南京市大气细颗粒物化学成分分析

为了解南京大气细粒子的污染水平和污染特征,在南京市中心鼓楼和北郊南京信息工程大学校内进行了连续1a、每季度5d的大气气溶胶同步采样。用称重法、离子色谱法和电感耦合等离子质谱法分别测得细颗粒物的质量浓度、水溶性离子和元素组成。结果表明,南京地区PM2.1污染比较严重,水溶性离子是细粒子的重要组分,所测6种离子质量浓度总和分别占市区和北郊PM2.1的46.99％、42.32％。PM2.1中的各离子最高浓度都出现在冬季。NH^＋4与SO^2-4的相关性好,可能主要以（NH4）2SO4形式存在。温度对SOR和NOR的影响显著,温度升高时SOR值增大而NOR显著减小。通过计算NO^-3与SO^2-4的质量比发现,南京市SO2和NOx主要来自于固定源（如煤的燃烧）。分析细颗粒物中元素含量和富集因子结果表明,Pb、As、Zn、Hg、Cu、Cr、Ni元素的人为污染较明显,且北郊的污染重于市区。比较PM2.1和PM3.3中的离子成分发现,SO^2-4、NH^＋4在PM2.1中占据绝对优势,F^-、Cl^-、NO^-2、NO^-3等不在细粒子中占明显优势。从元素组成来看,Pb、Zn在PM2.1细粒子中含量显著,而Ca、Mg、Na等在粗粒子中富集。     

Characteristics of Aerosol Pollution Under Different Visibility Conditions in Winter in a Coastal Mega-City in China

To investigate chemical profiles and formation mechanisms of aerosol particles in winter haze events,comprehensive measurements including hourly concentrations of PM2.5 and water-soluble inorganic ions and related gasphase precursors were conducted via an online monitoring system from January to March of 2016 in Shenzhen, a coastal mega-city in south China. In this study, high concentrations of PM2.5, NO2 and lower levels of O3 were observed during haze periods in comparison with clear days(Visibility15 km). The major secondary ionic species were NH+4、NO-3 and SO2-4, which varied significantly on haze and clear days. The ratio of NO-3/SO2-4 in haze days was greater than that on clear days and tended to be larger when air pollution became more serious. At the same time, compared with previous studies, it has been found that the ratio has been increasing gradually in Shenzhen, indicating that the motor vehicle exhaust emissions have a more and more important impact on air quality in Shenzhen. Sulfur oxidation rate(SOR) and nitrogen oxidation rate(NOR) was higher during the haze period than that in clean days, indicating efficient gas to particle conversion. Further analysis shows that high concentrations of sulfate might be explained by aqueous oxidation,but gas-phase reactions might dominate nitrate formation. This study also highlights that wintertime nitrate formation can be an important contributor to aerosol particles, especially during haze periods.     

Peroxyacetyl Nitrate (PAN) Measurements During the POPCORN Campaign

During the POPCORN campaign between 3 and 24 August 1994 we measured peroxyacetyl nitrate (PAN) in a rural area of Mecklenburg-Vorpommern (North-Eastern Germany) above a corn field. A total of about 5000 PAN measurements were carried out within the three weeks of the campaign. Measured PAN mixing ratios ranged from below the detection limit of 10 ppt up to an afternoon maximum of 1 ppb. The mean value of all data was 140 ppt. The daily mean PAN mixing ratios were typically in the range of 50 to 250 ppt, but during a clean air episode PAN mixing ratios of well below 40 ppt were observed. The characteristic relative diurnal variation of the PAN mixing ratios with a late night/early morning minimum and an afternoon maximum persisted during these episodes. The daily averages of the PAN mixing ratios showed clear episodic variations which coincided with the duration of typical synoptic episodes of two to six days duration. Based on the measurements of the various parameters determining the PAN formation and destruction rates, the local budget for PAN was calculated. During daytime the calculated net photochemical formation rate of PAN was nearly always significantly higher than the observed change of the PAN concentration. This demonstrates that substantial amounts of PAN (often in the range of several hundred ppt/h) were exported from the corn field. The resulting removal of NOx to some extent effects the budget of nitrogen oxides (NOx), but the export of odd oxygen radicals in the form of PAN during daytime often amounted up to 30–50% of the OH-radical formation by ozone photolysis. Thus the importance of PAN as reservoir and transport medium for odd oxygen radicals can be very substantial and may have a significant impact on the budget and distribution of odd oxygen radicals.     

