Aircraft measurements of oxides of nitrogen along the eastern rim of the Asian continent: Winter observations

Aircraft observations of oxides of nitrogen (NO _y ), measured with a ferrous sulfate converter, over the sea surrounding the Japanese islands (30–43° N, 131–141° E) were carried out in the winter of 1983 and 1984 at altitudes mostly between 3 and 8 km. NO _y defined here is the sum of NO, NO₂, and other unstable oxides of nitrogen that are converted to NO by ferrous sulfate. The main observations were:

1. Over the Pacific Ocean between the latitudes of 30–35° N, the observed NO _y mixing ratio between 3 and 8 km was a fairly constant 200 pptv. The NO mixing ratio increased with altitude from 15 pptv at 3 km to 35 pptv at 7 km.
2. Over the Sea of Japan, tropospheric NO _y mesured between 1 and 6 km started increasing with latitude North of 35° N and reached about 1000 pptv at 40° N.
3. NO _y was measured in an air mass transported from the stratosphere near a tropopause fold region. When the ozone mixing ratio was between 80 and 140 ppbv, the NO _y mixing ratio was about 200 pptv.

     

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.     

The tropospheric distribution of carbon monoxide as observed during the Tropoz II experiment

As part of the TROPOZ II large-scale measurement campaign in January 1991 we deployed a Four Laser Airborne Infra Red (FLAIR) tunable diode laser spectrometer on board a Caravelle 116 research aircraft. We report here in situ CO measurements which were obtained with one of the four channels of the FLAIR instrument at a time resolution of either one or two minutes. The flight route of the TROPOZ II campaign followed the Atlantic coasts of North America, the Pacific and Atlantic coasts of South America and the Atlantic coasts of West Africa and Europe. A total of 48 CO vertical profiles extending from the surface to 10.5 km altitude were obtained. In the meridional direction adjacent profiles were separated by less than 10° latitude. Polewards of 30°S the CO distribution was very homogeneous with a mean mixing ratio of 55 ppbv. Between 30°S and the equator, the CO mixing ratio above 8 km altitude ranged up to 130 ppbv and was 20–60 ppbv higher than in the mid free troposhere. Three day backward trajectories for these CO rich airmasses originated over Amazonia. Earlier trace gas measurements as well as circulation studies suggested that these airmasses were of Northern Hemispheric origin and had been rapidly convected to the upper troposphere over central South America. The influence of biomass burning is clearly apparent from the measurements performed at 10°N on the African side of the Atlantic with CO mixing ratios being 100–300% higher than on the Central American side. CO mixing ratios further north ranged from 80 to 130 ppbv in the free troposphere and increased to 130–150 ppbv at lower altitudes.     

The altitude distribution of nitric acid at Churchill

The altitude distribution of nitric acid vapour was measured from observations of atmospheric thermal emission in the 11.3‐μm band during a balloon ascent launched at 2317 GMT on 22 July 1974 from Churchill, Manitoba (latitude 58.7°N). The total amount of nitric acid above the tropopause was 0.32 matmcm. The nitric acid layer was peaked at 24 km with a maximum mixing ratio of 5.5 ppbv. This measurement is similar to other available measurements of nitric acid in terms of layer shape and peak concentrations. The total amount of 0.32 matmcm is consistent with aircraft measurements of the latitudinal variation of nitric acid.     

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.     

Study of Ozone and NO2 over Gadanki – a rural site in South India

We have studied long-term changes in tropospheric NO₂ over South India using ground-based observations, and GOME and OMI satellite data. We have found that unlike urban regions, the region between Eastern and Western Ghat mountain ranges experiences statistically significant decreasing trend. There are few ground-based observatories to verify satellite based trends for rural regions. However, using a past study and recent measurements we show a statistically significant decrease in NO_X and O₃ mixing ratio over a rural location (Gadanki; 13.48° N, 79.18° E) in South India. In the ground-based records of surface NO_X, the concentration during 2010–11 is found to be lower by 0.9 ppbv which is nearly 60 % of the values observed during 1994–95. Small but statistically significant decrease in noon-time peak ozone concentration is also observed. Noon-time peak ozone concentration has decreased from 34?±?13 ppbv during 1993–96 to 30?±?15 ppbv during 2010–11. NO_X mixing ratios are very low over Gadanki. In spite of low NO_X values (0.5 to 2 ppbv during 2010–11), ozone mixing ratios are not significantly low compared to many cities with high NO_X. The monthly mean ozone mixing ratio varies from 9 ppbv to 37 ppbv with high values during Spring and low values during late Summer. Using a box-model, we show that presence of VOCs is also very important in addition to NO_X in determining ozone levels in rural environment and to explain its seasonal cycle.     

