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.     

Numerical analysis of ESR spectra from atmospheric samples

Improvements of the matrix isolation/electron spin resonance technique for the measurement of NO₂, NO₃, and RO₂ radicals in the atmosphere are described. The use of D₂O instead of H₂O as the matrix yields a better spectral resolution and, as a consequence, larger a signal-to-noise ratio as well as better identification of the different species. Reference spectra of the different radicals in H₂O and D₂O matrices are compared. While a large degree of correlation exists amongst the spectra of the different (unsubstituted and substituted) alkylperoxy radicals, the spectra of HO₂, CH₃C(O)O₂, and NO₃ show significant differences that allow their distinction in atmospheric samples.A numerical procedure for the analysis of the composite ESR spectra obtained from atmospheric samples was developed. Subtraction of the dominant NO₂ signal is performed by matching a reference NO₂ spectrum with respect to amplitude, spectral position, and line width to the sample spectrum. The manipulations are performed with the virtually noise-free reference spectrum and are based on physical information. The residual spectrum is then analyzed for RO₂ (and/or NO₃) by simultaneously fitting up to six different reference spectra.The method was applied to laboratory samples as well as to atmospheric samples in order to demonstrate the ability of retrieving small amounts of HO₂ in the presence of large amounts of NO₂ and other peroxy radicals. The new algorithm allowed, for the first time, the identification of the HO₂ and CH₃C(O)O₂ radical in tropospheric air at concentrations ranging up to 40 ppt.     

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.     

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.     

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.     

An improved method of measuring tropospheric NO2 and RO2 by matrix isolation and electron spin resonance

A cryogenic system for the airborne and ground based sampling of ambient radicals by matrix isolation is described. The trapped radicals, e.g., NO₂ and RO₂, are analyzed by ESR. The technique has been improved, mainly by addition of water vapor to the sampled air, to yield a collection efficiency of (90±10)% and a lower detection limit of about 20 ppt, but it still does not distinguish between the different RO₂. Careful calibration reduced the measurement error (1 ) to ±10% for NO₂ and ±15% for HO₂. Two diurnal variations of RO₂ and NO₂ at ground level and vertical profiles in the lower troposphere are presented.     

Stratospheric and total NO2 column measurements with a modified Canterbury filter photometer

A programme of ground-based stratospheric and total NO₂ column measurements was instituted at the Laboratory of Atmospheric Physics (40.5° N, 22.9° E) in August 1985. We present here the results of the first two years of measurements with a modified Canterbury filter photometer, details of which are given in the text. The stratospheric NO₂ column, obtained at twilight during low local NO₂ levels, shows the seasonal variation with monthly mean values of about 6×10^-15 molec. cm^-2 in the summertime to about 2.2×10^-15 molec. cm^-2 in the wintertime. These measurements compare well with measurements obtained with different instruments by other groups at similar latitudes (about 40° N) but in different places. Also, the asymmetry of the evening-to-morning stratospheric NO₂ over Thessaloniki was found to be on the average equal to 1.58. Total NO₂ column over Thessaloniki has a pronounced seasonal variation with amplitude of 0.68 matm. cm which can be explained partly from measured local NO₂ sources which discharge in the mixing layer and partly from photolysis of the NO₂ reservoir species.     

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.     

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. IV: The 200–400 nm Region at 220 K

Previous experiments in the 400–500 nm region (Coquart et al., 1995) have been extended to the 200–400 nm region to determine the absorption cross-sections of NO₂ at 220 K. The NO₂ and N₂O₄ cross-sections are obtained simultaneously from a calculation applied to the data resulting from measurements at low pressures. A comparison between the NO₂ cross-sections at 220 K and at ambient temperature shows that the low temperature cross-sections are generally lower, except in the region of the absorption peaks. Comparisons are also made with previous data at temperature close to 220 K.     

