Carbonyls and nonmethane hydrocarbons at rural European sites from the mediterranean to the arctic

Results of regular measurements during 1992–1995 of hydrocarbons and carbonyl compounds for a number of rural European monitoring sites are presented. The measurements are part of the EMEP programme for VOC measurements in Europe. In addition, several years of regular measurements are included from the Norwegian stations Birkenes at the south coast, and Zeppelin Mountain on Spitsbergen in the Arctic. The sampling frequency has been about twice per week throughout the years, implying that a substantial amount of measurement data are available. Almost all the chemical analyses have been performed by one laboratory, the EMEP Chemical Co-ordinating Centre located at NILU, which avoids problems of intercomparison and intercalibration among different laboratories. For the measured concentrations both seasonal and geographical variations are shown and discussed. The diurnal cycles of the hydrocarbon concentrations were studied in detail at one site, where the grab samples by EMEP where compared with a parallel continuous sampler, operated by EMPA, Switzerland. Hydrocarbons linked to natural gas and fuel evaporation become well mixed into the Arctic in the winter, whereas combustion products show a latitudinal gradient. The sum of oxygenated species constitutes about 5–15% of the sum of C₂–C₅ hydrocarbons in winter. In summer they are almost equal in magnitude, consistent with an increasing oxidation of hydrocarbons.     

The marine source of C2-C6 aliphatic hydrocarbons

C₂-C₆ Nonmethane hydrocarbon (NMHC) concentrations in the atmospheric boundary layer and in surface seawater were simultaneously measured during an oceanographic cruise in the intertropical Indian Ocean. NMHC were found to be mainly C₂-C₄ alkenes and C₂-C₃ alkanes. Their concentrations ranged from 1 to 30×10^–9 l/l in the seawater and 0.1 to 15 ppbv in the atmosphere. Seawater appeared to be a source because the C₂-C₆ NMHC were supersaturated with respect to the atmosphere by 2 or 3 orders of magnitude.After a selection of the pure marine atmospheric samples, performed with the help of stable and radioactive continental tracers, we found an identical composition in NMHC of surface air and seawater. This observation enabled us to establish that the gas transfer between sea and air occurred according to nonsteady state processes, and that the fluxes cannot be deduced only from atmospheric measurements. An order of magnitude value of the oceanic source for the different NMHC is however derived from the comparison of their sea water concentrations to that of propane and an independent evluation of the marine source of this last compound.     

Measurements of selected C2-C5 hydrocarbons in the background troposphere: Vertical and latitudinal variations

Meridional cross sections of the concentration of light hydrocarbons are reported. They were obtained from 20. April to 10. May, 1980, during the French research flight STRATOZ II, and cover the latitudes between 60° N and 60° S and the altitudes between 800 mb and 200 mb. The mixing ratios of ethane, ethene, acetylene, propane, propene, n-butane, i-butane, n-pentane, and i-pentane range between 2.0 and 0.02 ppb. Globally, a decrease in concentration with increasing altitude and -in most cases-with decreasing latitude is observed. In addition the 2-dimensional concentration fields show structures of different scales. In particular, isolated maxima of high concentrations are found in the upper troposphere. They point to fast vertical transport between the boundary layer and the upper troposphere. In the present case these maxima seem to be correlated with large scale meteorological systems, such as low pressure regions or the Inter Tropical Convergence Zone. It is argued that the NMHC provide a set of tracers well suited to the detection of fast vertical transport.     

NMHC in the marine atmosphere: Preliminary results of monitoring at Amsterdam Island

Between January 1984 and May 1987, C₂ to C₅ NMHC concentrations, and Radon-222 activities were measured at Amsterdam Island in the Indian Ocean. A large variability of about one order of magnitude was observed in the NMHC concentrations. Most of the samples were collected under marine influence. Using ethene as a reference compound for marine emissions, it appears that the NMHC/ethene composition of the air and its variability directly reflect the composition of dissolved gases in surface seawater. Only the ethane/ethene ratio presents a significant deviation from this typical composition and this can be attributed to a continental component. At sea level, the reation frequency of OH radicals with the NMHC is similar to that of methane and carbon monoxide. Thus, the contribution of marine NMHC should be taken into account in the modelling of oxidants in remote atmospheres.     

