Stratospheric N2O5, CH4, and N2O profiles from IR solar occultation spectra

Stratospheric volume mixing ratio profiles of N₂O₅, CH₄, and N₂O have been retrieved from a set of 0.052 cm^–1 resolution (FWHM) solar occultation spectra recorded at sunrise during a balloon flight from Aire sur l'Adour, France (44° N latitude) on 12 October 1990. The N₂O₅ results have been derived from measurements of the integrated absorption by the 1246 cm^–1 band. Assuming a total intensity of 4.32×10^–17 cm^–1/molecule cm^–2 independent of temperature, the retrieved N₂O₅ volume mixing ratios in ppbv (parts per billion by volume, 10^–9), interpolated to 2 km height spacings, are 1.64±0.49 at 37.5 km, 1.92±0.56 at 35.5 km, 2.06±0.47 at 33.5 km, 1.95±0.42 at 31.5 km, 1.60±0.33 at 29.5 km, 1.26±0.28 at 27.5 km, and 0.85±0.20 at 25.5 km. Error bars indicate the estimated 1- uncertainty including the error in the total band intensity (±20% has been assumed). The retrieved profiles are compared with previous measurements and photochemical model results.Laboratoire associé aux Universités Pierre et Marie Curie et Paris Sud.     

Vertical column abundances of HCN deduced from ground-based infrared solar spectra: Long-term trend and variability

A set of high-resolution IR solar spectra recorded at the International Scientific Station of the Jungfraujoch, Switzerland, from 84/06 to 93/06, and at the National Solar Observatory McMath-Pierce solar telescope facility on Kitt Peak, Arizona, U.S.A. from 78/05 to 92/07 have been analyzed to determine the vertical column abundances of hydrogen cyanide, HCN, above the two stations. The analysis was based on least-squares curve fitting of calculated spectra to the observations encompassing the P4 and the P8 lines of HCN respectively located at 3299.5273 and 3287.2483 cm^–1. The results obtained for the two stations indicate that no significant long-term trend affects either of the two databases; however, this analysis reveals variable increases during springtime of up to a factor of 2 in the HCN total column above the Jungfraujoch and even up to 3 above Kitt Peak. The calculated mean vertical column abundances, excluding the spring observations, are equal to (2.55±0.30)×10¹⁵ molec./cm² (S.D.) and (2.75±0.30)×10¹⁵ molec./cm² respectively above the Jungfraujoch and the Kitt Peak observatories. Based on a realistic volume mixing ratio profile, these columns translate into mean volume mixing ratios equal to 190×10^–12 ppv at the respective altitudes of the stations.     

Secular evolution of the vertical column abundances of CHCIF2 (HCFC-22) in the Earth's atmosphere inferred from ground-based IR solar observations at the Jungfraujoch and at Kitt Peak,and comparison with model calculations

Series of high-resolution infrared solar spectra recorded at the International Scientific Station of the Jungfraujoch, Switzerland, between 06/1986 and 11/1992, and at Kitt Peak National Observatory, Tucson, Arizona (U.S.A.), from 12/1980 to 04/1992, have been analyzed to provide a comprehensive ensemble of vertical column abundances of CHCIF₂ (HCFC-22; Freon-22) above the European and the North American continents. The columns were derived from nonlinear least-squares curve fittings between synthetic spectra and the observations containing the unresolved 2v ₆ Q-branch absorption of CHCIF₂ at 829.05 cm^–1. The changes versus time observed in these columns were modeled assuming both an exponential and a linear increase with time. The exponential rates of increase at one-sigma uncertainties were found equal to (7.0±0.35)%/yr for the Junfraujoch data and (7.0±0.23)%/yr for the Kitt Peak data. The exponential trend of 7.0%/yr found at both stations widely separated in location can be considered as representative of the global increase of the CHCIF₂ burden in the Earth's atmosphere during the period 1980 to 1992. When assuming two realistic vertical volume mixing ratio profiles for CHCIF₂ in the troposphere, one quasi constant and the other decreasing by about 13% from the ground to the tropopause, the concentrations for mid-1990 were found to lie between 97 and 111 pptv (parts per trillion by volume) at the 3.58 km altitude of the Jungfraujoch and between 97 and 103 pptv at Kitt Peak, 2.09 km above sea level. Corresponding values derived from calculations using a high vertical resolution-2D model and recently compiled HCFC-22 releases to the atmosphere, were equal to 107 and 105 pptv, respectively, in excellent agreement with the measurements. The model calculated lifetime of CHCIF₂ was found equal to 15.6 years. The present results are compared critically with similar data found in the literature. On average, the concentrations found here are lower by 15–20% than those derived from in situ investigations; this difference cannot be explained by the absolute uncertainty of ±11% assigned presently to the infrared remote measurements.     

