Potential of secondary aerosol formation from Chinese gasoline engine exhaust

Light-duty gasoline vehicles have drawn public attention in China due to their significant primary emissions of particulate matter and volatile organic compounds(VOCs). However,little information on secondary aerosol formation from exhaust for Chinese vehicles and fuel conditions is available. In this study, chamber experiments were conducted to quantify the potential of secondary aerosol formation from the exhaust of a port fuel injection gasoline engine. The engine and fuel used are common in the Chinese market, and the fuel satisfies the China V gasoline fuel standard. Substantial secondary aerosol formation was observed during a 4–5 hr simulation, which was estimated to represent more than 10 days of equivalent atmospheric photo-oxidation in Beijing. As a consequence, the extreme case secondary organic aerosol(SOA) production was 426 ± 85 mg/kg-fuel, with high levels of precursors and OH exposure. The low hygroscopicity of the aerosols formed inside the chamber suggests that SOA was the dominant chemical composition. Fourteen percent of SOA measured in the chamber experiments could be explained through the oxidation of speciated single-ring aromatics. Unspeciated precursors, such as intermediate-volatility organic compounds and semi-volatile organic compounds, might be significant for SOA formation from gasoline VOCs. We concluded that reductions of emissions of aerosol precursor gases from vehicles are essential to mediate pollution in China.     

An economic assessment of the health effects and crop yield losses caused by air pollution in mainland China

Air pollution is severe in China, and pollutants such as PM_(2.5) and surface O_3 may cause major damage to human health and crops, respectively. Few studies have considered the health effects of PM_(2.5) or the loss of crop yields due to surface O_3 using model-simulated air pollution data in China. We used gridded outputs from the WRF-Chem model, high resolution population data, and crop yield data to evaluate the effects on human health and crop yield in mainland China. Our results showed that outdoor PM_(2.5) pollution was responsible for 1.70–1.99 million cases of all-cause mortality in 2006. The economic costs of these health effects were estimated to be 151.1–176.9 billion USD, of which 90% were attributed to mortality. The estimated crop yield losses for wheat, rice, maize, and soybean were approximately 9, 4.6, 0.44, and 0.34 million tons, respectively, resulting in economic losses of 3.4 billion USD. The total economic losses due to ambient air pollution were estimated to be 154.5–180.3 billion USD, accounting for approximately 5.7%–6.6% of the total GDP of China in 2006. Our results show that both population health and staple crop yields in China have been significantly affected by exposure to air pollution. Measures should be taken to reduce emissions, improve air quality, and mitigate the economic loss.     

Characterization of a new smog chamber for evaluating SAPRC gas-phase chemical mechanism

A new state-of-the-art indoor smog chamber facility (CAPS-ZJU) has been constructed and characterized at Zhejiang University, which is designed for chemical mechanism evaluation under well-controlled conditions. A series of characterization experiments were performed to validate the well-established experimental protocols, including temperature variation pattern, light spectrum and equivalent intensity (J_NO2), injection and mixing performance, as well as gases and particle wall loss. In addition, based on some characterization experiments, the auxiliary wall mechanism has been setup and examined. Fifty chamber experiments were performed across a broad range of experimental scenarios, and we demonstrated the ability to utilize these chamber data for evaluating SAPRC chemical mechanism. It was found that the SAPRC-11 can well predict the O₃ formation and NO oxidation for almost all propene runs, with 6 hr Δ(O₃ – NO) model error of –3% ± 7%, while the final O₃ was underestimated by ~20% for isoprene experiments. As for toluene and p-xylene experiments, it was confirmed that SAPRC-11 has significant improvement on aromatic chemistry than earlier version of SAPRC-07, although the aromatic decay rate was still underestimated to some extent. The model sensitivity test has been carried out, and the most sensitive parameters identified are the initial concentrations of reactants and the light intensity as well as HONO offgasing rate and O₃ wall loss rate. All of which demonstrated that CAPS-ZJU smog chamber could derive high quality experimental data, and could provide insights on chamber studies and chemical mechanism development.     