北京大气甲烷季变化及发展趋势

近年来北京大气中CH4含量仍在上升,但平均增长率已从1985～1989年的1.76%.a-1,下降到1990～1997年的0.50%.a-1;冬季和夏季两次出现峰值,表现出明显的双峰模态季节变化。但北京大气CH4变化的最大特点是年际季变化不均一,12年中,北京大气CH4共计增长185×10-9混和体积比,其中冬季增长的贡献为69×10-9混和体积比,约占总增长的37%;而夏季的增长贡献不足40×10-9混和体积比,约占总增长的21%。90年代以后,北京大气CH4增长率进一步减慢,主要原因是生物源排放不再增加,而非生物源排放量的增长是大气CH4继续增长的主要原因。     

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.     

Small-particle concentration fluctuations at a coastal site

Aerosol size spectra (d=10 nm–10 μm) were measured with an electrical aerosol spectrometer (EAS) at Mace Head on the west coast of Ireland. Several small aerosol particle (diameter 10–32 nm) concentration bursts were observed during the measurement period. Relationships between the events, air mass trajectories, tide height, and meteorological parameters are examined. Series of bursts were observed when a spectral transformation due to subsequent particle growth from 10 to 56–100 nm can be identified in an Eulerian experiment. Particle growth rates of between 1 and 3 nm/h were determined. These bursts appear in cold and comparatively clean arctic or polar air masses with temperature and relative humidity fluctuations, and do not correlate with low tide in some cases. These episodes, similar to those frequently found in the continental boundary layer, are thought to occur over a wide area and, for clear detection, require stable airflow for a few days. Elevated small-particle concentration events are more common during low tide or shortly after, and are typically associated with low wind speeds. Here, the increased shore exposure during low tide is thought to influence the nucleation and the subsequent growth of these aerosol particles. The occurrences of the bursts are found to depend on local wind direction. The highest d=10–32 nm particle concentrations appeared for wind sectors furthest from the tidal regions when the wind direction was 150–160°(south-easterly). Most of the events occurred during daytime when solar irradiation is most intense.     

Atmospheric concentrations of PAHs, their possible sources and gas-to-particle partitioning at a residential site of Bursa, Turkey

Atmospheric PAH concentrations were determined in Gulbahce district of Bursa, Turkey between August 2004 and April 2005. Measured PAH concentrations were classified as heating and non-heating season samples. The concentrations of total PAHs in heating season were almost ten times higher than those in non-heating season. Diagnostic ratios and factor analysis results show that in the heating season traffic along with residential heating emissions heavily influence PAH concentrations. The plot of logK_p versus logP_L⁰ for all the data set of heating and non-heating season samples gave significantly different slopes. The slope for the heating season samples (− 0.92) was steeper than the one for the non-heating season samples (− 0.78). The partitioning results for individual samples further indicated that slope values varied depending on air parcel trajectories. Air parcels traveled over water (either over the Black Sea or Aegean Sea) prior to arriving at the sampling site had less steep slopes. Partitioning of PAHs was also investigated by comparing experimentally determined K_p values with the results obtained both from octanol-based model (K_p(Oct.)) and soot and octanol-based model (K_p (Soot + Oct.)). Both models were useful in predicting the experimental K_p values. However, they did not explain the observed variability in the experimental K_p values.     

根据Brewer和TOMS资料分析、验证瓦里关地区大气臭氧总量变化特征

通过对1 9 9 3年9月~2 0 0 3年1 1月瓦里关地区(3 6.1 7°N,1 0 0.5 3°E)Brewer资料和TOMS资料的比较分析,结果表明:1)瓦里关Brewer臭氧光谱仪的观测数据与卫星的TOMS观测数据之间存在一定的差异,两者的差异8 0%以上集中在-2.5%~2.5%之间;2)1 9 9 3~2 0 0 3年瓦里关地区的大气臭氧总量有着明显的下降趋势,这与北半球中纬度地区观测到的平流层臭氧减少的趋势相吻合;3)瓦里关地区大气臭氧总量存在明显的年际变化和季节变化,且每年的2~4月较高,8~1 0月较低,一年中振荡的幅度达到6 0 DU;4)TOMS两个版本的观测数据与地面观测结果呈现出较好的一致性和相关性,相关系数达到0.9以上。     

大气季节内振荡研究进展

在简单回顾大气季节内振荡(MJO)的特征、热带和中高纬MJO的联系及其在半球间相互作用的基础上,较系统地总结了近年来关于MJO的研究进展,涉及MJO和ElNino的关系、MJO的动力学机制及其季节变化和年际异常,并简单讨论了MJO研究中存在的问题及未来的研究前景。     

大气季节内振荡研究进展

在简单回顾大气季节内振荡(MJO)的特征,热带和中高纬MJO的联系及其在半球间相互作用的基础上,较系统地总结了近年来关于MJO的研究进展,涉及MJO和El Nino的关系,MJO的动力学机制及其季节变化和年际异常,并简单讨论了MJO研究中存在的问题及未来的研究前景.     

