香河地区冬季NO2光解速率的变化特征及其估算方法的建立

NO₂的光解速率j(NO₂)是对流层化学研究中的一个重要的参数，它是对流层臭氧（O₃）和OH自由基的形成关键影响因子之一。本文利用香河站2017年11月至2018年1月的观测资料对NO₂的光解速率j(NO₂)、太阳辐射的变化特征，及光解速率与分波段辐射相关性进行分析，在此基础上建立了一套适合于构建香河地区j(NO₂)的参数化方案。结果表明，香河地区的j(NO₂)与太阳辐射的变化趋势基本一致，日变化均呈正午高、早晚低的单峰型。香河地区冬季j(NO₂)的变化范围是0.00046～0.0044 s-1，平均值为0.0029 s-1。j(NO₂)与晴空指数（K_S）和定义的紫外辐射晴空指数（K_UV）存在很好的相关性，因此，利用j(NO₂)与大气质量数和晴空指数的相互依赖关系，基于K_UV构建了适合于香河地区j(NO₂) 的估算方程。由于总辐射是气象站的常规观测要素，晴空指数K_S更容易获取，继而建立了通过K_S参数化计算j(NO₂)的估算方程。利用K_UV和K_S建立的j(NO₂)估算方程的瞬时估算值与观测值的平均相对误差分别为6.5%和13.9%，均方根误差分别为0.00029和0.00051。     

太阳紫外辐射观测及预报研究

简要介绍和分析了国内外太阳紫外辐射观测及预报的发展现状,并对影响到达地面紫外辐射的因子进行了分析。介绍了辽宁省气象科研所研制的辽宁地区紫外辐射强度预报模式,给出了紫外辐射对人体影响的指数级别。     

长春地区紫外光谱（UV-A，UV-B）辐射观测和初步分析

利用我们研制的太阳—大气紫外光谱辐射计，从1992年5月在长春开始试验了野外观测，监视到达地表的太阳直射和大气散射紫外光谱辐射，主要给出长春地区地面紫外辐射，特别是紫外（UV）B段（280～320 nm）光谱辐射的一些基本特点和初步统计特征。由于地表UV-B辐射对生态系统和人类健康有危害作用，其强度随着臭氧减少而增加。该项观测分析将有助于监测和研究臭氧层变薄的实际效应。     

蒸发对比观测及折算系数

利用邢台国家基准气候站1992-2001年4-10月E-601B型与小型蒸发器10年蒸发量观测资料,分别进行了对比分析、离差分析和线性回归分析.结果表明:①两种蒸发器测定的平均蒸发量小型为232.9mm.E 601B型为117.4 mm,差值为115.5 mm.偏大率98.4％;②两种蒸发量4-10月的折算系数为0.504,折算系数与相对湿度、日照时数和风速等气象条件有关;③统计了历年E 601B型4-10月蒸发量的气候估计值,可为刑台地区的气候评价、水量平衡分析和水资源调查等提供依据,并为邢台地区有效利用长序列小型蒸发资料提供了应用途径.     

大气折射率湍流结构系数C_n~2的观测试验

以美国ＮＯＡＡ波传播实验室估算大气折射率湍流结构系数的模式为基础，经过数值试验和观测对比调试，给出了一个得到我国雷达测值验证的实用的估算模式．     

我国西部清洁大气中SO2 和NO2的观测和分析

在我国青海省瓦里关大气本底基准观象台（海拔3810 m,100°54′E,36°17′N）,利用浸渍膜法采集大气中的SO2和NO2，使用离子色谱分析其浓度。1994年8月至1995年7月的测量结果表明，SO2和NO2的平均浓度分别为0.147×10-9和0.055×10-9,SO2和NO2两者具有较好的相关性，其相关系数r=0.87,它们的平均比值为2.6左右。SO2和NO2的浓度受季节和风向的影响，偏东风时浓度较高，偏西风时浓度较低。冬季SO2和NO2的浓度水平较低，而夏季浓度较高。     