NUMERICAL SIMULATION OF OZONE DISTRIBUTIONS AND ITS VARIATION MECHANISM

A 2-D global chemistry-transport model is set up in this paper.The model simulates theatmospheric ozone distributions well with specified dynamical conditions.The analysis of ozonevariation mechanism shows that ozone is chemically in quasi-equilibrium except for the polar nightregion where the variation of ozone concentration is under the control of dynamical processes,thatthe oxygen atoms which produce ozone are mainly provided by the photolysis of O_2 in the upperstratosphere and by the photolysis of NO_2 in the lower stratosphere and the troposphere.and thatthe ozone is destroyed mainly by NO_x:the reactions between NO_x and O_3 and the odd oxygen cyclecontribute 80% to more than 90% of the ozone destruction.     

Enhancements of Major Aerosol Components Due to Additional HONO Sources in the North China Plain and Implications for Visibility and Haze

The Weather Research and Forecasting/Chemistry model(WRF-Chem) was updated by including photoexcited nitrogen dioxide(NO2) molecules,heterogeneous reactions on aerosol surfaces,and direct emissions of nitrous acid(HONO) in the Carbon-Bond Mechanism Z(CBM-Z).Five simulations were conducted to assess the effects of each new component and the three additional HONO sources on concentrations of major chemical components.We calculated percentage changes of major aerosol components and concentration ratios of gas NO y(NOyg) to NO y and particulate nitrates(NO-3) to NO y due to the three additional HONO sources in the North China Plain in August of 2007.Our results indicate that when the three additional HONO sources are included,WRF-Chem can reasonably reproduce the HONO observations.Heterogeneous reactions on aerosol surfaces are a key contributor to concentrations of HONO,nitrates(NO 3),ammonium(NH + 4),and PM 2.5(concentration of particulate matter of 2.5 μm in the ambient air) across the North China Plain.The three additional HONO sources produced a～5%-20% increase in monthly mean daytime concentration ratios of NO-3 /NO y,a ～15%-52% increase in maximum hourly mean concentration ratios of NO-3 /NO y,and a ～10%-50% increase in monthly mean concentrations of NO-3 and NH+4 across large areas of the North China Plain.For the Bohai Bay,the largest hourly increases of NO-3 exceeded 90%,of NH+4 exceeded 80%,and of PM 2.5 exceeded 40%,due to the three additional HONO sources.This implies that the three additional HONO sources can aggravate regional air pollution,further impair visibility,and enhance the incidence of haze in some industrialized regions with high emissions of NO x and particulate matter under favorable meteorological conditions.     

Surface ozone concentrations in Agra: links with the prevailing meteorological parameters

Measurements of surface ozone (O₃), nitric oxide (NO), nitrogen dioxide (NO₂), oxides of nitrogen (NO_x=NO+NO₂) and meteorological parameters have been made at Agra (North Central India, 27°10??N, 78°05??E) in post monsoon and winter season. The diurnal variation in O₃ concentration shows daytime in situ photochemical production with diurnal maximum in noon hours ranging from 51 to 54 ppb in post monsoon and from 76 to 82 ppb in winter, while minimum (16?C24 ppb) during nighttime and early morning hours. Average 8-h O₃ concentration varied from 12.4 to 83.9 ppb. The relationship between meteorological parameters (solar radiation intensity, temperature, relative humidity, wind speed and wind direction) and surface O₃ variability was studied using principal component analysis (PCA), multiple linear regression (MLR) and correlation analysis (CA). PCA and MLR of daily mean O₃ concentrations on meteorological parameters explain up to 80 % of day to day ozone variability. Correlation with meteorology is strongly emphasized on days having strong solar radiation intensity and longer sunshine time.     