Tropospheric ozone and oxides of nitrogen over the north-western Pacific in summer

In summer, atmospheric ozone was measured from an aircraft platform simultaneously with nitric oxide (NO), oxides of nitrogen (NO _y ), and water vapor over the Pacific Ocean in east Asia from 34° N to 19° N along the longitude of 138±3°E. NO _y was measured with the aid of a ferrous sulfate converter. The altitude covered was from 0.5 to 5 km. A good correlation in the smoothed meridional distributions between ozone and NO _y was seen. In particular, north of 25° N, ozone and NO _y mixing ratios were considerably higher than those observed in tropical marine air south of 25° N. NO _y and O₃ reached a minimum of 50 pptv and 4 ppbv respectively in the boundary layer at a latitude of 20° N. The NO concentration between 2 and 5 km at the same latitude was 30 pptv. The profiles of ozone and water vapor mixing ratios were highly anti-correlated between 25° N and 20° N. In contrast, it was much poorer at the latitude of 33° N, suggesting a net photochemical production of ozone there.     

Altitude profile and sunset decay measurements of stratospheric nitric oxide

In July 1974 an NO/O₃ chemiluminescent instrument was used to obtain measurements of NO in the stratosphere during two balloon flights launched from Churchill (59°N, 95°W). On the first flight, an altitude profile was obtained in which the NO volume mixing ratio was observed to increase from 0.3 to 2.7 ppbv between 19 and 29.5 km. On the second flight, the mixing ratio was observed to increase from 0.25 to 2.7 ppbv between 19 and 29 km and to remain almost constant at about 2.7 ppbv from 29 to 34.5 km. On this flight, the sunset decay of NO was also obtained while the payload was at a constant float altitude of 34.5 km. These decay measurements are compared satisfactorily with the results obtained from a time dependent stratospheric model.     

The NO2 absorption spectrum. II. Absorption cross-sections at low temperatures in the 400–500 nm region

With improved experimental conditions already used for measurements at ambient temperature (Mérienneet al., 1994), new values have been found for the absorption cross-sections of NO₂ at 240 and 220 K in the 400–500 nm spectral region. Using a better resolution than in previous studies we show that the temperature effect is not negligible and should be taken into account for the optical measurements of atmospheric NO₂ amounts by differential absorption methods.Unité de Recherche Associée au CNRS.     

Processing of oxidised nitrogen compounds by passage through winter-time orographic cloud

Four case studies are described, from a three-site field experiment in October/November 1991 using the Great Dun Fell flow-through reactor hill cap cloud in rural Northern England. Measurements of total odd-nitrogen nitrogen oxides (NO _y ) made on either side of the hill, before and after the air flowed through the cloud, showed that 10 to 50% of the NO _y , called NO _z , was neither NO nor NO₂. This NO _z failed to exhibit a diurnal variation and was often higher after passage through cloud than before. No evidence of conversion of NO _z to NO₃ ^- in cloud was found. A simple box model of gas-phase chemistry in air before it reached the cloud, including scavenging of NO₃ and N₂O₅ by aerosol of surface area proportional to the NO₂ mixing ratio, shows that NO₃ and N₂O₅ may build up in the boundary layer by night only if stable stratification insulates the air from emissions of NO. This may explain the lack of evidence for N₂O₅ forming NO₃ ^- in cloud under well-mixed conditions in 1991, in contrast with observations under stably stratified conditions during previous experiments when evidence of N₂O₅ was found. Inside the cloud, some variations in the calculated total atmospheric loading of HNO₂ and the cloud liquid water content were related to each other. Also, indications of conversion of NO _x to NO _z were found. To explain these observations, scavenging of NO _x and HNO₂ by cloud droplets and/or aqueous-phase oxidation of NO₂ ^- by nitrate radicals are considered. When cloud acidity was being produced by aqueous-phase oxidation of NO _x or SO₂, NO₃ ^- which had entered the cloud as aerosol particles was liberated as HNO₃ vapour. When no aqueous-phase production of acidity was occurring, the reverse, conversion of scavenged HNO₃ to particulate NO₃ ^-, was observed.     

