Products and Mechanism of the NO<Subscript>3</Subscript> Reaction with Thiophene

Products of the gas-phase reaction of the NO₃ radical with thiophene have been investigated using different experimental systems. On the one hand, experiments have been conducted in our laboratory using two different methods, a Teflon static reactor coupled to a gas chromatograph combined with mass-spectrometry (GC-MS) and a discharge flow tube with direct MS spectroscopic detection. A qualitative analysis in these cases indicates that possible products for the reaction of thiophene+NO₃ at room temperature include: sulphur dioxide, acetic and formic acids, a short-chain aldehyde, 2-nitrothiophene and 3-nitrothiophene. On the other hand, quantitative experiments have been performed in the European Photoreactor (EUPHORE) in Valencia, Spain. In this case, the major products were: HNO₃ (≈80%), nitrothiophenes (≈30%), SO₂ (≈20%), propanal (3%) and a fraction of particles (≈10%). The results obtained indicate that at least 70% of the reaction of NO₃ with thiophene proceeds by an H-abstraction process at room temperature. The mechanism of the reaction studied is proposed on the basis of experimental results.     

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.     

The Heterogeneous Reaction of NO<Subscript>2</Subscript> with NH<Subscript>4</Subscript>Cl: A Molecular Diffusion Tube Study

The heterogeneous interaction of nitrogen dioxide with ammonium chloride was investigated in a molecular diffusion tube experiment at 295–335 K and interpreted using Monte Carlo trajectory calculations. The surface residence time (τ_surf) of NO₂ on NH₄Cl is equal to 15 μs at 295 K, increases with temperature up to 323 K (τ_surf = 45 μs) and probably decreases beyond 323 K. The same experiment also yields uptake coefficients, γ, which are derived from the absolute number of surviving molecules effusing out of the diffusion tube. The rate of uptake of NO₂ on NH₄Cl followed a rate law first order in [NO₂] and the uptake coefficient γ is equal to 7 × 10⁻⁵ at 295 K, increases with temperature up to 323 K (γ = 2.1 × 10⁻⁴) and probably decreases beyond 323 K. Nitrous acid, water and nitrogen were detected as products. From these products, it is concluded that the reaction of NO₂ with NH₄Cl is a reverse disproportionation reaction where two moles of NO₂ result in ammonium nitrite, NH₄NO₂, as an intermediate, and nitryl chloride, NO₂Cl. NH₄NO₂ decomposes in two pathways, one to nitrous acid, HONO and NH₃, the other to nitrogen and water. The branching ratio for the production of HONO + NH₃ to that of N₂ + H₂O is approximately 20 at 298 K and increases with increasing temperature.     

Sensitivity Analysis of Photochemical Indicators for O<Subscript>3</Subscript> Chemistry Using Automatic Differentiation

Photochemical indicators for determination of O₃–NO_x–ROG sensitivity and their sensitivity to model parameters are studied for a variety of polluted conditions using a comprehensive mixed-phase chemistry box model and the novel automatic differentiation ADIFOR tool. The main chemical reaction pathways in all phases, interfacial mass transfer processes, and ambient physical parameters that affect the indicators are identified and analyzed. Condensed mixed-phase chemical mechanisms are derived from the sensitivity analysis.Our results show that cloud chemistry has a significant impact on the indicators and their sensitivities, particularly on those involving H₂O₂, HNO₃, HCHO, and NO_z. Caution should be taken when applying the established threshold values of indicators in regions with large cloud coverage. Among the commonly used indicators, NO_y and O₃/NO_y are relatively insensitive to most model parameters, whereas indicators involving H₂O₂, HNO₃, HCHO, and NO_z are highly sensitive to changes in initial species concentrations, reaction rate constants, equilibrium constants, temperature, relative humidity, cloud droplet size, and cloud water content.     