区域化学输送模式中NO x和O3源示踪法的引入

发展了化学输送模式中氮氧化合物(NOx)和臭氧(O3)的一种源示踪方法,对这种示踪法及其应用模式作了详细介绍,并结合臭氧光化学反应机理的分析描述了NOx和O3示踪物浓度方程的推导过程。将这种示踪法引用到区域化学输送模式中,并以太原和石家庄地表NOx人为排放产生的活性氮化物和臭氧为例,演示了污染物向北京的输送过程,模拟的O3,NOx和NOz示踪物浓度时空分布与O3,NOx和NOz在大气中的衰减尺度分析一致,表明该示踪法是一种有效的研究区域氮氧化物以及臭氧来源和输送转化过程的方法。个例模拟分析结果显示:太原和石家庄的地表人为排放产生的NOx本身并不能输送到北京,但通过它们产生的O3和HNO3可以输送到北京,对北京地表附近大气污染造成影响。     

Measurements of Atmospheric Formaldehyde (HCHO) and Acetaldehyde (CH3CHO) during POPCORN 1994 Using 2.4-DNPH Coated Silica Cartridges

The 2.4-dinitrophenylhydrazine coated silica cartridge technique (DSC) was used for the measurements of HCHO and CH3CHO during the POPCORN campaign in August 1994. A total number of 505 measurements was carried out using an automatic sampling system. The sampling time for each measurement was 30 minutes. During the first two weeks of the campaign samples were taken every 3 hours and during the last two weeks every 30 minutes. No significant diurnal variation of HCHO and CH3CHO was observed. The average mixing ratios of HCHO and CH3CHO were 1.8 ±1.0 ppb and 1.4 ±1.3 ppb. The results for HCHO are in a good agreement with simultaneous measurements by differential optical absorption spectroscopy (DOAS). The absence of a strong diurnal variation of the HCHO mixing ratio can be explained by production and destruction processes during day and night. The measured mixing ratios of HCHO and CH3CHO, especially the mixing ratios during night, are a strong indication that during the POPCORN campaign the maize was a local source of HCHO and CH3CHO.     

临安本底站微量气体浓度分布特征及其对气溶胶的影响

该文讨论了1991年8月下旬至11月上旬在浙江临安大气污染本底站（属WMO）所监测的微量气体SO2、NO2和O3浓度分布特征，微量气体化学转化过程对气溶胶浓度的影响，同时还讨论了空气质点轨迹特征和风向对上述过程的影响。结果表明:临安站微量气体浓度在一定条件下有明显的日变化，而且这种变化影响到气溶胶浓度的分布。     

长江三角洲区域本底大气中致酸气体体积分数变化特征

利用2003-12—2004-11浙江临安区域大气本底站大气NOx、SO2体积分数的连续观测资料,分析其季节变化和日变化特征。结果表明：长江三角洲区域本底大气中致酸气体NOx、SO2体积分数值均为冬季最高,分别为23.81×10^-9和37.3×10^-9,主要受来自东北方向宁、沪区域城市群的相对高浓度污染物随气团传输影响;夏季最低,主要是局地源的贡献。降水对SO2去除作用明显,对NOx去除效果不大。NOx体积分数值冬季的日变化最为明显,呈现出一低一高的双峰型,09：00出现较高体积分数值,18：00出现最高体积分数值;而夏季为单峰型日变化,07：00出现最高体积分数值。SO2冬、春季的日变化明显,最高体积分数值出现在06：00左右,最低体积分数值出现在15：00左右。该区域NO2全年空气质量达到《环境空气质量标准》（GB 30952—1996）一级标准,SO2冬、春季超标较多,受到人类活动影响较明显。NO2和SO2空气污染指数在12月最大,分别为50和93。该区域NO2和SO2并未出现“周末效应”。     

阿克达拉区域大气本底站反应性气体在线观测

为了促进大气成分业务观测水平的提高,对阿克达拉区域大气本底站新建设的NO_x、SO_2、CO和O_3 4种反应性气体集成观测系统的构造、功能以及质量控制方法进行了介绍,分析了在站址科学论证期间观测到的O_3和CO的浓度水平和变化特征,并与其他本底站的观测结果进行了比较,给出了新观测系统的一些初步观测结果。结果表明,阿克达拉站观测到的O_3和CO的浓度水平及其变化特征有别于中国东部几个大气本底站的观测结果,反映了该站与其他站的差异;新的观测系统自动化程度较高、易于实现质量控制,其性能指标能够满足该偏远站点观测的需求。     

