NO2 total column evolution during the 1989 spring at Antarctica Peninsula

Ground-based visible differential absorption spectrometry during twilight has been used for NO₂ total column observations at the Antarctica Peninsula, Marambio Base (64S, 56W), during the austral spring of 1989 (9 September to 25 November).Results show moderate NO₂ vertical column levels of 1.5 to 2.5×10¹⁵ molec cm^-2 in the morning and 2 to 3×10¹⁵ molec cm^-2 in the evening until middle October, highly modulated by planetary wave activity. From that date until the end of the period, a steady increase occurs which is associated with the rising of lower stratosphere temperature as the vortex weakens, reaching values of 5×10¹⁵ molec cm^-2 in late November, with small a.m.-p.m. differences. NO₂ is found to be positively correlated to both total ozone and 50 hPa temperature during the entire spring. However, when analyzing the departures from linear trends, a highly negative correlation has been observed from day 301 onwards.     

Fourier transform measurement of NO2 absorption cross-section in the visible range at room temperature

New laboratory measurements of NO₂ absorption cross-section were performed using a Fourier transform spectrometer at 2 and 16 cm^-1 (0.03 and 0.26 nm at 400 nm) in the visible range (380–830 nm) and at room temperature. The use of a Fourier transform spectrometer leads to a very accurate wavenumber scale (0.005 cm^-1, 8×10^-5 nm at 400 nm). The uncertainty on the new measurements is better than 4%. Absolute and differential cross-sections are compared with published data, giving an agreement ranging from 2 to 5% for the absolute values. The discrepancies in the differential cross-sections can however reach 18%. The influence of the cross-sections on the ground-based measurement of the stratospheric NO₂ total amount is also investigated.     

Satellite Measurements of Tropospheric Column O<Subscript>3</Subscript> and NO<Subscript>2</Subscript> in Eastern and Southeastern Asia: Comparison with a Global Model (MOZART-2)

Satellite measurements of tropospheric column O₃ and NO₂ in eastern and southeastern Asia are analyzed to study the spatial and seasonal characteristics of pollution in these regions. Tropospheric column O₃ is derived from differential measurements of total column ozone from Total Ozone Mapping Spectrometer (TOMS), and stratospheric column ozone from the Microwave Limb Sounder (MLS) instrument on the Upper Atmosphere Research Satellite (UARS). The tropospheric column NO₂ is measured by Global Ozone Monitoring Experiment (GOME). A global chemical and transport model (Model of Ozone and Related Chemical Tracers, version 2; MOZART-2) is applied to analyze and interpret the satellite measurements. The study, which is based on spring, summer, and fall months of 1997 shows generally good agreement between the model and satellite data with respect to seasonal and spatial characteristics of O₃ and NO₂ fields. The analysis of the model results show that the industrial emission of NO_x (NO + NO₂) contributes about 50%–80% to tropospheric column NO₂ in eastern Asia and about 20%–50% in southeastern Asia. The contribution of industrial emission of NO_x to tropospheric column O₃ ranges from 10% to 30% in eastern Asia. Biomass burning and lightning NO_x emissions have a small effect on tropospheric O₃ in central and eastern Asia, but they have a significant impact in southeastern Asia. The varying effects of NO_x on tropospheric column ozone are attributed to differences in relative abundance of volatile organic compounds (VOCs) with respect to total nitrogen in the two regions.     

Latitudinal variation of measured NO2 photolysis frequencies over the Atlantic Ocean between 50° N and 30° S

Using a filter radiometer, the meridional profile of the NO₂ photolysis frequency, J(NO₂), was measured between 50° N and 30° S during the cruise ANTVII/1 September/October 1988 of the research vessel Polarstern on the Atlantic Ocean. Simultaneously, global broadband irradiance and acrosol were monitored. Clean marine background air with low aerosol loads (b _sp=(1–2)×10^-5 m^-1) was encountered at the latitudes 25° N–30° N and 18° S–27° S, respectively. Under these conditions and an almost cloudless sky J(NO₂) reached 7.3×10^-3 s^-1 (2 sr) for a zenith angle of 30°. Between 30° N and 30° S, the latitudinal variation of the J(NO₂) noontime maxima was less than ± 10%, while the mean value at noon was 7.8×10^-3 s^-1. For the set of all data between 50° N and 30° S, a nearly linear correlation of J(NO₂) vs. global broadland irradiance was found. The slope of (8.24±0.03)×10^-5 s^-1/mW cm^-2 agrees within 10% with observations in Jülich (51° N, 6.2° E).     