Vertical Column Abundances of COF2 Above the Jungfraujoch Station, Derived from Ground-Based Infrared Solar Observations

Total vertical column abundances of carbonyl fluoride (COF₂) have been derived from observations made at the International Scientific Station of the Jungfraujoch (ISSJ; altitude 3.58 km, latitude 46.5°N, longitude 8.0°E), Switzerland. A systematic analysis of two microwindows containing lines of the ₁ band was performed, based on a large set of high resolution infrared solar absorption spectra recorded with Fourier transform spectrometers, from 1985 to 1995. Examination of the whole available database indicates a significant increase of the burden of COF₂ during the 1988–1995 period. The average exponential rate and the average linear rate referenced to 1992, calculated from daily mean measurements, are both equal to (4.0 ± 0.5)% yr^-1 (one error). The results are also evaluated and discussed within the context of seasonal variability and correlation between carbonyl fluoride and hydrogen fluoride (HF) columns above the ISSJ.     

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.     

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.     

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.     

Chlorine-hydrocarbon photochemistry in the marine troposphere and lower stratosphere

A one-dimensional photochemical model was used to explore the role of chlorine atoms in oxidizing methane and other nonmethane hydrocarbons (NMHCs) in the marine troposphere and lower stratosphere. Where appropriate, the model predictions were compared with available measurements. Cl atoms are predicted to be present in the marine troposphere at concentrations of approximately 10³ cm^-3, mostly as a consequence of the reaction of OH with HCl released from sea spray. Despite this low abundance, our results indicate that 20 to 40% of NMHC oxidation in the troposphere (0–10 km) and 40 to 90% of NMHC oxidation in the lower stratosphere (10–20 km) is caused by Cl atoms. At 15 km, NMHC-Cl reactions account for nearly 80% of the PAN produced.The model was also used to test the longstanding hypothesis that NOCl is an intermediate to HCl formation from sea salt aerosols. It was found that the NOCl concentration required (10 ppt) would be incompatible with field observations of reactive nitrogen and ozone abundance. Chlorine nitrate (ClONO₂) and methyl nitrate (CH₃ONO₂) were shown to be minor components of the total NO _y abundance. Heterogeneous reactions that might enhance photolysis of halocarbons or convert ClONO₂ to HOCl or Cl₂ were determined to be relatively unimportant sources of Cl atoms. Specific and reliable measurements of HCl and other reactive chlorine species are needed to better assess their role in tropospheric chemistry.     

A smog chamber for studies of the reactions of terpenes and alkanes with ozone and OH

The design and performance of a smog chamber for the study of photochemical reactions under simulated environmental conditions is described. The chamber is thermostated for aerosol experiments, and it comprises a gas chromatographic sample enrichment system suitable for monitoring hydrocarbons at the ppbv level. By irradiating NO _x /alkane-mixtures rate constants for the reaction of OH radicals with n-alkanes are determined from n-pentane to n-hexadecane to be (k±2)/10^–12 cm³ s^–1=4.29±0.16, 6.2±0.6, 7.52 (reference value), 8.8±0.3, 10.2±0.3, 11.7±0.4, 13.7±0.3, 15.1±0.5, 17.5±0.6, 19.3±0.7, 22.3±1.0, and 25.0±1.3, respectively at 312 K. Rate constants, (k±2)/10^–17 cm³ s^–1, for the reaction of ozone with trans-2-butene (21.2±1.0), cis-3-methylpentene-(2) (47.2±1.7), cyclopentene (62.4±3.5), cyclohexene (7.8±0.5), cycloheptene (28.3±1.5), -pinene (8.6±1.3), and -pinene (1.4±0.2) are determined in the dark at 297 K using cis-2-butene (13.0) as reference standard.     