An ozone depletion event in the sub-arctic surface layer over Hudson Bay,Canada

During the Tropospheric Ozone Production about the Spring Equinox (TOPSE) program, aircraft flights during April 7–11, 2000 revealed a large area air mass capped below ∼500 m altitude over Hudson Bay, Canada in which ozone was reduced from normal levels of 30–40 ppbv to as low as 0.5 ppbv. From some of the in-situ aircraft measurements, back-trajectory calculations, the tropospheric column of BrO derived from GOME satellite measurements, and results from a regional model, we conclude that the event did not originate from triggering of reactive halogen release in the sub-Arctic region of Hudson Bay but resulted from such an event occurring at higher latitudes over the islands of the northern Canada Archipelago and nearby Arctic Ocean with subsequent transport over a distance of 1,000–1,500 km to Hudson Bay. BrO _x remained active during this transport despite considerable changes in the conditions of the underlying surface suggesting that chemical recycling during transport dominated any local halogen input from the surface. If all of the tropospheric column density of BrO is distributed uniformly within the surface layer, then the mixing ratio of BrO derived from the satellite measurements is at least a factor of 2–3 larger than derived indirectly from in situ aircraft measurements of the NO/NO₂ ratio.     

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.     

Variations in surface ozone and NOx at Kannur: a tropical, coastal site in India

Continuous measurements of surface ozone (O₃), NOx (NO + NO₂) and meteorological parameters have been made in Kannur (11.9?°N, 75.4?°E, 5?m asl), India from November 2009 to October 2010. It was observed that O₃ and NOx showed distinct diurnal and seasonal variabilities at this site. The annual average diurnal profile of O₃ showed a peak of (30.3?±?10.4) ppbv in the late afternoon and a minimum of (3.2?±?0.7) ppbv in the early morning. The maximum value of O₃ mixing ratio was observed in winter (44?±?3.1) ppbv and minimum during monsoon (18.46?±?3.5) ppbv. The rate of production of O₃ was found to be higher in December (10.1?ppbv/h) and lower in July (1.8?ppbv/h) during the time interval 0800?C1000?h. A correlation coefficient of 0.52 for the relationship between O₃ and [NO₂]/[NO] reveals the role of NO₂ photolysis that generates O₃ at this site. The correlation between O₃ and meteorological parameters indicate the influence of seasonal changes on O₃ production. Investigations were further extended to explore the week day weekend variations in O₃ mixing ratio at an urban site reveals the enhancement of O₃. The variations of O₃ mixing ratio with seasonal air mass flows were elucidated with the aid of backward air trajectories. This study also indicates how vapor phase organic species present in the ambient air at this location may influence the complex chemistry involving (VOCs) that enhances the production of O₃ at this location.     

Aircraft measurements and model simulations of stratospheric ozone and N2O: implications for chemistry and transport processes in the models

Airborne measurements of stratospheric ozone and N₂O from the SCIAMACHY (Scanning Imaging Absorption Spectrometer) Validation and Utilization Experiment (SCIA-VALUE) are presented. The campaign was conducted in September 2002 and February–March 2003. The Airborne Submillimeter Radiometer (ASUR) observed stratospheric constituents like O₃ and N₂O, among others, spanning a latitude from 5°S to 80°N during the survey. The tropical ozone source regions show high ozone volume mixing ratios (VMRs) of around 11 ppmv at 33 km altitude, and the altitude of the maximum VMR increases from the tropics to the Arctic. The N₂O VMRs show the largest value of 325 ppbv in the lower stratosphere, indicating their tropospheric origin, and they decrease with increasing altitude and latitude due to photolysis. The sub-tropical and polar mixing barriers are well represented in the N₂O measurements. The most striking seasonal difference found in the measurements is the large polar descent in February–March. The observed features are interpreted with the help of SLIMCAT and Bremen Chemical Transport Model (CTMB) simulations. The SLIMCAT simulations are in good agreement with the measured O₃ and N₂O values, where the differences are within 1 ppmv for O₃ and 15 ppbv for N₂O. However, the CTMB simulations underestimate the tropical middle stratospheric O₃ (1–1.5 ppmv) and the tropical lower stratospheric N₂O (15–30 ppbv) measurements. A detailed analysis with various measurements and model simulations suggests that the biases in the CTMB simulations are related to its parameterised chemistry schemes.     