Chemical characterization and multivariate analysis of atmospheric PM<Subscript>2.5</Subscript> particles

The new European Council Directive (PE-CONS 3696/07) frames the inhalable (PM₁₀) and fine particles (PM_2.5) on priority to chemically characterize these fractions in order to understand their possible relation with health effects. Considering this, PM_2.5 was collected during four different seasons to evaluate the relative abundance of bulk elements (Cl, S, Si, Al, Br, Cu, Fe, Ti, Ca, K, Pb, Zn, Ni, Mn, Cr and V) and water soluble ions (F⁻, Cl⁻, NO₂ ⁻, NO₃ ⁻, SO₄ ²⁻, Na⁺, NH₄ ⁺, Ca²⁺ and Mg²⁺) over Menen, a Belgian city near the French border. The air quality over Menen is influenced by industrialized regions on both sides of the border. The most abundant ionic species were NO₃ ⁻, SO₄ ²⁻ and NH₄ ⁺, and they showed distinct seasonal variation. The elevated levels of NO₃ ⁻ during spring and summer were found to be related to the larger availability of the NO_x precursor. The various elemental species analyzed were distinguished into crustal and anthropogenic source categories. The dominating elements were S and Cl in the PM_2.5 particles. The anthropogenic fraction (e.g. Zn, Pb, and Cu) shows a more scattered abundance. Furthermore, the ions and elemental data were also processed using principal component analysis and cluster analysis to identify their sources and chemistry. These approach identifies anthropogenic (traffic and industrial) emissions as a major source for fine particles. The variations in the natural/anthropogenic fractions of PM_2.5 were also found to be a function of meteorological conditions as well as of long-range transport of air masses from the industrialized regions of the continent. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

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.     

A modified profile method for determining the vertical fluxes of NO,NO2, ozone,and HNO3 in the atmospheric surface layer

A modified profile method for determining the vertical deposition (or/and exhalation) fluxes of NO, NO₂, ozone, and HNO₃ in the atmospheric surface layer is presented. This method is based on the generally accepted micrometeorological ideas of the transfer of momentum, sensible heat and matter near the Earth's surface and the chemical reactions among these trace gases. The analysis (aerodynamic profile method) includes a detailed determination of the micrometeorological quantities (such as the friction velocity, the fluxes of sensible and latent heat, the roughness length and the zero plane displacement), and of the height-invariant fluxes of the composed chemically conservative trace gases with group concentrations c ₁=[NO]+[NO₂]+[HNO₃], c ₂=[NO₂]+[O₃]+3/2·[HNO₃], and c ₃=[NO]–[O₃]–1/2·[HNO₃]. The fluxes of the individual species are finally determined by the numerical solution of a system of coupled nonlinear ordinary differential equations for the concentrations of ozone and HNO₃ (decoding method). The parameterization of the fluxes is based on the flux-gradient relationships in the turbulent region of the atmospheric surface layer. The model requires only the vertical profile data of wind velocity, temperature and humidity and concentrations of NO, NO₂, ozone, and HNO₃.The method has been applied to vertical profile data obtained at Jülich (September 1984) and collected in the BIATEX joint field experiment LOVENOX (Halvergate, U.K., September 1989).     

Investigating the Halogen Chemistry From High-Latitude Nighttime Stratospheric Measurements of OClO and NO2

Two cases of simultaneous nighttime measurements of NO₂ and OClO in the winter polar stratosphere are analyzed in order to test our present knowledge of halogen chemistry in the presence of high amount of NO₂ at low temperature. Comparisons with Lagrangian model calculations using several hypotheses are performed. First simulations, using the admitted constant rates of chemical reaction, strongly underestimate the measured OClO while the NO₂ profiles are correctly reproduced. If uncertainties in actinic fluxes calculations are taken into account, simulation results do not show a significant reduction of the underestimation. A better agreement can be achieved if the formation of unstable isomers of ClONO₂ and of BrONO₂ occurs in the cold conditions of the polar stratosphere. An approximate value of the branching ratios of the channels leading to ClONO₂ and ClOONO, and to BrONO₂ and BrOONO, necessary to reproduce both OClO and NO₂ is given and discussed.     