Hygroscopicity of particles generated from photooxidation of α-pinene under different oxidation conditions in the presence of sulfate seed aerosols

Smog chamber experiments were conducted to investigate the hygroscopicity of particles generated from photooxidation of α-pinene/NOx with different sulfate seed aerosols or oxidation conditions. Hygroscopicity of particles was measured by a tandem differential mobility analyzer （TDMA） in terms of hygroscopic growth factor （Gf）, with a relative humidity of 85%. With sulfate seed aerosols present, Gf of the aerosols decreased very fast before notable secondary organic aerosols （SOA） formation was observed, indicating a heterogeneous process between inorganic seeds and organic products might take place as soon as oxidation begins, rather than only happening after gas-aerosol partition of organic products starts. The final SOA-coated sulfate particles had similar or lower Gf than seed-free SOA. The hygroscopicity of the final particles was not dependent on the thickness but on the hygroscopicity properties of the SOA, which were influenced by the initial sulfate seed particles. In the two designed aging processes, Gf of the particles increased more significantly with introduction of OH radical than with ozone. However, the hygroscopicity of SOA was very low even after a long time of aging, implying that either SOA aging in the chamber was very slow or the Gf of SOA did not change significantly in aging. Using an aerosol composition speciation monitor （ACSM） and matrix factorization （PMF） method, two factors for the components of SOA were identified, but the correlation between SOA hygroscopicity and the proportion of the more highly oxidized factor could be either positive or negative depending on the speciation of seed aerosols present.     

Hygroscopicity of particles generated from photooxidation of α-pinene under diferent oxidation conditions in the presence of sulfate seed aerosols

Smog chamber experiments were conducted to investigate the hygroscopicity of particles generated from photooxidation of α-pinene/NOx with diferent sulfate seed aerosols or oxidation conditions. Hygroscopicity of particles was measured by a tandem diferential mobility analyzer(TDMA) in terms of hygroscopic growth factor(Gf), with a relative humidity of 85%. With sulfate seed aerosols present, Gf of the aerosols decreased very fast before notable secondary organic aerosols(SOA) formation was observed, indicating a heterogeneous process between inorganic seeds and organic products might take place as soon as oxidation begins, rather than only happening after gas-aerosol partition of organic products starts. The final SOA-coated sulfate particles had similar or lower Gf than seed-free SOA. The hygroscopicity of the final particles was not dependent on the thickness but on the hygroscopicity properties of the SOA, which were influenced by the initial sulfate seed particles. In the two designed aging processes, Gf of the particles increased more significantly with introduction of OH radical than with ozone. However, the hygroscopicity of SOA was very low even after a long time of aging, implying that either SOA aging in the chamber was very slow or the Gf of SOA did not change significantly in aging. Using an aerosol composition speciation monitor(ACSM) and matrix factorization(PMF) method, two factors for the components of SOA were identified, but the correlation between SOA hygroscopicity and the proportion of the more highly oxidized factor could be either positive or negative depending on the speciation of seed aerosols present.     

Comparisons of two serious air pollution episodes in winter and summer in Beijing

Characteristics of two serious air pollution episodes(9–15 January, as the winter case; and30 June to 1 July, as the summer case), which occurred in Beijing in 2013 were investigated and compared using multi-method observations and numerical simulations. During these two air pollution episodes, PM_(2.5) concentrations varied significantly within Beijing, with PM_(2.5) concentrations in southern parts of Beijing being significantly higher than in northern areas. Typically, heavy air pollution episodes begin in the southern parts and disperse towards the northern parts of Beijing. Clearly, synoptic patterns and the stability of atmospheric circulation patterns were the main factors controlling air pollution in Beijing.During the winter case, a warm center above 900 h Pa occurred over Beijing. Meanwhile, in the summer case, although there was only a weak inversion, the convective inhibition energy was strong(over 200 J/k G). This clearly influenced the duration of the air pollution event. Except for the local accumulation and secondary atmospheric reactions in both cases, regional straw burnings contributed a lot to the PM_(2.5) concentrations in summer case.Using the CAMxmodel, we established that regional transport contributed almost 59% to the PM_(2.5) averaged concentration in Beijing in the winter case, but only 31% in the summer case. Thus, the winter case was a typical regional air pollution episode, while the summer case resulted from local accumulation straw burnings transportation and strong secondary atmospheric reactions. Given that air pollution is a regional problem in China, consistent and simultaneous implementation of regional prevention and control strategies is necessary to improve regional air quality.     

Photochemical pollution in Lanzhou, China - A case study

The photochemical air pollution in Xigu district of Lanshou city, Gansu Province was studied during a period of 1981-1984. The extremely high NMHC/NOx ratio and ozone level elevation after rain have been noticed. A series of outdoor and indoor reaction chamber simulation experiments conducted in order to understand the specific conditions. The ozone formation under NMHC/NOx condition and the possible reason for high ozone concentration after rain are discussed.     