Measurements of stratospheric HO2 and NO2 by matrix isolation and ESR spectroscopy

Vertical profiles of stratospheric HO₂ and NO₂ concentrations were determined using matrix isolation and ESR. Up to 10 different samples per flight were collected in situ by a balloon borne cryosampler. Free radicals and trace constituents which are condensable at 68 K are trapped in a polycristalline H₂O or D₂O matrix. After collection, the samples are stored at a temperature below 83 K until they are analysed in the laboratory by X-band ESR spectroscopy at 4 K. The HO₂ and NO₂ were identified and calibrated by comparison with standard samples collected in the laboratory under typical stratospheric sampling conditions. From several flights over Southern France (44°N) we obtained two profiles of the stratospheric NO₂ mixing ratio. One, from 21 October 1982, agrees well with previous measurements. The other, from 8 October 1981, is lower by one order of magnitude. The few HO₂ data obtained around 35 km altitude agree with previous measurements. An isolated measurement at 17 km altitude is one order of magnitude higher than the model predicted HO₂ concentration.     

Measurement of the photodissociation coefficient of NO2 in the atmosphere: II,stratospheric measurements

The photodissociation coefficient of NO₂, J _{NO 2}, has been measured from a balloon platform in the stratosphere. Results from two balloon flights are reported. High Sun values of J _{NO 2} measured were 10.5±0.3 and 10.3±0.3×10^-3 s^-1 at 24 and 32 km respectively. The decrease in J _{NO 2} at sunset was monitored in both flights. The measurements are found to be in good agreement with calculations of J _{NO 2} using a simplified isotropic multiple scattering computer routine.     

Simultaneous measurements of peroxy and nitrate radicals at Schauinsland

We present simultaneous field measurements of NO₃ and peroxy radicals made at night in a forested area (Schauinsland, Black Forest, 48° N, 8° N, 1150 ASL), together with measurements of CO, O₃, NO _x , NO _y , and hydrocarbons, as well as meteorological parameters. NO₂, NO₃, HO₂, and (RO₂) radicals are detected with matrix isolation/electron spin resonance (MIESR). NO₃ and HO₂ were found to be present in the range of 0–10 ppt, whilst organic peroxy radicals reached concentrations of 40 ppt. NO₃, RO₂, and HO₂ exhibited strong variations, in contrast to the almost constant values of the longer lived trace gases. The data suggest anticorrelation between NO₃ and RO₂ radical concentrations at night.The measured trace gas set allows the calculation of NO₃ and peroxy radical concentrations, using a chemical box model. From these simulations, it is concluded that the observed anthropogenic hydrocarbons are not sufficient to explain the observed RO₂ concentrations. The chemical budget of both NO₃ and RO₂ radicals can be understood if emissions of monoterpenes are included. The measured HO₂ can only be explained by the model, when NO concentrations at night of around 5 ppt are assumed to be present. The presence of HO₂ radicals implies the presence of hydroxyl radicals at night in concentrations of up to 10⁵ cm^–3.     

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.     