Intercomparison of NO,NO2 and HNO3 measurements with photochemical theory

The simultaneous measurements of NO, NO₂ and HNO_A mixing‐ratio profiles carried out on the Stratoprobe balloon flight of 22 July 1974 have been simulated with a time‐dependent model using the measured temperature and ozone profiles. The calculated ratios of NO/NO₂, HNO₃/NO₂ using currently accepted photochemistry are consistent with the measured ratios within the experimental errors of the measurements. The measured NO₂/NO ratio is almost a factor of two smaller than predicted, although the discrepancy is still within the experimental errors. A remarkable proportionality in the NO₂ and O₃ profiles has been noted and is unexplained. A time‐dependent simulation has been employed to convert the measurements into diurnally‐averaged profiles suitable for intercomparison with two‐dimensional stratospheric models and a comparison with constituent profiles from Prinn et al. (1975) is carried out as an example. The NO_V mixing ratio, formed from the sum of the NO, NO₂ and HNO₂ measurements is similar to the NO_V mixing ratio from several one‐ and two‐dimensional models used to predict the effects of SST's on the ozone layer. The odd nitrogen mixing ratio is roughly constant from 20 to 35 km at 11 ppbv.     

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.     

Atmospheric trace gas analysis using matrix isolation-fourier transform infrared spectroscopy

A novel cryogenic sampling method combining the matrix isolation technique with FTIR spectroscopy has been developed for atmospheric trace gas analysis. It is applicable to a wide range of molecules with detection limits typically in the 10–50 ppt range. The method is described along with some measurements of N₂O, CFCl₃, CF₂Cl₂, OCS, CS₂, SO₂ and PAN from samples collected at ground level and from an aircraft between 9 and 14 km.     

A study of the vertical distribution of methyl chloride (CH3Cl) in the midlatitude stratosphere

The vertical distribution of the CH₃Cl mixing ratio in the stratosphere has been measured from samples collected during two balloon flights on the 21 October 1982 and 10 September 1983. Measurements were made with two analytical techniques that were also employed for previous analyses of stratospheric samples: gas chromatography (GC) and a gas chromatograph/mass spectrometer (GC/MS) combination. The results from all balloon flights performed to date are combined to derive an average experimental profile of CH₃Cl at midlatitudes. The profile shows that the CH₃Cl mixing ratio decreases by about one order of magnitude between 20 and 30 km altitude. A comparison of the new observations with model profiles reveals discrepancies in the lower stratosphere that amount to a factor of about 3. Possible causes for these discrepancies are discussed.     

NO<Subscript>3</Subscript> Vertical Profile Measurements from Remote Sensing Balloon-Borne Spectrometers and Comparison with Model Calculations

Eleven vertical profiles of stratospheric NO₃ have been obtained since 1992 using the AMON and SALOMON balloon-borne UV-visible spectrometers. The measurements are compared to the SLIMCAT 3D model and calculations based on the steady-state hypothesis for NO₃. The calculations cannot reproduce some parts of the profiles which exhibit strong concentration fluctuations over few kilometres, as a consequence of the dependence of NO₃ on local temperature variations. A statistical use of the data allows us to estimate the influence of the temperature dependence of the absorption cross-section on the data analysis, and the validity of the recommended reaction rates available in the literature. Discrepancies exist between the model based on recommended kinetics and observations at warmer temperatures. Nevertheless, the analysis is biased by local temperature inhomogeneities, and only a low-resolution vertical shape of the NO₃ profiles can be retrieved.     

Photochemistry of N2O4 Adsorbed on Ice Surfaces at 193 nm

A multi-layer deposited ice film was prepared through water vapor deposition on a Ni plate in a vacuum chamber at 90 K, and was used as it was or after annealing at 140 K. NO₂ was adsorbed as N₂O₄ approximately 90 K on the ice film prepared as above, and irradiated by 193 nm excimer laser light. The time-of-flight (TOF) spectra of the desorbed species, i.e., NO₂, NO, O₂ and O, were measured by a quadrupole mass spectrometer. The photochemical process obeyed an one-photon process. The relative yields of the products and their TOF spectra were dependent on the preparation condition of the ice film and also varied with the continuation of the laser irradiation. From the ice film annealed at 140 K, NO₂, NO and O₂ were desorbed with an approximate ratio of 1:1:0.01. From the non-annealed film, the relative yield of NO₂ was much smaller than that of NO. The TOF spectrum of NO from the non-annealed ice film consisted of distinctly different two components corresponding to the 1700 and 100 K translational temperature, respectively. The fast component was lost when additional ice was deposited on the adsorbed N₂O₄. NO was supposed to be a predissociation product from the electronically excited NO₂ prepared through the photodissociation of N₂O₄.