Effects of seed aerosols on the growth of secondary organic aerosols from the photooxidation of toluene

Hydroxyl radical （.OH）-initiated photooxidation reaction of toluene was carried out in a self-made smog chamber. Four individual seed aerosols such as ammonium sulfate, ammonium nitrate, sodium silicate and calcium chloride, were introduced into the chamber to assess their influence on the growth of secondary organic aerosols （SOA）. It was found that the low concentration of seed aerosols might lead to high concentration of SOA particles. Seed aerosols would promote rates of SOA formation at the start of the reaction and inhibit its formation rate with prolonging the reaction time. In the case of ca. 9000 pt/cm^3 seed aerosol load, the addition of sodium silicate induced a same effect on the SOA formation as ammonium nitrate. The influence of the four individual seed aerosols on the generation of SOA decreased in the order of calcium chloride〉sodium silicate and ammonium nitrate〉ammonium sulfate.     

Effects of elevated ozone on growth and yield of field-grown rice in Yangtze River Delta, China

With rapid industrialization and urbanization in the Yangtze Delta, China, the tropospheric ozone concentration has increased to levels that induce crop yield loss. Rice, a widely grown crop in China, was investigated in field-established, open-top chambers. Four treatments were used： charcoal-filtered air （CF）, non-charcoal-filtered air （NF）, and charcoal-filtered air with two levels of additional ozone （O3-1 and O3-2）. The AOT40s （accumulated hourly mean ozone concentration above 40 ppbv） were 0, 0.91, 23.24, and 39.28 ppmv.h for treatment of CE NF, O3-1, and O3-2, respectively. The rice height and biomass were reduced in the elevated ozone concentration. Less organic matter partitioning to roots under the elevated ozone significantly decreased rice root activity. The yield loss was 14.3% and 20.2% under O3-1 and O3-2 exposure, respectively. This was largely caused by a reduction in grain weight per panicle.     

Differences of the oxidation process and secondary organic aerosol formation at low and high precursor concentrations

Current atmospheric quality models usually underestimate the level of ambient secondary organic aerosol(SOA), one of the possible reasons is that the precursors at different concentrations may undergo different oxidation processes and further affect SOA formation. Therefore, there is a need to perform more chamber studies to disclose the influence. In this work, SOA formation over a wide range of initial precursor concentrations(tens of ppb to hundreds of ppb levels) was investigated in a 30 m3 indoor smog chamber,and mainly through the analysis of multiple generations of VOCs detected from HR-To FPTRMS to expound the difference in the oxidation process between low and high precursor concentrations. Compared to high initial concentrations, gas-phase intermediates formed at low concentrations had a higher intensity by about one order of magnitude, and the lowvolatility compounds also had a higher formation potential due to the competition between semi-volatile intermediates and precursors with oxidants. In addition, the formed SOA was more oxidized with higher f44 value(0.14 ± 0.02) and more relevant to real atmosphere than that formed at high concentrations. This work should help to deeply understand SOA formation and improve the performance of air quality models for SOA simulation.     

我国大气环境中汞污染现状

综述了最近几十年中国大气汞的排放、分布、传输和沉降方面的研究.中国人为源每年汞排放量为世界最高,达到500~700t左右,超过全球人为排放量的25%~30%,并以每年4.2%的速度增加.通过已有观测和模型估算,中国来自自然地表过程(包括裸露地、地表水和森林土壤等)的汞排放量与人为源汞排放量相当,不容忽视.中国城市、农村和偏远地区大气汞浓度分布和变化范围很大,城市地区的总气态汞(TGM)浓度是北美和欧洲地区相似城市类型TGM的1.5~5倍左右;中国城市颗粒态汞(PHg)浓度比北美和欧洲地区高出2个数量级;中国沿海地区和偏远的背景区TGM、PHg和活性汞(RGM)低于中国内地城市地区,但是也明显高于背景值和北美和欧洲地区.相应地,高含量的大气汞浓度导致大量的大气汞沉降到地表,城市地区和背景区大气汞沉降分别比北美地区高出1~2个数量级和1~2倍.     