SPATIOTEMPORAL VARIATION OF NO2 AND SUB-REGIONAL TRANSPORT DURING WINTER POLLUTION EVENTS IN HAIKOU, CHINA

An ensemble of satellite measurements, statistic data from government and meteorological diagnosis in regional background site (Haikou, China) has revealed the spatial and temporal characteristics of NO2 and associated synoptic transport patterns over southern China from January 2013 to February 2014. The result shows that: (1) Ozone Monitoring Instrument (OMI) satellite products had a good correlation with observation NO2 in Haikou. The correlation coefficients between Observation NO2 and tropospheric column NO2 and ratio of TroNO2/ TotNO2(tropospheric column NO2/ total column NO2) had all passed the confidence level of 99.9% test. (2) TroNO2 over southern China has an obvious seasonal variation, which is closely coupled with regional meteorology in each season. (3) NO2 concentration in Haikou revealed three pollution periods during December 2013 and January 2014. The variation of NO2 concentration in Haikou is related to the meteorological elements closely. (4) Compared to the monthly mean meteorological fields of the pollution periods, the results indicate that NO2 pollution event in Haikou is directly related to the exogenous transportation from PRD region. An ensemble analysis of meteorological dynamic factors, wind vectors and backward trajectories during the pollution periods further verified this conclusion.     

Influence of Atmospheric Particulate Matter on Ozone in Nanjing,China:Observational Study and Mechanistic Analysis

Particulate matter with diameters of 2.5 μm or smaller(PM_(2.5)) and ozone(O_3) are major pollutants in the urban atmosphere. PM_(2.5) can affect O_3 by altering the photolysis rate and heterogeneous reactions. However, these two processes and their relative importance remain uncertain. In this paper, with Nanjing in China as the target city, we investigate the characteristics and mechanism of interactions between particles and O_3 based on ground observations and numerical modeling.In 2008, the average concentrations of PM_(2.5) and O_3 at Caochangmen station are 64.6 ± 47.4 μg m~(-3) and 24.6 ± 22.8 ppb,respectively, while at Pukou station they are 94.1 ± 63.4 μg m~(-3) and 16.9 ± 14.9 ppb. The correlation coefficient between PM_(2.5) and O_3 is -0.46. In order to understand the reaction between PM_(2.5) and O_3, we construct a box model, in which an aerosol optical property model, ultraviolet radiation model, gas phase chemistry model, and heterogeneous chemistry model,are coupled. The model is employed to investigate the relative contribution of the aforementioned two processes, which vary under different particle concentrations, scattering capability and VOCs/NOxratios(VOCs: volatile organic compounds;NOx: nitric oxide and nitrogen dioxide). Generally, photolysis rate effect can cause a greater O_3 reduction when the particle concentrations are higher, while heterogeneous reactions dominate O_3 reduction with low-level particle concentrations.Moreover, in typical VOC-sensitive regions, O_3 can even be increased by heterogeneous reactions. In Nanjing, both processes lead to O_3 reduction, and photolysis rate effect is dominant. Our study underscores the importance of photolysis rate effect and heterogeneous reactions for O_3, and such interaction processes should be fully considered in future atmospheric chemistry modeling.     

Observation of Filterable Bromine Variabilities During Arctic Tropospheric Ozone Depletion Events in High (1hour) Time Resolution