Global financial crisis making a V-shaped fluctuation in NO<Subscript>2</Subscript> pollution over the Yangtze River Delta

The Yangtze River Delta (YRD), China’s main cultural and economic center, has become one of the most seriously polluted areas in the world with respect to nitrogen oxides (NO_x), owing to its rapid industrialization and urbanization, as well as substantial coal consumption. On the basis of nitrogen dioxide (NO₂) density data from ozone monitoring instrument (OMI) and ground-based observations, the effects of industrial fluctuations due to the financial crisis on local NO₂ pollution were quantitatively assessed. The results were as follows. (1) A distinct V-shaped fluctuation of major industrial products, thermal generating capacity, electricity consumption, and tropospheric NO₂ densities was associated with the global financial crisis from May 2007 to December 2009, with the largest anomalies 1.5 times more than standard deviations at the height of the crisis period from November 2008 to February 2009. (2) Among all industrial sectors, thermal power plants were mainly responsible for fluctuations in local NO₂ pollution during the crisis period. Thermal generating capacity had its greatest decrease of 12.10% at the height of the crisis compared with that during November 2007–February 2008, leading to local tropospheric NO₂ density decreasing by 16.97%. As the crisis appeased, thermal generating capacity increased by 29.63% from November 2009 to February 2010, and tropospheric NO₂ densities correspondingly increased by 30.07%. (3) Among all industrial sectors in the YRD, the thermal power sector has the greatest coal consumption of about 65.96%. A decline in thermal power of about 10% can induce a decrease of about 30% in NO_x emissions and NO₂ densities, meaning that a relative small fluctuation in industrial production can lead to a large decrease in tropospheric NO₂ densities over industrially developed areas like the YRD region. Since electricity is mainly obtained from local coal-burning thermal plants without NO_x-processing equipment, installing NO_x-removal devices for all thermal power plants is an important and feasible way of controlling local NO_x pollution at present.     

Comparison of two algorithms for calculating photolysis frequencies including the effects of clouds

Summary Two complex models to determine photolysis frequencies for chemical transport models are used to study the effects of input data and the consideration of relevant physical processes on the derived photolysis frequencies. Within the model CTM photolysis frequencies are calculated on a coarse latitudinal grid with climatological input data (monthly mean or seasonal mean values) and are then interpolated linearly in space to derive photolysis frequencies for each grid cell of the chemical transport model. These clear sky photolysis frequencies are then corrected to account for cloud effects. The model STAR calculates photolysis frequencies for each grid cell considering the relevant physical processes on the basis of actual profiles computed with a mesoscale meteorological model and other available geophysical data.The comparison of the O₃ and NO₂ photolysis frequencies shows that the approach used within the CTM model compares to STAR only under certain conditions, as climatological input data can be less suitable for episodic photolysis frequencies calculations. The ozone column content significantly alters the photolysis frequency of ozone itself and climatological Dobson data limit the quality of the calculations. The temperature dependence of the quantum yields and the absorption cross sections lead to increased uncertainties when climatological temperature profiles are used. This is especially the case for sunrise/sunset conditions. The use of one surface albedo for all landuse types and seasons within the CTM model restricts the quality of the calculations close to the surface. If clouds are present the CTM model over-/underestimates the cloud effects on the photolysis frequencies and differences up to an order of magnitude are found for below cloud values.With 11 Figures     