A Seasonal Comparison of the Ozone Photochemistry in Clean and Polluted Air Masses at Mace Head, Ireland

Measurements of the sum of peroxy radicals [HO₂ + RO₂],NO_x (NO + NO₂) and NO_y (the sum of oxidisednitrogen species) made at Mace Head, on the Atlantic coast of Ireland in summer 1996 and spring 1997 are presented. Together with a suite of ancillary measurements, including the photolysis frequencies of O₃ O(¹D)(j(O¹D)) and NO₂ (j(NO₂)), the measured peroxy radicals are used to calculate meandailyozone tendency (defined as the difference of the in-situphotochemical ozone production and loss rates); these values are compared with values derived from the photochemical stationary state (PSS) expression. Although the correlation between the two sets of values is good, the PSS values are found to be significantly larger than those derived from the peroxy radical measurements, on average, in line with previous published work. Possible sources of error in these calculations are discussed in detail. The data are further divided up into five wind sectors, according to the instantaneous wind direction measured at the research station. Calculation of mean ozone tendencies by wind sector shows that ozone productivity was higher during spring (April–May) 1997 than during summer (July–August) 1996across all airmasses, suggesting that tropospheric photochemistry plays an important role in the widely-reported spring ozone maximum in the Northern Hemisphere. Ozone tendencies were close to zero for the relatively unpolluted south-west, west and north-west wind sectors in the summer campaign, whereas ozone productivity was greatest in the polluted south-east sector for both campaigns. Daytime weighted average ozone tendencies were +(0.3± 0.1) ppbv h^–1 for summer 1996 and +(1.0± 0.5) ppbvh^–1 for spring 1997. These figures reflect the higher mixing ratios of ozone precursors in spring overall, as well as the higher proportion of polluted air masses from the south-east arriving at the site during the spring campaign. The ozone compensation point, where photochemical ozone destruction and production processes are in balance, is calculated to be ca. 14 pptv NO for both campaigns.     

Kinetics of the Reactions of IO with HO2 and O(3P)

A discharge-flow tube coupled with resonance fluorescence and chemiluminescence detection has been used to investigate the reactions IO + HO₂ products (1) and IO + O(³P) I + O₂(2), at T = 296 ± 1 K and P = 1.7 - 2 Torr. The rate constants k_-1 and k₂ have been found to be (7.1 ± 1.6) × 10^-11 cm³ molecule^-1 s^-1 and (1.35 ± 0.15) × 10^-10 cm³ molecule^-1 s^-1, respectively.     

DMS and SO2 Measurements in the Tropical Marine Boundary Layer

Dimethyl sulfide (DMS) and sulfur dioxide (SO₂) mixing ratios were measured in the boundary layer on Oahu, Hawaii in April and May 2000. Average DMS and SO₂ levels were 22 ± 7 (n = 488) pmol/mol and 23 ± 7 (n = 471) pmol/mol respectively. Anti-correlated DMS and SO₂ diurnal cycles, consistent with DMS + OH oxidation were observed on most days. Photochemical box model simulations suggest that the yield of SO₂ and total SO₂ sink are ∼85% and ∼2 × 10⁴ molec cm^{− 3} s^{− 1} respectively. On several days the rate of decrease in DMS and increase in SO₂ levels in the early morning were larger that predicted by the model. Dynamical and chemical causes for the anomalous early morning data are explored.     