Vertical column abundances and seasonal cycle of acetylene,C2H2, above the Jungfraujoch station,derived from IR solar observations

Monthly mean total vertical column abundances of acetylene have been determined from series of infrared solar spectra recorded at the Jungfraujoch station, Switzerland, between June 1986 and April 1991. The data have been obtained by nonlinear least-squares fittings of the ₅ band R19 transition of C₂H₂ at 776.0818 cm^-1. The average of 22 monthly mean total vertical columns of C₂H₂ retrieved during that time interval of almost 5 years was found to be equal to (1.81±0.12)×10¹⁵ molec/cm², which corresponds to an average mixing ratio of (0,22±0.013) ppbv (parts per billion by volume) in a troposphere extending from the altitude of the station (3.58 km), up to 10.5 km. Despite the large variability found from year to year, a least-squares sine fit to the data reveals a seasonal variation with an amplitude of about ±40% of the mean; the maximum occurs during mid-winter and the minimum in the summer. The present results are compared critically with similar in-situ data found in the literature. A sinusoidal fit to all such free troposphere measurements made in-situ between 30°N and 60°N indicates good agreement in shape and phase with the seasonal variation derived above the Jungfraujoch, but their average column abundance, 2.3×10¹⁵ molec/cm², is about 30% higher; this difference is explained on the basis of non-upwelling meteorological conditions generally prevailing during ground-based remote solar observations.     

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.     

Simulations of seasonal variations of sulfur compounds in the remote marine atmosphere

A photochemical box model is used to simulate seasonal variations in concentrations of sulfur compounds at latitude 40° S. It is assumed that the hydroxyl radical (OH) addition reaction to sulfur in the dimethyl sulfide (DMS) molecule is the predominant pathway for methanesulfonic acid (MSA) production, and that the rate constant increases as the air temperature decreases. Concentration of the nitrate radical (NO₃) is a function of the DMS flux, because the reaction of DMS with NO₃ is the most important loss mechanism of NO₃. While the diurnally averaged concentration of OH in winter is a factor of about 8 smaller than in summer, due to the weak photolysis process, the diurnally averaged concentration of NO₃ in winter is a factor of about 4–5 larger than in summer, due to the decrease of DMS flux. Therefore, at middle and high latitudes in winter, atmospheric DMS is mainly oxidized by the reaction with NO₃. The calculated ratio of the MSA to SO₂ production rates is smaller in winter than in summer, and the MSA to non-sea-salt sulfate (nssSO₄ ^2-) molar ratio varies seasonally. This result agrees with data on the seasonal variation of the MSA/nssSO₄ ^2- molar ratio obtained at middle and high latitudes. The calculations indicate that during winter the reaction of DMS with NO₃ is likely to be a more important sink of NO_x (NO+NO₂) than the reaction of NO₂ with OH, and to serve as a significant pathway of the HNO₃ production. If dimethyl sulfoxide (DMSO) is produced through the OH addition reaction and is heterogeneously oxidized in aqueous solutions, half of the nssSO₄ ^2- produced in summer may be through the oxidation process of DMSO. It is necessary to further investigate the oxidation products by the reaction of DMS with OH, and the possibility of the reaction of DMS with NO₃ during winter.     

长三角地区典型城市臭氧及其前体物时空分布特征

基于美国宇航局NASA/AURA卫星臭氧监测仪OMI数据,分析了2005—2014年长三角地区及其典型城市对流层O_3、NO_2柱浓度和HCHO大气总柱浓度的时空分布特征。结果表明:10 a间,长三角地区对流层O_3柱浓度和HCHO总柱浓度呈现增长趋势,O_3增量为0.23ppbv/10 a,HCHO增量为0.07×10~(16) mol/(cm~2·10 a),对流层NO_2柱浓度呈现降低趋势,减量为0.06×10~(15)mol/(cm~2·10 a);长三角地区对流层O_3柱浓度最大值出现在3、4、5月,而对流层NO_2柱浓度最大值出现在1、12月,HCHO总柱浓度最大值出现在6、7月;对流层O_3柱浓度的高值区分布在长三角中部、北部区域,对流层NO_2柱浓度高值区分布于长三角中部,HCHO总柱浓度高值区相对分散,且四季的分布各不相同。O_3与NO_2和HCHO在时间和空间上呈现一定的相关性。     

Measurements of stratospheric NO2 profiles using a gas correlation radiometer in the solar occultation mode