欧洲地区夏季热浪的特征及其与阻塞环流的联系

选取了一个热浪指数,利用地面2 m气温场和500 h Pa位势高度场的美国环境预报中心和国家大气研究中心(NCEP/NCAR)再分析资料,通过聚类分析发现欧洲大陆容易产生6类热浪:西欧型(WE)、俄罗斯型(RU)、东欧型(EE)、斯堪的纳维亚半岛型(SC)、北海型(NS)、伊比利亚半岛型(IB);这些热浪事件都与欧洲大陆阻塞的位置有关。同时我们发现这6类热浪发生的频率出现明显的年代际变化,特别在20世纪80年代以后欧洲大陆热浪发生频率明显的增多趋势可能与欧洲大陆增暖背景有关,而欧洲大陆热浪发生频率的年代际变化可能是夏季北大西洋涛动(NAO)的年代际变化的结果。夏季NAO偶极子通过欧洲地区的阻塞异常对欧洲大陆气温有重要的调制作用。当夏季NAO指数处于正位相阶段时,欧洲大陆容易产生高纬度热浪,反之则容易产生低纬度热浪,并且欧洲大陆增暖趋势并不影响NAO对欧洲气温的调制作用。同时还发现:大西洋夏季NAO事件可以是欧洲热浪发生的前期条件,欧洲大陆阻塞异常落后于NAO事件1~5 d,其中IB型和WE型与NAO同期相关,其余4类型热浪对应阻塞落后于NAO 4~5 d。另外,也发现大西洋—欧洲大陆定常波列正距平的位置通过对欧洲阻塞的影响,而影响欧洲热浪发生的频率和位置。     

Variation Characteristics of Ambient NMHCs at Shangdianzi and Lin＇an Regional GAW Sites

In order to study the variation characteristics of concentration of the atmospheric non-methane hydrocarbons (NMHCs) in background area of China, the atmospheric concentrations of NMHCs were measured at Lin'an (LA) regional GAW (Global Atmosphere Watch) Station (30°25'N, 119°44'E; 132.0 m ASL) and Shangdianzi (SDZ) regional GAW Station (40°19'N, 117°07'E; 286.5 m ASL) with the sorbent sorp-tion/thermal desorption/gas chromatographic method. Totally 145 samples were collected during the period of October 2003 and July 2004. Among the 52 NMHC species of C2-C10 detected there were 26 alkanes, 17 alkenes, and 9 aromatics. The average concentrations of total NMHCs (TNMHCs) at LA and SDZ were (238.5±126.0)×KT9C and (278.7±185.5)x10-9C, respectively. The results showed the ambient concentrations of TNMHCs at LA regional GAW Station increased notably over the last decade. The compositions of NMHCs at SDZ and LA were relatively similar. The proportions of alkanes, alkenes, and aromatics for SDZ and LA were hi ranges of (27.3±4.0)%, (10.3±3.5)%, and (62.5±4.8)%, respectively, with features of vehicle exhaust emissions. The concentrations of NMHCs at the two sites showed obvious diurnal and seasonal variations. The TNMHC concentrations in October-November were high at the two sites, and relatively low in April and July. The diurnal variation patterns at the sites were different. The high TNMHC concentrations at SDZ normally appeared in evening and night, but appeared in morning at LA. The TNMHCs concentrations at the two sites were significantly influenced by the meteorological condition. The high TNMHC concentration associated with the local wind from the urban areas or traffic in upper reaches.     