闪电产生氮氧化物对青藏高原臭氧低谷形成的影响

为了进一步了解青藏高原闪电的产生氮氧化物（LNO_x）经由光化学反应对O₃浓度变化及夏季O₃低谷形成的可能影响,本文利用2005~2013年由OMI卫星得到的对流层NO₂垂直浓度柱（NO₂ VCD）、O₃总浓度柱（TOC）和O₃廓线以及星载光学瞬变探测器OTD和闪电成像仪LIS获取的总闪电数资料,对青藏高原和同纬度长江中下游地区的TOC和NO₂ VCD月均值时空分布特征、闪电与NO₂ VCD的相关性和O₃的垂直分布特征及其与LNO_x的关系进行了对比分析。结果表明,青藏高原的O₃低谷主要出现在夏季和秋季,其TOC值比同纬度长江中下游地区低约10~15 DU（Dobson unit）。青藏高原NO₂VCD总体较小,表现为夏高冬低的分布特征。青藏高原夏季O₃浓度受南亚高压的影响总体呈减小趋势,但因强雷暴天气导致对流层中上部LNO_x浓度升高,并随强上升气流向对流层顶输送,同时通过光化学反应使O₃浓度增加,缩小了青藏高原和同纬度地区的O₃浓度差,减缓了O₃总浓度的下降,抑制了夏季O₃低谷的进一步深化。     

Spectra of CO<Subscript>2</Subscript> and Water Vapour in the Marine Atmospheric Surface Layer

Spectra of CO₂ and water vapour fluctuations from measurements made in the marine atmospheric surface layer have been analyzed. A normalization of spectra based on Monin–Obukhov similarity theory, originally developed for wind speed and temperature, has been successfully extended also to CO₂ and humidity spectra. The normalized CO₂ spectra were observed to have somewhat larger contributions from low frequencies compared to humidity spectra during unstable stratification. However, overall, the CO₂ and humidity spectra showed good agreement as did the cospectra of vertical velocity with water vapour and CO₂ respectively. During stable stratification the spectra and cospectra displayed a well-defined spectral gap separating the mesoscale and small-scale turbulent fluctuations. Two-dimensional turbulence was suggested as a possible source for the mesoscale fluctuations, which in combination with wave activity in the vertical wind is likely to explain the increase in the cospectral energy for the corresponding frequency range. Prior to the analysis the turbulence time series of the density measurements were converted to time series of mixing ratios relative to dry air. Some differences were observed when the spectra based on the original density measurements were compared to the spectra based on the mixing ratio time series. It is thus recommended to always convert the density time series to mixing ratio before performing spectral analysis.     

Uptake of the NO <Subscript>3</Subscript> Radical on Aqueous Surfaces

Using a single drop experiment, the uptake of NO₃ radicals on aqueous solutions of the dye Alizarin Red S and NaCl was measured at 293 K. Uptake coefficients in the range (1.7–3.1) ⋅ 10^{− 3} were measured on Alizarin Red S solutions. The uptake coefficients measured on NaCl solutions were in the range of (1.1–2.0) ⋅ 10⁻³ depending on the salt concentration. Both experiments lead to a consistent result for the mass accommodation coefficient of α_NO3 = (4.2_{− 1.7}^+2.2)⋅ 10⁻³. The product H(D_l k_Cl−^II)^0.5 for the NO₃ radical was determined to be (1.9 ± 0.2) M atm^{− 1} cm s^−0.5 M^−0.5 s^−0.5 by fitting the uptake data for the NaCl solutions to the so-called resistance model. The yield of the chemical NO₃ radical source was characterized using UV-VIS and FT-IR spectroscopy. The amount of gas-phase NO₃ radicals measured at elevated humidities was less than expected. Instead, a rise of the gas-phase HNO₃ concentration was found indicating a conversion of gas-phase NO₃ radicals to gas-phase HNO₃ on the moist reactor walls.     

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.     

A vertical profile of Ozone concentration in the atmosphericboundary layer over central Taiwan

Summary  In the central region of Taiwan, ozone episodes occur most often during autumn. Two field experiments were conducted during the autumns of 1998 and 1999 to analyze the vertical profile of the boundary layer and determine its effects on ozone concentration over the region. The vertical virtual potential temperature and wind profiles were derived from tethersonde data. The NO_x, NMHC and O₃ concentration vertical profiles were monitored up to a height of 500 meters using black-covered Teflon tedler sampling bags. During the experimental periods, nighttime terrestrial long wave radiation could cause the inversion height to reach 500 meters by the following morning. It was shown that these types of synoptic structures suppress the vertical diffusion of NO_x, NMHC and O₃. During the daytime, measurements indicate that pollutants were well mixed in the upper portion of the mixing layer. At night, the ground level ozone concentration was on the decrease but increased with altitude to a height of 500 m. The NO_x decreased with altitude whereas the NMHC showed no significant variations. Received April 13, 2000 Revised July 24, 2000     