The halogen ions Br^- and Cl^- together with NO₃ ^-, SO₄ ⁼, MSA^- (methane sulfonate), Na⁺ and NH₄ ⁺ were analysed by ion chromatography in extracts of more than 800 aerosol cellulose filter samples taken at Ny Ålesund, Svalbard (79°N, 12°E) in spring 1996 (March 27 - May 16) within the European Union project ARCTOC (Arctic Tropospheric Ozone Chemistry). Anticorrelated variations between f-Br (filterable bromine, i.e. water soluble bromine species that can be collected by aerosol filters) and ozone within the arctic troposphere were evaluated at a resolution of 1 or 2 hours for periods with depleted ozone and 4 hours at normal ozone. A mean f-Br concentration of 11 ng m^-3 (0.14 nmol m^-3) was observed for the whole campaign, while maximum concentrations of 80 ng m^-3 (1 nmol m^-3) were detected during two total O₃-depletion events (O₃ drop to mixing ratios below the detection limit of < 2 ppb). Anticorrelation between f-Br and O₃ was also seen during minor O₃-depletion episodes (sudden drop in O₃ by at least 10 ppb, but O₃ still exceeding the detection limit) and even for ozone variations near its background level (40-50 ppb). A time lag of about 10 hours between the change of ozone and of f-Br concentrations could only be found during a total ozone depletion event, when f-Br reached its maximum values several hours after ozone was totally destroyed. Bromine oxide (BrO) concentrations, measured by DOAS (Differential Optical Absorption Spectroscopy), and f-Br showed a coincident variability during almost the entire campaign (except in the case of total O₃-loss). Frequently enhanced anthropogenic nitrate and sulphate concentrations were observed during O₃-depletion periods. At O₃ concentrations < 10 ppb sulphate and nitrate exceed their typical mean level by 54% and 77%, respectively. This may indicate a possible connection between acidity and halogen release.     

A study of marine aerosols over the Pacific Ocean

Aerosol samples were collected on a Pacific cruise from 47°N to 55°S. Particle morphology, concentrations, and size distributions were analyzed with an electron microscope; elemental compositions of individual particles were determined with an X-ray energy spectrometer; and chemical compositions of bulk samples were measured with an ion chromatograph. Temporal and spatial variations of aerosol physico-chemical characteristics were studied in relation to ocean currents and atmospheric parameters. The results show that number and mass concentrations of primary particles depend mainly on surface wind speeds. However the ratios between the major ions, e.g., Na⁺, Cl^-, and Mg⁺⁺, are similar to the ratios in seawater regardless of location or meteorological conditions. The concentrations of secondary aerosols, e.g., non-seasalt sulfate, nitrate, and ammonium particles, show maxima at upwelling regions, such as along the California coast, at the Equator, and near the Chatham Rise where ascending motion brings nutrient-riched deep water into the surface layer. The number concentrations of small sulfate particles and large nitrate-coated particles showed diurnal variations with maxima in the early afternoon and minima at night, indicating that the particles are the products of photo-chemical reactions. Their precursor gases, e.g., CH₃SCH₃, NO, and NH₃ are known to be released from seawater in upwelling regions where biological activities thrive.     

Nitrous Oxide Evolution from Agricultural Soil: A Regression Approach

N_2O emission from soil is affected by many factors. In this study, N_2O flux, soil temperature, water content, NO_3~- and NH_4~+ concentrations were simultaneously measured in winter wheat field. N_2O flux, NO_3~- and NH_4~+ concentrations were all lognormally distributed, while water content was normally distributed. The relationship between N_2O flux and soil factors was also studied. N_2O flux was most highly correlated with soil temperature. Regression model was developed to explain the variability of N_2O emission from agricultural soil using multifactorial analysis.     

Seasonal and Diurnal Variation of Surface Ozone and a Preliminary Analysis of Exceedance of its Critical Levels at a Semi-arid Site in India

The mixing ratios of surface O₃ were measured at St. John's College, Agra, an urban and traffic influenced area for the period of 2000–2002. The monthly averaged O₃ mixing ratios ranged between 8 to 40 ppb with an annual average of 21 ppb. Strong diurnal and seasonal variations in O₃ mixing ratios were observed throughout the year except for monsoon season. The mixing ratios of O₃ follow the surface temperature cycle and solar radiation (r = 0.72 and r = 0.65 with temperature and solar radiation, respectively). Concentrations were higher with winds associated with NE and NW direction indicating the impact of pollution sources on surface O₃ concentration. Exceedance of ozone critical level was calculated using the AOT 40 index and found to be 840 ppb.h and 2430 ppb.h for summer and winter seasons, respectively. The present O₃ exposures are lower than the critical level of O₃ and suggest that the present level of O₃ does not have any impact on reduction in crop yields.     