Compact two-channel IR radiometers for solar occultation experiments have been constructed in order to measure concentration profiles of stratospheric trace gases. The instruments can be used as filter-or gas correlation-type radiometers depending on the trace gas under investigation. Within the LIMS correlative measurement program, balloon flights were performed with a payload of up to four of these two-channel radiometers. From the gas correlation-type measurements, profiles of the trace gas NO₂ are inferred for the altitude region between about 20 km and the balloon float level. The data evaluation also includes a comprehensive analysis of the error sources and their effect on the accuracy of the NO₂ profiles. The derived profiles are compared among themselves and are assessed against the observations of other authors by accounting for the diurnal, latitudinal and seasonal changes of NO₂. As a by-product of our measurements, the mean absorption of the O₂ collision-induced band at 6.4 m was determined within the range of the interference filter used and compared with calculations based on known absorption coefficients.     

临安冬夏季SO2、NO2和O3体积分数特征及与气象条件的关系

对临安大气本底站2003-2004年冬、夏季二氧化氮(NO2)、二氧化硫(SO2)、臭氧(O3)进行了分析.结果表明:冬季NO2和SO2平均体积分数分别为19.48×10-9和35.74 x10-9,而夏季的平均体积分数分别为4.81×10-9和8.12×10-9,冬季高于夏季;O3在夏季的平均体积分数为33.55×10-9,略高于冬季的25.44×10-9;夜间NO2和SO2体积分数比白天高,并且NO2呈明显的单峰单谷型分布,O3也呈单峰型但峰值出现在白天.NO2、SO2体积分数存在着明显的“假日效应”,假日比非假日低,周五高于假日和非假日;但O3体积分数没有明显的假日效应.降水对SO2有明显的清除作用,但对NO2的清除作用不明显.与风向对比发现,夏季高体积分数的NO2、SO2都受到NW、WNW风的影响,冬季则分别受NE和SW、SSW风的影响;而O3受风向的影响较复杂,与局地光化学反应有关.     

华北地区香河站对流层NO_2的MAX-DOAS光谱仪观测及变化特征分析

利用中国科学院大气物理研究所香河大气探测综合试验站2010年3月至2012年2月(2年)的多轴差分吸收光谱仪(MAX-DOAS)观测数据和32 m高塔常规气象资料,反演了华北地区香河站对流层NO2柱浓度,分析了该区域NO2柱浓度的季节变化特征。研究表明:可见光455~485 nm、紫外330~370 nm都可以作为MAX-DOAS工作波段很好地反演NO2;香河地区NO2柱浓度夏季最低,几乎保持在2×1016 cm–2以下,春、秋季次之,在3×1016 cm–2上下小范围浮动,冬季最高,可达4.5×1016 cm–2;月平均最低值出现在7月,最高值出现在11月。NO2柱浓度与风速、风向密切相关:来自东边唐山方向的风,风速越大时NO2浓度越高,因为唐山是NO2的高值区之一;其它方向风速越大,浓度越低。春、夏两季NO2柱浓度日变化趋势比较平缓,秋、冬两季日变化明显,秋季正午偏高,冬季早晚偏高。     

Intercomparison of instruments for tropospheric measurements using differential optical absorption spectroscopy

The results of an intercomparison campaign of eight different long path UV-visible DOAS instruments measuring NO₂, O₃ and SO₂ concentrations in a moderately polluted urban site are presented. For effective optical path lengths of 230 and 780 m the overall spread of these measurements (±1) are 5×10¹⁰, 6×10¹⁰ and 1×10¹⁰ molec·cm^-3 (2.0, 2.4, and 0.4 ppb) for these molecules respectively when all instruments used a common set of absorption cross sections. The remaining differences are not completely random and the systematic differences are attributed to the different retrieval methods used for each instrument.     