上海地区地面太阳紫外辐射的观测和分析

通过对上海地区2001～2003年地面太阳总辐射和紫外辐射观测资料的分析表明：（1）上海地区太阳辐射和紫外辐射年总量分别为4487．1MJ／m^2和149．6MJ/m^2。（2）紫外辐射的季节变化特征十分明显,夏半年（4-9月）各月极大紫外辐射强度远大于冬半年（10月～次年3月）,7月份最强,12月份最弱。（3）不同天气条件下,紫外辐射日变化显示出明显的差异,晴天强且稳定,多云天气波动较大,阴天则次之。（4）紫外辐射占总辐射的比例（η）也显示冬半年低,夏半年高的分布特征。（5）影响上海地区到达地面紫外辐射的主要因子有：太阳高度角的大小大致决定了到达地面紫外辐射的强弱,两者具有相近的年变化趋势;云、雨等天气类型是影响紫外辐射的重要因子;大气能见度对紫外辐射也有比较明显的影响。     

北京地区太阳紫外辐射的观测与分析研究

利用北京地区太阳辐射和其它常规气象观测资料，得到了到达地面的太阳紫外辐射的计算公式，并将计算值与观测值进行了比较，两者吻合得比较好。最后给出了北京地区地面太阳紫外总辐射的变化趋势，计算结果表明，地面太阳紫外总辐射对大气浑浊度的变化比对大气臭氧总量的变化敏感得多。     

CO2激光辐射谱线的大气衰减特性

我们于1986年8月在成都市实地测量了CO_2激光辐射00°l—10°0和00°1—02°0振动带内40条谱线在大气中的衰减。文中给出了各谱线衰减系数的一般值并描述了衰减特征。在八月份成都地区的特定条件下,水蒸汽的吸收和气溶胶粒子的吸收与散射构成了衰减的主要部分。测得的各谱线的衰减系数可为CO_2激光的大气应用提供有益的参考。     

大气折射率湍流结构系数C2n的观测试验

以美国NOAA波传播实验室估算大气折射率湍流结构系数的模式为基础，经过数值试验和观测对比调试，给出了一个得到我国雷达测值验证的实用的C2_n估算模式。     

Near UV absorption spectra and photolysis products of difunctional organic nitrates: Possible importance as NO x reservoirs

Difunctional organic nitrates are important products of the atmospheric reaction of NO₃ radicals with unsaturated hydrocarbons about which relatively little is known. In a continuation of the investigation of the atmospheric chemistry of such compounds, the UV absorption spectra of the following organic dinitrates and keto nitrates have been quantitively measured in the gas phase at 298±2 K and atmospheric pressure: 1,2-propandiol dinitrate, CH₃CH(ONO₂)CH₂(ONO₂); 1,2-butandiol dinitrate, CH₃CH₂CH(ONO₂)CH₂(ONO₂); 2,3-butandiol dinitrate, CH₃CH(ONO₂)CH(ONO₂)CH₃;cis 1,4-dinitrooxy-2-butene, CH₂(ONO₂)CH=CHCH₂(ONO₂); 3,4-dinitrooxy-1-butene, CH₂(ONO₂CH(ONO₂)CH=CH₂; -nitrooxy acetone, CH₃COCH₂(ONO₂); 1-nitrooxy-2-butanone, CH₃CH₂COCH₂(ONO₂); 3-nitrooxy-2-butanone, CH₃CH(ONO₂)COCH₃.Although the UV spectra of the nitrates are all very similar in shape those of the keto nitrates are red-shifted compared to the dinitrates and in the spectral range of atmospheric interest (>290 nm) their absorption cross-sections are approximately a factor of 5 higher. The cross-sections of the dinitrates are a factor of 2 higher than those reported in the literature for the corresponding alkyl mononitrates.The UV absorption cross-sections of the difunctional nitrates were used in combination with solar actinic flux data to estimate photolysis frequencies and consequently atmospheric lifetimes for these compounds. The results indicate that for the saturated difunctional nitrates studied in this work photolysis will generally be somewhat some important than reaction with OH radicals as an atmospheric removal process. However, for unsaturated nitrates loss due to reaction with OH will dominate over photolysis as an atmospheric sink.Preliminary FT-IR analyses of the photolysis products of -nitrooxy acetone, 3-nitrooxy-2-butanone and 2,3-butandiol dinitrate using both mercury and fluorescent lamps indicate that NO₂ is released in the primary step. The further reactions of the radicals thus produced result in the formation of CO, aldehydes and PAN. The possible significance of the results for difunctional organic nitrate as reservoirs for reactive odd nitrogen NO _y in the atmosphere, especially during the night, is briefly discussed.     