基于CALPUFF大气扩散模式空气环境总量控制对策研究

本文基于CALPUFF大气扩散模式与MM5气象模拟技术,深入开发、解析污染源普查数据,通过对主要污染物源解析和环境质量实测数据拟合,分析区域污染源排放对空气环境质量的影响,研究各类污染源总量控制多种方案,最终提出与环境容量相适应的总量分配方案和相关控制对策,并为包头市中心城区环境质量达标制定控制方案,为科学利用区域大气环境容量提供技术支持。     

Chlorophyll-bleaching by atmospheric pollutants and sunlight

The Science of Nature -     

戈壁荒漠上大气稳定度分类方法探讨和大气湍流变化特征

 为了研究戈壁荒漠上大气扩散规律和边界层结构。根据气象铁塔常规气象观测和湍流观测的结果，分析戈壁荒漠大气边界层温度梯度和湍流变化的一些特征。分析结果表明，同其它下垫面相比温度梯度日变化大，与风速的关系较为奇特。采用通常P─T分类标准直接应用该地区作大气稳定度分类，与实际情况有较大误差，须经适当修改后才能使用。湍流统计量的日夜变化强，表明戈壁荒漠下垫面的热力作用对湍流混合的助长和抑制。这些特征为进一步分析戈壁荒漠上大气边界层结构和大气扩散研究提供了依据。     

大气气溶胶干沉降研究进展

从干沉降速度定义出发,综述了过去几十年来国内外在气溶胶干沉降实验技术和理论方面的主要进展.气溶胶粒子从大气向地表沉降的过程决定于颗粒物的粒径、密度和空气粘性系数,同时受空气动力学阻力、粘滞层阻力和表面收集阻力的影响,这些阻力分别与大气层温度、风速、相对湿度等微气象条件密切相关.获取干沉降速度的方法主要有示踪法、梯度法和涡流相关法等.风速的三维瞬时量、动能、摩擦速度、温度和涡旋扩散系数可由超声风速温度仪测定.由于气溶胶具有很宽的粒径谱分布,通常使用几台仪器（如串联式多级采样器、空气动力学粒径谱分布仪和扫描电迁移率颗粒物粒径谱仪）进行联合测量.干沉降参数化方案中,基于斯托克斯定律的物理模型着重于平衡重力、浮力和阻力的作用,半经验方案则进一步考虑了大气湍流、分子运动以及表面捕获机制包括布朗扩散、碰撞、截留、反弹、热泳和扩散泳.然而,参数化方案预测结果在某些粒径段与外场测量数据仍存在显著差异.结合目前干沉降研究存在的问题,对今后气溶胶干沉降的研究方向和技术方法进行了展望.     

大气中痕量烯烃的观测与分析

 采用两步深冷冻浓缩自动进样系统,配以气相色谱/质谱联机对北京大气中的烯烃进行了连续观测.结果表明,北京市大气中浓度最高的烯烃为C4烯烃,2000年日平均浓度为3.5×10^-9±3.0×10^-9(V/V).2h平均浓度的日变化在春、夏、秋、冬4季各有特点,但基本上呈双峰型模态,峰值分别出现在上午和傍晚;在季节变化中,1、10月份大气中C4烯烃的浓度最高,为6.0×10-9±1.2×10^-9(V/V),3、9月份最低,为0.31×10^-9±0.13×10^-9(V/V).     

大气中有机硫酸酯研究进展

介绍了国内外大气环境中有机硫酸酯（OSs）的研究现状,分别简述了OSs的理化特征及影响因素、不同分析方法及对应特征、OSs的分类、来源及形成机制、OSs在大气中的转化及归趋等内容,并对目前常见的OSs分子式和结构式以及三种典型的形成机制进行了归纳总结.聚焦目前OSs研究的前沿领域,探讨了目前OSs研究中有待解决的热点问题,并对未来的研究工作提出建议与展望.     

林地大气氮沉降的观测研究

 2004年11月～2005年10月,以小叶栎林地为研究对象,研究了大气沉降氮通量及其3种物理形态(气态、颗粒态、雨水)4种氮化物(NH₃,NH₄⁺-N,NO₃^--N,NO₂)的相对贡献.结果表明,大气氮沉降总量为82.8kg/(hm²·a),其中干沉降占67%;NH3-N是氮沉降的主要贡献者,占干沉降的82%,占总氮沉降量的56%;还原态的氮化物(NH₃,NH₄⁺-N)占总氮沉降量65%.