Variation Characteristics of Ambient NMHCs at Shangdianzi and Lin''an Regional GAW Sites

In order to study the variation characteristics of concentration of the atmospheric non-methane hydrocarbons (NMHCs) in background area of China, the atmospheric concentrations of NMHCs were measured at Lin'an (LA) regional GAW (Global Atmosphere Watch) Station (30°250'N , 119° 440'E; 132.0 m ASL)and Shangdianzi (SDZ) regional GAW Station (40°190'N , 117°07'E; 286.5 m ASL) with the sorbent sorption/thermal desorption/gas chromatographic method. Totally 145 samples were collected during the period of October 2003 and July 2004. Among the 52 NMHC species of C2-C10 detected there were 26 alkanes,17 alkenes, and 9 aromatics. The average concentrations of total NMHCs (TNMHCs) at LA and SDZ were(238.5±126.0) 10-9C and (278.7±185.5) 10-9C, respectively. The results showed the ambient concentrations of TNMHCs at LA regional GAW Station increased notably over the last decade. The compositions of NMHCs at SDZ and LA were relatively similar. The proportions of alkanes, alkenes, and aromatics for SDZ and LA were in ranges of (27.3±4.0)%, (10.3±3.5)%, and (62.5±4.8)%,respectively, with features of vehicle exhaust emissions. The concentrations of NMHCs at the two sites showed obvious diurnal and seasonal variations. The TNMHC concentrations in October-November were high at the two sites, and relatively low in April and July. The diurnal variation patterns at the sites were different. The high TNMHC concentrations at SDZ normally appeared in evening and night, but appeared in morning at LA. The TNMHCs concentrations at the two sites were significantly influenced by the meteorological condition. The high TNMHC concentration associated with the local wind from the urban areas or trafic in upper reaches.     

河南省近11年大气可降水量变化特征

利用2000-2010年1°×1°的NCEP FNL分析资料,分析了河南大气可降水量的时空分布特征及变化趋势。结果表明：河南省年大气可降水量为270.48 kg/m2,从西北向东南逐渐增加。可降水量季节变化显著,夏季最大,月平均为41.77 kg/m2;冬季最少,月平均为8.54 kg/m2。1月份大气可降水量最少,平均为8.04 kg/m2;7月最多,平均为47.19 kg/m2。11 a来,大气可降水量最多年份是最少年份的1.12倍,大气可降水量年际变化特征不明显,总体上有所减少。     

Climatology of Ozone, PAN, CO, and NMHC in the Free Troposphere Over the Southern North Atlantic

Free tropospheric measurements of ozone, peroxyacetylnitrate andprecursors (CO, NMHC) that were made within the framework of the EUROTRACsub-project TOR (Tropospheric Ozone Research) between 1990 and 1995 at theGAW station Izana, Tenerife (28°18N, 16°30W) arediscussed. The average annual cycles reveal the importance of transport fromnorthern mid-latitudes and the role of photo-chemistry. According toair-mass trajectories, which were supplied to us from AEROCE(Atmosphere/Ocean Chemistry Experiment), transport from northernmid-latitudes is associated with high precursor concentrations in winter,whereas ozone concentrations in winter are not much influenced by transportpatterns, suggesting a rather uniform distribution over the northern part ofthe Northern Hemisphere around mean value of 43 ± 5 ppb. In summer,high ozone concentrations of up to 90 ppb are often encountered duringtransport from north, while the levels of precursors are much lower than inwinter, because of photochemical destruction. Trajectories from southerlylatitudes and the Sahara usually have the lowest ozone concentrationsassociated with them.     

Measurement and calculation of OH reactivity at a United Kingdom coastal site

Measurements of OH reactivity were made at the Weybourne Atmospheric Observatory on the North Norfolk coast, UK in May 2004. A wide range of supporting species was also measured concurrently as part of the TORCH-2 field campaign, allowing a detailed study of the OH oxidation chemistry to be carried out. Measurements were made in a variety of air masses, with the 3 most prevalent being air from the Atlantic that arrived at the site from over mainland UK in a South Westerly direction, and much cleaner Northerly air that originated over the far North Sea or Arctic, passed over the North Sea and arrived at the site from a North/North Easterly direction. Direct OH reactivity measurements were made on 6 days during the campaign and with influence of 2 of the 3 air masses prevalent during the study period. The average, minimum and maximum measured OH reactivity are: 4.9, 1.3 and 9.7 respectively. The measured OH reactivity was compared to key OH sinks such as NO₂ and CO and a general positive correlation was observed. OH reactivity (k′) was then calculated using the full range of OH sinks species that were measured (including >30 NMHCs) and their pseudo first order rate constants for reaction with OH. For much of the measurement period there is a significant difference between the measured and calculated k′, with an average value of k′_meas- k′_calc?=?1.9 s^-1, indicative of unmeasured OH sinks. A zero-dimensional box model containing a subset of the Master Chemical Mechanism was used to calculate the OH reactivity more accurately. The simultaneously measured trace species were used as inputs to the model and their oxidative degradation was described by a chemical mechanism containing ~5,000 species. The extra OH sinks species produced by the model, resulted in an improvement in the agreement between k′_meas and k′_calc, however the averaged missing OH reactivity across the entire measurement period remained at 1.4 s^-1. Speculation is made as to the source of this missing reactivity, including reference to studies showing that a potentially large number of high molecular weight aromatic species could be unmeasured by standard instrumentation.     