Field Measurements of Atmospheric Photolysis Frequencies for O3, NO2, HCHO, CH3CHO, H2O2, and HONO by UV Spectroradiometry

A calibrated spectroradiometer was used for the measurement of spectra of the absolute actinic flux F during the POPCORN field campaign in Pennewitt (53.8° N, 11.7° E, sea level) in August 1994. The obtained set of actinic flux spectra was used to determine the photolysis frequencies J(O1D), J(NO2), J(HCHO), J(H2O2), J(HONO), and J(CH3CHO), using molecular photodissociation data from literature. The accuracy of the actinic flux measurement was about ±5%. The accuracy of the photolysis frequency determination is limited by the uncertainties of the molecular absorption cross section and quantum yield data. A good agreement within the experimental uncertainties was found in comparison with measurements of J(O1D) and J(NO2) by filterradiometer which were calibrated absolutely against chemical actinometer. A comparison of this work's photolysis frequency measurements at 40° solar zenith angle with respective measured and modeled data from the literature also shows good agreement for most of the processes considered in this work. However, in the case of J(NO2) data reported in the literature as a function of solar zenith angle differences up to a factor of 1.6 with respect to this work's J(NO2) data are observed. Since this is far beyond the estimated experimental uncertainties, other atmospheric variables, such as aerosols, seem to affect J(NO2) to an extent that is underestimated by now and make indirect comparisons of J(NO2) measurements difficult.     

Intercomparison of remote measurements of stratospheric NO and NO2

During the 1982 and 1983 Balloon Intercomparison Campaigns, the vertical profile of stratospheric NO₂ was measured remotely by nine instruments and that of NO by two. Total overhead columns were measured by two more instruments. Between 30 and 35km, where measurements overlapped, agreement between NO profiles was within ±30%, which is better than the accuracies claimed by the experimenters. Between 35 and 40km there was similarly good agreement between NO₂ profiles, but below 30km, differences of greater than a factor three were found. In the second Campaign, NO₂ values from most instruments agreed within their quoted errors, except that the Oxford radiometer gave much lower values; but the first Campaign and the column measurements show a more uniform spread of results.These differences below 30km could not be resolved, but new laboratory measurements are planned which should do so.     

Slant Column Measurements of O3 and NO2 During the NDSC Intercomparison of Zenith-Sky UV-Visible Spectrometers in June 1996

In June 1996, 16 UV-visible sensors from 11 institutes measured spectra of the zenith sky for more than 10 days. Spectra were analysed in real-time to determine slant column amounts of O3 and NO2. Spectra of Hg lamps and lasers were measured, and the amount of NO2 in a cell was determined by each spectrometer. Some spectra were re-analysed after obvious errors were found. Slant columns were compared in two ways: by examining regression analyses against comparison instruments over the whole range of solar zenith angles; and by taking fractional differences from a comparison instrument at solar zenith angles between 85° and 91°. Regression identified which pairs of instruments were most consistent, and so which could be used as universal comparison instruments. For O3, regression slopes for the whole campaign agreed within 5% for most instruments despite the use of different cross-sections and wavelength intervals, whereas similar agreement was only achieved for NO2 when the same cross-sections and wavelength intervals were used and only one half-day's data was analysed. Mean fractional differences in NO2 from a comparison instrument fall within ±7% (1-sigma) for most instruments, with standard deviations of the mean differences averaging 4.5%. Mean differences in O3 fall within ±2.5% (1- sigma) for most instruments, with standard deviations of the mean differences averaging 2%. Measurements of NO2 in the cell had similar agreement to measurements of NO2 in the atmosphere, but for some instruments measurements with cell and atmosphere relative to a comparison instrument disagreed by more than the error bars.     