Ballon-borne and aircraft infrared measurements of ethane (C2H6) in the upper troposphere and lower stratosphere

Quantitative infrared measurements of ethane (C₂H₆) in the upper troposphere and lower stratosphere are reported. The results have been obtained from the analysis of absorption features of the ₉ band at 12.2 m, which have been identified in high-resolution ballon-borne and aircraft solar absorption spectra. The ballon-borne spectral data were recorded at sunset with the 0.02 cm^-1 resolution University of Denver interferometer system from a float altitude of 33.5 km near Alamogordo, New Mexico, on 23 March 1981. The aircraft spectra were recorded at sunset in July 1978 with a 0.06 cm^-1 resolution interferometer aboard a jet aircraft at 12 km altitude, near 35°N, 96°W. The balloon analysis indicates the C₂H₆ mixing ratio decreased from 3.5 ppbv near 8.8 km to 0.91 ppbv near 12.1 km. The results are consistent with the colum value obtained from the aircraft data.     

Sampling of Chemical Constituents in Electrically Active Convective Systems: Results and Cautions

On flights of a P3-B turboprop and a WB-57F jet aircraft within thunderstorm systems, short term spikes (1–2 sec or less in duration) in NO and O₃ were recorded and are attributed to hot or cold discharges occurring on the aircraft fuselage or air sampling inlets. One such spike of only ∼300 msec duration reached 325 ppbv of NO on the flight of the jet aircraft while at 13.8 km altitude. In a lightning flash to the P3-B aircraft, production of NO (expected) and NO₂ (unexpected) were directly observed. The NO production was ∼ 1.7 x 10²² molecules/m of flash length. In the P3-B flight at 5.5 km altitude and over a distance of ∼ 275 km within a highly electrically active thunderstorm complex in the equatorial central Pacific Ocean, there was no evidence of production of O₃ or CO by lightning flashes or by any type of hot or cold discharge involved in the development of free-air lightning flashes.     

Ammonia measurements at Niwot Ridge,Colorado and point arena,California using the tungsten oxide denuder tube technique

The applicability of the tungsten oxide denuder tube technique for the measurement of ammonia in the rural troposphere was investigated. The technique is based on selective chemisorption of NH₃ from a gas stream, thermal desorption, conversion to NO, and analysis by NO–O₃ chemiluminescence. Nitric acid, which is also collected and desorbed as NO, was distinguished from NH₃ by differences in desorption temperature. Substituted amines were also collected, but desorbed at a slightly lower temperature than NH₃ in dry air. At high relative humidities, alkylamines may be hydrolyzed to NH₃ on the denuder surface and hence detected as NH₃. Overheating of the denuder tube during the temperature-programmed desorption was found to cause significant irreversible degradation of system performance.The technique was used to measure NH₃ mixing ratios at two rural locations in the United States. At a mountain site in Colorado during the winter of 1984, the average NH₃ mixing ratio was 0.20 ppbv (=0.08 ppbv). At an isolated coastal site in northern California during the spring of 1985, the average NH₃ mixing ratio was 0.36 ppbv (=0.17 ppbv). Correlations of the latter measurements with wind direction and NO _x level suggest that the NH₃ mixing ratio in Pacific marine air at 40°N is <-0.25 ppbv.     