Estimates of anthropogenic CO<Subscript>2</Subscript> uptake in a global ocean model

A global ocean general circulation model (L30T63) is employed to study the uptake and distribution of anthropogenic CO₂ in the ocean. A subgrid-scale mixing scheme called GM90 is used in the model. There are two main GM90 parameters including isopycnal diffusivity and skew (thickness) diffusivity. Sensitivities of the ocean circulation and the redistribution of dissolved anthropogenic CO₂ to these two parameters are examined. Two runs estimate the global oceanic anthropogenic CO₂ uptake to be 1.64 and 1.73 Pg C yr^-1 for the 1990s, and that the global ocean contained 86.8 and 92.7 Pg C of anthropogenic CO₂ at the end of 1994, respectively. Both the total inventory and uptake from our model are smaller than the data-based estimates. In this presentation, the vertical distributions of anthropogenic CO₂ at three meridional sections are discussed and compared with the available data-based estimates. The inventory in the individual basins is also calculated. Use of large isopycnal diffusivity can generally improve the simulated results, including the exchange flux, the vertical distribution patterns, inventory, storage, etc. In terms of comparison of the vertical distributions and column inventory, we find that the total inventory in the Pacific Ocean obtained from our model is in good agreement with the data-based estimate, but a large difference exists in the Atlantic Ocean, particularly in the South Atlantic. The main reasons are weak vertical mixing and that our model generates small exchange fluxes of anthropogenic CO₂ in the Southern Ocean. Improvement in the simulation of the vertical transport and sea ice in the Southern Ocean is important in future work.     

Modelling of the vertical fluxes of nitric acid,ammonia, and ammonium nitrate

Results from numerical investigations regarding the exchange of HNO₃, NH₃, and NH₄NO₃ between the atmosphere and the biosphere are presented. The investigations were performed with a modified inferential method which is based on the generally accepted micrometeorological ideas of the transfer of momentum, sensible heat and matter near the Earth's surface and the chemical reactions among these nitrogen compounds. This modified inferential method calculates the micrometeorological quantities (such as the friction velocity and the fluxes of sensible and latent heat), the height-invariant fluxes of the composed chemically conservative trace species with group concentrationsc ₁=[HNO₃]+[NH₄NO₃] (total nitrate),c ₂=[NH₃]+[NH₄NO₃] (total ammonia), andc ₃=[HNO₃]-[NH₃] as well as the fluxes of the individual nitrogen compounds. The parameterization of the fluxes is based on the flux-gradient relationships in the turbulent region of the atmospheric surface layer. The modified inferential method requires only the data of wind velocity, temperature, humidity and concentrations (HNO₃, NH₃, and NH₄NO₃) measured at a reference height by stations of a monitoring network.     

Global NOx Production by Lightning

Lightning is thought to represent an important source of tropospheric reactive nitrogen species NO_x (NO + NO₂),but estimates of global production of NO_x by lightning varyconsiderably. We evaluate the production of NO_x by lightning using a global chemical/transport model, satellite lightning observations, and airborne NO_x measurements. Various model calculations are conducted toassess the global NO_x production rate of lightning by comparing the model calculations with airborne measurements. The results show that the simulated NO_x in the tropical middle and upper troposphere are very sensitiveto the amount and altitude of the lightning NO_x used in the model. A global lightning NO_x production of 7 Tg N yr^–1uniformly distributed in convective clouds or 3.5 Tg N yr^–1 distributedin the upper cloud regions produces good agreement between calculated and measured NO_x concentrations in the tropics.