Field measurements of NO and NO2 emissions from fertilized and unfertilized soils

Field measurements of NO and NO₂ emissions from soils have been performed in Finthen near Mainz (F.R.G.) and in Utrera near Seville (Spain). The applied method employed a flow box coupled with a chemiluminescent NO _x detector allowing the determination of minimum flux rates of 2 g N m^-2 h^-1 for NO and 3 g m^-2 h^-1 for NO₂.The NO and NO₂ flux rates were found to be strongly dependent on soil surface temperatures and showed strong daily variations with maximum values during the early afternoon and minimum values during the early morning. Between the daily variation patterns of NO and NO₂, there was a time lag of about 2 h which seem to be due to the different physico-chemical properties of NO and NO₂. The apparent activation energy of NO emission calculated from the Arrhenius equation ranged between 44 and 103 kJ per mole. The NO and NO₂ emission rates were positively correlated with soil moisture in the upper soil layer.The measurements carried out in August in Finthen clearly indicate the establishment of NO and NO₂ equilibrium mixing ratios which appeared to be on the order of 20 ppbv for NO and 10 ppbv for NO₂. The soil acted as a net sink for ambient air NO and NO₂ mixing ratios higher than the equilibrium values and a net source for NO and NO₂ mixing ratios lower than the equilibrium values. This behaviour as well as the observation of equilibrium mixing ratios clearly indicate that NO and NO₂ are formed and destroyed concurrently in the soil.Average flux rates measured on bare unfertilized soils were about 10 g N m^-2 h^-1 for NO₂ and 8 g N m^-2 h^-1 for NO. The NO and NO₂ flux rates were significantly reduced on plant covered soil plots. In some cases, the flux rates of both gases became negative indicating that the vegetation may act as a sink for atmospheric NO and NO₂.Application of mineral fertilizers increased the NO and NO₂ emission rates. Highest emission rates were observed for urea followed by NH₄Cl, NH₄NO₃ and NaNO₃. The fertilizer loss rates ranged from 0.1% for NaNO₃ to 5.4% for urea. Vegetation cover substantially reduced the fertilizer loss rate.The total NO _x emission from soil is estimated to be 11 Tg N yr^-1. This figure is an upper limit and includes the emission of 7 Tg N yr^-1 from natural unfertilized soils, 2 Tg N yr^-1 from fertilized soils as well as 2 Tg N yr^-1 from animal excreta. Despite its speculative character, this estimation indicates that NO _x emission by soil is important for tropospheric chemistry especially in remote areas where the NO _x production by other sources is comparatively small.     

The NO2 absorption spectrum. III: The 200–300 nm region at ambient temperature

Absorption cross-section measurements of NO₂ performed in our laboratory have been extended to the 200–300 nm region at ambient temperature. Low pressures have been used, limiting the effects of the dimer N₂O₄ which has an absorption cross-section from one to two orders of magnitude larger than that of NO₂ in this region. The results have been compared to those of previous authors and are now available for atmospheric purposes at 0.01 nm intervals.Unité de Recherche Associée au CNRS.     

The NO2 absorption spectrum. I: Absorption cross-sections at ambient temperature in the 300–500 nm region

New laboratory measurements of NO₂ absorption cross-sections have been performed between 300 and 500 nm at ambient temperature with improved experimental conditions: low gas pressures, long absorption paths, suitable absorbance values, narrow spectral bandwidths. The data, stored at 0.01 nm intervals, have been compared to those of the more recent studies and some reasons of disagreement are discussed.In the photolysis region below 400 nm, our absorption cross-sections are larger than those previously published, suggesting that the photodissociation coefficient calculated from the current data sets is underestimated. In the structured region of the spectrum above 400 nm, improvement of the resolution gives more precise values useful for optical measurements in atmosphere.Unité de Recherche Associée au CNRS.     