Aqueous Phase Reaction of HNO4: The Impact on Tropospheric Chemistry

We use a global atmospheric chemistry transport model to study the possible influence of aqueous phase reactions of peroxynitric acid (HNO₄) on the concentrations and budgets of NO_x, SO_x, O₃ and H₂O₂. Laboratory studies have shown that the aqueous reaction of HNO_4aq withHSO^– _3aq, and the uni-molecular decomposition of the NO₄ ^– anion to form NO₂ ^– (nitrite) occur on a time scale of about a second. Despite a substantial contribution of the reaction of HSO^– _3aq with HNO_4aq to the overall in-cloud conversion of SO₂ to SO₄ ^2–, a simultaneous decrease of other oxidants (most notably H₂O₂) more than compensated the increase in SO₄ ^2– production. The strongest influence of heterogeneous HNO₄ chemistry was found in the boundary layer, where calculated monthly average ozone concentrations were reduced between 2% to 10% andchanges of H₂O₂ between –20% to +10%compared to a simulation which ignores this reaction. Furthermore, SO₂ was increased by 10% to 20% and SO₄ ^2–depleted by up to 10%. Since the resolution of our global model does not enable a detailed comparison with measurements in polluted regions, it is not possible to verify whether considering heterogeneous HNO₄ reactions results in a substantial improvement of atmospheric chemistry transport models. However, the conversion of HNO₄ in the aqueous phase seems to be efficient enough to warrant further laboratory investigations and more detailed model studies on this topic.     

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.     

西太平洋地区大气边界层内臭氧的季节变化及其影响因子分析

利用臭氧探空资料,分析了西太平洋地区香港(Hong Kong)、那霸(Naha)和札幌(Sapporo)三个站点2000~2010年期间大气边界层内臭氧(O₃)的季节分布和年变化趋势。结果表明,三个站点O₃的季节分布存在明显的差异。其中,那霸和香港大气边界层内O₃季节平均呈双峰值分布,其峰值分别出现在春季和秋季;而札幌站为单峰分布,峰值出现在春季。造成季节分布差异的主要原因包括人为污染源和自然因素如气象条件。另外,三个站点大气边界层内O₃均呈上升趋势。其中札幌、那霸上升最快,分别达0.80 ppb a-1和0.77 ppb a-1。(ppb表示10-9,下同)香港的年际增长较不明显,但秋季增长却非常明显,高达1.21 ppb a-1。结合GOME (Global Ozone Monitoring Experiment) 和SCIAMACHY (Scanning Imaging Absorption Spectro Meter for Atmospheric Chartography)卫星反演的NO₂数据发现,过去10年中国京津唐和东北地区的对流层内NO₂柱总量增加极为迅速。这些O₃前体物通过远距离输送是导致札幌、那霸O₃浓度增加的主要原因之一。珠江三角洲人为污染源的增加及偏北气流的影响,是导致香港地区秋季O₃增加的主要原因。     

Measurements of stratospheric chlorine monoxide (ClO) from groudbased FTIR observations

Infrared absorption features due to ClO in the lower stratosphere have been identified from groundbased solar absorption spectra taken from Aberdeen, U.K. (57° N, 2° W) on 20 January 1995. A vertical column abundance of 3.42 (±0.47)×10¹⁵ molec cm^-2 has been derived from 13 independent absorption features in the P and R branches of the (0–1) vibration-rotation band of ³⁵ClO, spanning the spectral region 817–855 cm^-1. The observed absorption features are consistent with very high levels of ClO (approximately 2.6 parts per billion by volume (ppbv)) in the altitude range 16–22 km. A comparison of this profile with a 3D chemical transport model profile indicates the observation was made inside the polar vortex and shows good qualitative agreement but the model underestimates the concentrations of ClO. Simultaneous measurements of other species were made including HCl, HF and ClONO₂. These columns yield a value for HCl+ClONO₂+ClO of 7.02±0.65×10¹⁵ molec cm^-2. This is lower than the total inorganic chlorine (ClO _y ) column of 10.7±1.6×10¹⁵ molec cm^-2 estimated from mean measured (HCl+ClONO₂)/HF ratios together with in-vortex HF measurements. The discrepancy is probably due to significant amounts of the ClO dimer (Cl₂O₂) in the lower part of the stratosphere. The measurements of highly elevated levels of ClO are used to estimate O₃ loss rates at the 400, 475 and 550 K levels making assumptions about the probable distribution of ClO and Cl₂O₂. These are compared with loss rates derived from ozone sonde data.