Variability of surface roughness and turbulence intensities at a coastal site in India

Surface-layer features with different prevailing wind directions for two distinct seasons (Southwest Monsoon and Northeast Monsoon) on the west coast of India are studied using data obtained from tower-based sensors at a site located about 500 m from the coast. Only daytime runs have been used for the present analysis. The surface boundary-layer fluxes have been estimated using the eddy correlation method. The surface roughnessz ₀ obtained using the stability-corrected wind profiles (Paulson, 1970) has been found to be low for the Southwest monsson season. For the other season,z ₀ is relatively high. The drag coefficientC _D varies with height in the NE monsoon season but not in the season with lowz ₀. This aspect is reflected in the wind profiles for the two seasons and is discussed in detail. The scaling behaviour of friction velocityu _* and the turbulence intensity of longitudinal, lateral and vertical winds _u, _v and _w, respectively) are further examined to study their dependence on fetch. Our study shows that for the non-dimensional case, _u/u_* and _v/u_* do not show any surface roughness dependence in either season. On the other hand, for _w/u_* for the season with lowz ₀, the values are seen to agree well with that of Panofskyet al. (1977) for homogeneous terrain whereas for the other season with highz ₀, the results seem to conform more to the values observed by Smedman and Högström (1983) for coastal terrain. The results are discussed in the light of observations by other investigators.     

Seasonal variations of atmospheric sulfur dioxide and dimethylsulfide concentrations at Amsterdam Island in the southern Indian Ocean

Daily measurements of atmospheric sulfur dioxide (SO₂) concentrations were performed from March 1989 to January 1991 at Amsterdam Island (37°50 S–77°30 E), a remote site located in the southern Indian Ocean. Long-range transport of continental air masses was studied using Radon (²²²Rn) as continental tracer. Average monthly SO₂ concentrations range from less than 0.2 to 3.9 nmol m^-3 (annual average = 0.7 nmol m^-3) and present a seasonal cycle with a minimum in winter and a maximum in summer, similar to that described for atmospheric DMS concentrations measured during the same period. Clear diel correlation between atmospheric DMS and SO₂ concentrations is also observed during summer. A photochemical box model using measured atmospheric DMS concentrations as input data reproduces the seasonal variations in the measured atmospheric SO₂ concentrations within ±30%. Comparing between computed and measured SO₂ concentrations allowed us to estimate a yield of SO₂ from DMS oxidation of about 70%.     

A Modeling Study of Seasonal Variation of Atmospheric Aerosols over East Asia

In this study, a regional air quality model system (RAQMS) wasapplied to investigate the spatial distributions and seasonal variations ofatmospheric aerosols in 2006 over East Asia. Model validations demonstratedthat RAQMS was able to reproduce the evolution processes of aerosol componentsreasonably well. Ground-level PM₁₀ (particles with aerodynamic diameter≤10 μm) concentrations were highest in spring and lowest insummer and were characterized by three maximum centers: the Taklimakan Desert(～1000 μg m^-3), the Gobi Desert (～400 μg m^-3), andthe Huabei Plain (～300 μm^-3) of China. Vertically, highPM₁₀ concentrations ranging from 100 μg m^-3 to 250 μgm^-3 occurred from the surface to an altitude of 6000 m at30^o--45^oN in spring. In winter, the vertical gradient was solarge that most aerosols were restricted in the boundary layer. Both sulfateand ammonium reached their highest concentrations in autumn, while nitratereached its maximum level in winter. Black carbon and organic carbon aerosolconcentrations reached maximums in winter. Soil dust were strongest in spring,whereas sea salt exerted the strongest influence on the coastal regions ofeastern China in summer. The estimated burden of anthropogenic aerosols waslargest in winter (1621 Gg) and smallest in summer (1040 Gg). The sulfateburden accounted for ～42% of the total anthropogenic aerosol burden. Thedust burden was about twice the anthropogenic aerosol burden, implying thepotentially important impacts of the natural aerosols on air quality andclimate over East Asia.