北京奥运会期间NO2浓度降低原因分析

2002～2008年,北京市城区和近郊8月的NO2月均浓度大体呈现逐年下降趋势,其中前5年二者均以每年约10%的降幅下降,2008年发生显著下降,降幅达40%左右。利用嵌套网格空气质量模式系统(NAQPM/IAP),采用敏感性试验方法,评估了气象条件与污染控制措施对北京奥运会期间大气NO2浓度降低的影响,评估不同污染控制措施对NO2浓度降低的作用。研究结果表明,污染控制措施是NO2浓度降低的主要影响因素,其中面源的污染控制措施对于NO2浓度降低的作用最明显。     

The equilibrium constant of NO2 with N2O4 and the temperature dependence of the visible spectrum of NO2: A critical review and the implications for measurements of NO2 in the polar stratosphere

Measurements of stratospheric NO₂ by ground-based visible spectrometers rely on laboratory measurements of absorption cross-sections. We review low-temperature laboratory measurements, which disagree by amounts claimed to be significant. Our recalculation of their errors shows that in general disagreements are not significant and that errors in the ratios of cross-sections at low to room temperature are between ±3% and ±8.8%. Of these errors, up to ±3.5% was contributed by errors in the equilibrium constant,K _p, in those measurements where the pressure was above 0.1 mbar.We review measurements and calculations ofK _p, which were accurate to ±5% from 300 to 233 K. Each method was potentially flawed. For example, infrared measurements of the partial pressure of NO₂ ignored the dependence of absorption on total pressure. From thermodynamic theory, formulae forK _pcan be derived from expressions for the variation of heat capacity with temperature. Contrary to common belief, coefficients in the formulae used by spectroscopists were not derived from the thermodynamic quantities. Rather, they were fitted to measurements or to calculations. Hence, they are empirical and it is dangerous to extrapolate below 233 K, the lowest temperature of the measurements.There are no measurements of NO₂ cross-sections below 230 K. Extrapolation of these cross-sections to analysis of measurements of NO₂ at the low temperatures of the Arctic and Antarctic stratosphere is also dangerous. For satisfactory analysis of polar spectra, the NO₂ cross-sections should be measured at temperatures down to 190 K with a relative accuracy of ±1%. This difficult experiment would need a cell of minimum length 32 m whose length can be adjusted. Because their effects are circular, many errors cannot be removed simply. Although circular errors also arise in the measurements ofK _pand of the infrared spectrum, their weights differ from those in the visible spectrum. The optimum experiment might therefore simultaneously measure the visible and infrared spectra andK _p.     

Effect of clouds on the photodissociation of NO2: Observations and modelling

The role of clouds in photodissociation is examined by both modelling and observations. It is emphasized that the photodissociation rate is proportional to the actinic flux rather than to the irradiance. The actinic flux concerns the energy that is incident on a molecule, irrespective of the direction of incidence. The irradiance concerns the energy that is incident on a plane.As far as the modelling aspect is concerned, a multi-layer delta-Eddington model is used to calculate irradiances, actinic fluxes, and photodissociation rates of nitrogen dioxide J(NO₂) as a function of height in inhomogeneous atmospheres. For the considered wavelength interval [290–420 nm], Rayleigh scattering, ozone absorption, and Mie scattering and absorption by cloud drops and aerosols should be taken into account.Further, a three-layer model is used to calculate the actinic flux above and below a cloud, relative to the incident flux, in terms of cloud albedo, zenith angle, and the albedo of the underlying and overlying atmosphere. Cloud albedo is mainly determined by cloud optical thickness. An expression for the incloud actinic flux is given as a function of in-cloud optical thickness. The three-layer model seems to be a useful model for the estimation of photodissociation rates in dispersion models.It is stressed that both models in their present form cannot handle partial cloudiness.It is shown that if no clouds are present, the actinic flux depends primarily on solar zenith angle. Further, the incident flux at the top of the atmosphere diminishes downward into the atmosphere due to the increasing effect of scattering. Therefore, the actinic flux usually increases with height, although above clouds the actinic flux sometimes decreases with height due to a large contribution of the upward scattered light.For cloudy atmospheres, another important parameter with respect to the actinic flux is added: cloud optical thickness. Cloud optical thickness determines cloud albedo. It can be shown that incloud characteristics and cloud height are less important while describing the effect of a cloud on the actinic flux (outside the cloud). The in-cloud values of the actinic flux can exceed the values outside the cloud.Finally, using the photostationary state relationship, a comparison is performed between model results and ground-based measurements as well as in-cloud air craft measurements.