A study of ozone in the Colorado mountains

The seasonal and diurnal variations of ozone mixing ratios have been observed at Niwot Ridge. Colorado. The ozone mixing ratios have been correlated with the NO _x (NO+NO₂) mixing ratios measured concurrently at the site. The seasonal and diurnal variations in O₃ can be reasonably well understood by considering photochemistry and transport. In the winter there is no apparent systematic diurnal variation in the O₃ mixing ratio because there is little diurnal change of transport and a slow photochemistry. In the summer, the O₃ levels at the site are suppressed at night due to the presence of a nocturnal inversion layer that isolated ozone near the surface, where it is destroyed. Ozone is observed to increase in the summer during the day. The increases in ozone correlate with increasing NO _x levels, as well as with the levels of other compounds of anthropogenic origin. We interpret this correlation as in-situ or in-transit photochemical production of ozone from these precursors that are transported to our site. The levels of ozone recorded approach 100 ppbv at NO _x mixing ratios of approximately 3 ppbv. Calculations made using a simple clean tropospheric chemical model are consistent with the NO _x -related trend observed for the daytime ozone mixing ratio. However, the chemistry, which does not include nonmethane hydrocarbon photochemistry, underestimates the observed O₃ production.     

Measurements of surface ozone at semi-arid site Anantapur (14.62°N, 77.65°E, 331 m asl) in India

In the present study, an attempt has been made to examine the governing photochemical processes of surface ozone (O₃) formation in rural site. For this purpose, measurements of surface ozone and selected meteorological parameters have been made at Anantapur (14.62°N, 77.65°E, 331 m asl), a semi-arid zone in India from January 2002 to December 2003. The annual average diurnal variation of O₃ shows maximum concentration 46 ppbv at noon and minimum 25 ppbv in the morning with 1σ standard deviation. The average seasonal variation of ozone mixing ratios are observed to be maximum (about 60 ppbv) during summer and minimum (about 22 ppbv) in the monsoon period. The monthly daytime and nighttime average surface ozone concentration shows a maximum (55 ± 7 ppbv; 37 ± 7.3 ppbv) in March and minimum (28 ± 3.4 ppbv; 22 ± 2.3 ppbv) in August during the study period. The monthly average high (low) O₃ 48.9 ± 7.7 ppbv (26.2 ± 3.5 ppbv) observed at noon in March (August) is due to the possible increase in precursor gas concentration by anthropogenic activity and the influence of meteorological parameters. The rate of increase of surface ozone is high (1.52 ppbv/h) in March and lower (0.40 ppbv/h) in July. The average rate of increase of O₃ from midnight to midday is 1 ppbv/h. Surface temperature is highest (43–44°C) during March and April months leading to higher photochemical production. On the other hand, relative humidity, which is higher during the rainy season, shows negative correlation with temperature and ozone mixing ratio. It can be seen that among the two parameters are measured, correlation of surface ozone with wind speed is better (R ²=0.84) in compare with relative humidity (R ²=0.66).     

Minor Constituent Concentrations Measured from a High Altitude Aircraft Using High Resolution Far-Infrared Fourier Transform Spectroscopy

Far-infrared emission spectroscopy has beendemonstrated to be a valuable method for remotesensing of trace species in the stratosphere, with theability to simultaneously detect a number of keychemical species. SAFIRE-A is a new far-infraredFourier Transform (FT) spectrometer which has beenspecifically designed to operate on board of a highaltitude aircraft in the lower stratosphere and uppertroposphere regions where relatively few remotesensing measurements have been made. Using newtechnology, the sensitivity of the FT spectrometermethod has been substantially improved for the longwavelength region. Results are reported formeasurements of O₃, HNO₃ and N₂O at 17and 19 km using a detection window near 23 cm^-1.Geographical and altitude variability of the volumemixing ratio of these constituents and their relativecorrelation are discussed. Ozone measurements agreewell with in situ measurements, except in regions ofstrong stirring and mixing associated with deformationof the northern vortex edge. Whilst SAFIREmeasurements of trace gases do not capture all of thelocal variability seen by rapid in-situ techniques,they can indicate horizontal variability close to, butnot intercepted by, the aircraft's flight path. Apossible detection of ClO at the low background levelsexpected outside the polar vortex is also reported.     