对流层光化学过程中的气粒转化研究

在MM5和RADM耦合的基础上，考虑了NH3的源排放，获得了NH3的时空分布、演变特征；在此基础上，讨论了气体向粒子的转化，结果表明:干气溶胶总量分布与大气中H2SO4、NH3的浓度分布有非常好的对应，富氨环境条件下，产生干气溶胶的多少是由H2SO4浓度决定的；气溶胶中的含水量与干气溶胶的浓度分布没有太多的联系，主要取决于大气中相对湿度的大小。     

Geochemistry of regional background aerosols in the Western Mediterranean

The chemical composition of regional background aerosols, and the time variability and sources in the Western Mediterranean are interpreted in this study. To this end 2002–2007 PM speciation data from an European Supersite for Atmospheric Aerosol Research (Montseny, MSY, located 40 km NNE of Barcelona in NE Spain) were evaluated, with these data being considered representative of regional background aerosols in the Western Mediterranean Basin. The mean PM₁₀, PM_2.5 and PM₁ levels at MSY during 2002–2007 were 16, 14 and 11 µg/m³, respectively. After compiling data on regional background PM speciation from Europe to compare our data, it is evidenced that the Western Mediterranean aerosol is characterised by higher concentrations of crustal material but lower levels of OM + EC and ammonium nitrate than at central European sites. Relatively high PM_2.5 concentrations due to the transport of anthropogenic aerosols (mostly carbonaceous and sulphate) from populated coastal areas were recorded, especially during winter anticyclonic episodes and summer midday PM highs (the latter associated with the transport of the breeze and the expansion of the mixing layer). Source apportionment analyses indicated that the major contributors to PM_2.5 and PM₁₀ were secondary sulphate, secondary nitrate and crustal material, whereas the higher load of the anthropogenic component in PM_2.5 reflects the influence of regional (traffic and industrial) emissions. Levels of mineral, sulphate, sea spray and carbonaceous aerosols were higher in summer, whereas nitrate levels and Cl/Na were higher in winter. A considerably high OC/EC ratio (14 in summer, 10 in winter) was detected, which could be due to a combination of high biogenic emissions of secondary organic aerosol, SOA precursors, ozone levels and insolation, and intensive recirculation of aged air masses. Compared with more locally derived crustal geological dusts, African dust intrusions introduce relatively quartz-poor but clay mineral-rich silicate PM, with more kaolinitic clays from central North Africa in summer, and more smectitic clays from NW Africa in spring.     

合肥市不同天气条件下大气气溶胶粒子理化特征分析

为探讨合肥市霾天气大气气溶胶粒子的组成及来源,在2012-2013年代表性月份用安德森分级采样器在合肥市区进行大气气溶胶粒子采样,并分析各样本中水溶性无机离子成分(NH4+、Mg2+、Ca2+、Na+、 K+、NO2-、NO3-、Cl-、SO42-)。根据同期气象资料把采样背景天气分为晴空、雾、霾、轻雾等4类,详细分析了这4种天气下大气细粒子(指PM2.1)和粗粒子(粒径大于2.1 μm部分)的浓度、组成以及主要离子组分的异同。结果表明:(1)观测期间晴空天多对应空气质量优良,雾、霾天对应轻度到重度污染,从晴空天到雾、霾天,PM2.1浓度大幅度上升,且其占总悬浮颗粒物(TSP)的比例显著上升。(2)从晴空天到雾、霾天,水溶性无机离子质量占PM2.1质量浓度的比例上升,分别为46%(晴空)、67%(霾)、61%(雾)、80%(轻雾)。PM2.1中水溶性无机离子浓度居前3位的雾、霾天是SO42-、NO3-和NH4+,晴空天为SO42-、Ca2+、NO3-。(3)与晴空天相比,霾天PM2.1中水溶性无机离子浓度变化倍数最大的是NO3-(为晴空的6.1倍,下同)、其次是NH4+(3.6倍)和SO42-(3.0倍);雾和轻雾天PM2.1中水溶性无机离子浓度变化最大的是NO3-(>10倍)、其次是NH4+(>5倍)和Cl-(>4.0倍)。(4)4种天气下,与人为污染有关的离子(SO42-、NO3-、Cl-、NH4+)尺度谱存在显著差异,呈双峰型、单峰型、三峰型等;而Ca2+的尺度谱无明显变化,基本上都呈双峰型。(5)在粒径3.3 μm以下,阳、阴离子平衡较好,随着尺度增大变差,且晴空天比雾、霾天差。主要阴离子浓度间、Cl-和Na+间的比值和相关性,在晴空天和雾、霾天差异较大。