Kinetics of the reactions of hydroxyl radicals with alkyl nitrates and with some oxygen-containing organic compounds studied under simulated atmospheric conditions

Rate constants have been measured for the reactions of hydroxyl radicals with alkyl nitrates and with some oxygen-containing organic compounds by a competitive technique. Mixtures of synthetic air containing a few ppm of nitrous acid, ethylene and the organic substrate were photolysed in a Teflon bag smog chamber. Based on the value k _HO+C2H₄}=8.1×10^-12 cm³ molecule^-1 s^-1 the following rate constants were obtained for the hydroxyl radical reactions at 750 Torr and at 303 K in units of 10^-12 cm³ molecule^-1: CH₃ONO₂, 0.37±0.09; C₂H₅ONO₂, 0.48±0.20; n-C₃H₇ONO₂, 0.70±0.22; C₂H₅OH, 3.6±0.4; CH₃COCH₃, 0.26±0.08; CH₃CO₂ i-C₃H₇, 3.0±0.8; CH₃CO₂ n-C₃H₇, 2.4±0.2. The results are discussed in relation to the available literature data and the implications of the results are considered in terms of the smog reactivity of these molecules.     

Autoxidation of N(III), S(IV), and other Species in Frozen Solution – A Possible Pathway for Enhanced Chemical Transformation in Freezing Systems

The chemistry of glycolaldehyde (hydroxyacetaldehyde) relevant to the troposphere has been investigated using UV absorption spectrometry and FTIR absorption spectrometry in an environmental chamber. Quantitative UV absorption spectra have been obtained for the first time. The UV spectrum peaks at 277 nm with a maximum cross section of (5.5± 0.7)×10^–20 cm² molecule^–1. Studies of the ultraviolet photolysis of glycolaldehyde ( = 285 ± 25 nm) indicated that the overall quantum yield is > 0.5 in one bar of air, with the major products being CH₂OH and HCO radicals. Rate coefficients for the reactions of Cl atoms and OH radicals with glycolaldehyde have been determined to be (7.6± 1.5)×10^–11 and (1.1± 0.3)×10^–11 cm³ molecule^–1 s^–1, respectively, in good agreement with the only previous study. The lifetime of glycolaldehyde in the atmosphere is about 1.0 day for reaction with OH, and > 2.5 days for photolysis, although both wet and dry deposition should also be considered in future modeling studies.     

Nitrogen dioxide column content measurements made from an aircraft between 5° and 82°N

In the first two weeks of May 1981, the research jet of the German Aerospace Research Establishment (DFVLR) was charted to fly a meridional section between 5° and 82°N. A scanning filter photometer, developed at the Max Planck Institut für Aeronomie to measure column content values of atmospheric ozone and nitrogen dioxide, using ultra violet and visible absorption techniques, constituted part of the experimental payload for this campaign that was called SIMOC. The vertical NO₂ column content above the aircraft, flying at approximately 10 km, was found to decrease rapidly from 6.9×10¹⁵ molecules cm^-2 to 2.5×10¹⁵ molecules cm^-2 around 50°N and then to increase again north of 75°N. A sharp rise in the NO₂ content was observed south of the subtropical jet but this could possibly be due to the increased depth of the troposphere above the aircraft in these regions.     

Cape Grim isotope measurements — A preliminary assessment

Measurements of the stable carbon isotope ratio in atmospheric CO₂ permit a distinction between variations resulting from biospheric and oceanic exchange. In situ extraction of CO₂ from Cape Grim air (41°S) for isotopic analysis commenced in 1977; however difficulties with technique reliability were experienced until 1982. Since 1982, 2.6 years of relatively consistent values have accumulated.For a preliminary assessment of the latter data, estimates of the isotopic behaviour from the global transport and inter-reservoir exchange model of Pearman and Hyson (1985) have been employed. The assessment demonstrates the precision requirements of a carbon isotope monitoring program and the relevance of the isotope measurements as a constraint on parameterization of the model.Clear evidence of the changes due to fossil fuel combustion is seen in the year-to-year differences in ¹³C, with the mean and standard error of the overall trend being –0.025±0.005 yr^-1. A significant seasonal variation in ¹³C is apparent, despite considerable inter-annual variability possibly associated with the 1982/83 ENSO phenomena. The average peak-to-peak amplitude is 0.055±0.014 with a maximum on day 85±15 (approx. 26 March).There is some evidence for a complex seasonal inter-relationship between concentration and isotope ratio, both in the Cape Grim data and in Mook et al. (1983) South Pole data, but with marked differences between the stations, and with both different from the model estimates.In particular, the Cape Grim results suggest that exchange with Southern Hemisphere biosphere is the main contributor to the seasonal variation in isotope ratio at this latitude.     