Volatile organic compounds at a rural site in western Senegal

The objectives of this study were to identify species and levels of volatile organic compounds (VOCs), and determine their oxidation capacity in the rural atmosphere of western Senegal. A field study was conducted to obtain air samples during September 14 and September 15, 2006 for analyses of VOCs. Methanol, acetone, and acetaldehyde were the most abundant detected chemical species and their maximum mixing ratios reached 6 parts per billion on a volume basis (ppbv). Local emission sources such as firewood and charcoal burning strongly influenced VOC concentrations. The VOC concentrations exhibited little temporal variations due to the low reactivity with hydroxyl radicals, with reactivity values ranging from 0.001 to 2.6 s⁻¹. The conditions in this rural site were rather clean. Low ambient NO _x levels limited ozone production. Nitrogen oxide (NO _x ) levels reached values less than 2 ppbv and maximum VOC/NO _x ratios reached 60 ppbvC/ppbv, with an overall average of 2.4 ± 4.5 ppbvC/ppbv. This indicates that the rural western Senegal region is NO _x limited in terms of oxidant formation potential. Therefore, during the study period photochemical ozone production became limited due to low ambient NO _x levels. The estimated ozone formation reactivity for VOCs was low and ranged between −5.5 mol of ozone/mol of benzaldehyde to 0.6 mol/mol of anthropogenic dienes.     

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.     

Stratospheric aerosol sulfuric acid: First direct in situ measurements using a novel balloon-based mass spectrometer apparatus

The first direct in situ measurements of the sulfuric acid contained in stratospheric aerosol particles were made using a novel balloon-based Ion Molecule Reaction Mass Spectrometer instrument (IMRMS) equipped with an aerosol vaporizer. The IMRMS method employed offers direct aerosol sulfuric acid measurements with high spatial resolution. The balloon flight took place on 23 October 1995 in middle latitudes (44°N) and reached a maximum altitude of 24 km. Measured molecular number densities of aerosol sulfuric acid decreased with increasing altitude from about 2.9 × 109 cm-3 at 15km altitude to about 2.4 × 108 cm-3 at 21 km. Corresponding mass mixing ratios are 2.5 and 0.6 ppbm, respectively. Calculated sulfuric acid mixing ratios from aerosol volumes inferred from aerosol size distribution measurements on the same balloon agree well with the IMRMS data using standard assumption aerosol composition.     

MANTRA ‐ A Balloon Mission to Study the Odd‐Nitrogen Budget of the Stratosphere

Abstract

The Middle Atmosphere Nitrogen TRend Assessment (MANTRA) series of high‐altitude balloon flights is being undertaken to investigate changes in the concentrations of northern hemisphere mid‐latitude stratospheric ozone, and of nitrogen and chlorine compounds that play a role in ozone chemistry. Four campaigns have been carried out to date, all from Vanscoy, Saskatchewan, Canada (52°01'N, 107°02'W, 511.0 m). The first MANTRA mission took place in August 1998, with the balloon flight on 24 August 1998 being the first Canadian launch of a large high‐altitude balloon in about fifteen years. The balloon carried a payload of instruments to measure atmospheric composition, and made measurements from a float altitude of 32–38 km for one day. Three of these instruments had been flown on the Stratoprobe flights of the Atmospheric Environment Service (now the Meteorological Service of Canada) in the 1970s and early 1980s, providing a link to historical data predating the onset of mid‐latitude ozone loss.

The primary measurements obtained from the balloon‐borne instruments were vertical profiles of ozone, NO₂, HNO₃, HCl, CFC‐11, CFC‐12, N₂O, CH₄, temperature, and aerosol backscatter. Total column measurements of ozone, NO₂, SO₂, and aerosol optical depth were made by three ground‐based spectrometers deployed during the campaign. Regular ozonesonde and radiosonde launches were also conducted during the two weeks prior to the main launch in order to characterize the local atmospheric conditions (winds, pressure, temperature, humidity) in the vicinity of the primary balloon flight. The data have been compared with the Model for Evaluating oZONe Trends (MEZON) chemical transport model, the University of California at Irvine photochemical box model, and the Canadian Middle Atmosphere Model (CMAM) to test our current understanding of model photochemistry and mid‐latitude species correlations. This paper provides an overview of the MANTRA 1998 mission, and serves as an introduction to the accompanying papers in this issue of Atmosphere‐Ocean that describe specific aspects and results of this campaign.