated extensive transport of anthropogenic pollution from the coastal regions of eastern/northern China and the Pearl River Delta (PRD) to Mt. Heng in spring, highlighting the need for regionally coordinated control measures for the secondary pollutants.

On the use of an explicit chemical mechanism to dissect peroxy acetyl nitrate formation

Peroxy acetyl nitrate (PAN) is a key component of photochemical smog and plays an important role in atmospheric chemistry. Though it has been known that PAN is produced via reactions of nitrogen oxides (NOx) with some volatile organic compounds (VOCs), it is difficult to quantify the contributions of individual precursor species. Here we use an explicit photochemical model--Master Chemical Mechanism (MCM) model--to dissect PAN formation and identify principal precursors, by analyzing measurements made in Beijing in summer 2008. PAN production was sensitive to both NOx and VOCs. Isoprene was the predominant VOC precursor at suburb with biogenic impact, whilst anthropogenic hydrocarbons dominated at downtown. PAN production was attributable to a relatively small class of compounds including NOx, xylenes, trimethylbenzenes, trans/cis-2-butenes, toluene, and propene. MCM can advance understanding of PAN photochemistry to a species level, and provide more relevant recommendations for mitigating photochemical pollution in large cities.