Mass transfer at the air/water interface: Mass accommodation coefficients of SO2, HNO3, NO2 and NH3

We present here experimental determinations of mass accommodation coefficients using a low pressure tube reactor in which monodispersed droplets, generated by a vibrating orifice, are brought into contact with known amounts of trace gases. The uptake of the gases and the accommodation coefficient are determined by chemical analysis of the aqueous phase.We report in this article measurements of _exp=(6.0±0.8)×10^–2 at 298 K and with a total pressure of 38 Torr for SO₂, (5.0±1.0)×10^–2 at 297 K and total pressure of 52 Torr for HNO₃, (1.5±0.6)×10^–3 at 298 K and total pressure of 50 Torr for NO₂, (2.4±1.0)×10^–2 at 290 K and total pressure of 70 Torr for NH₃.These values are corrected for mass transport limitations in the gas phase leading to =(1.3±0.1)×10^–1 (298 K) for SO₂, (1.1±0.1)×10^–1 (298 K) for HNO₃, (9.7±0.9)×10^–2 (290 K) for NH₃, (1.5±0.8)×10^–3 (298 K) for NO₂ but this last value should not be considered as the true value of for NO₂ because of possible chemical interferences.Results are discussed in terms of experimental conditions which determine the presence of limitations on the mass transport rates of gaseous species into an aqueous phase, which permits the correction of the experimental values.     

Kinetics of the Reaction of Hydroxyl Radicals with CH2Br2 and its Implications in the Atmosphere

Rate constants for the reaction of hydroxyl radicals with dibromomethanehave been measured by discharge flow-resonance fluorescence technique(DF-RF) over the temperature range 288–368 K. The derived Arrheniusequation is k₁=(1.51 ± 0.37)× 10^-12 exp(-(720 ±60)/T) cm³ molec.^-1 s^-1.The tropospheric lifetime of dibromomethane has been estimated to be 0.29years. An ozone depletion potential (ODP) value of 0.10 for dibromomethanehas been obtained.     

Variations in atmospheric CO2 at the Meteorological Research Institute, Tsukuba, Japan

Since April 1986, measurements of the CO₂ concentration in the surface air have been conducted at the Meteorological Research Institure (MRI, 36°04 N, 140°07 E, 25 m above sea level) in Tsukuba, located 50 km northeast of Tokyo, Japan. The CO₂ data measured over times between 11:00 Japan Standard Time (JST) and 16:00 JST (C _N ) were considered to be representative of the air (within a few ppmv) in the planetary boundary layer. To evaluate the representative CO₂ level on a spatial scale larger than that of the C _N record, the CO₂ data with hour-to-hour variation less than 1 ppmv were selected (C _P ). Comparison of these data with those of Ryori (39°02 N, 141°50 E), a continental station operated by the Japan Meteorological Agency, indicates that the C _P record provides a representative CO₂ level in the air on spatial scales of at least a few hundred kilometers.The C _N record allows an investigation of the internanual changes in photosynthesis/respiration against changes in climatological parameters. Within a small temperature anomaly (ca.±1 °C) respiration is sensitive to the temperature change, while photosynthesis is less sensitive. When the temperature anomaly is large, however, photosynthesis and respiration tend to be competitive.     

An Examination of the Atmospheric Chemistry of Mercury Using 210Pb and 7Be

Measurements of Hg (total gas-phase, precipitation-phase andparticulate-phase), aerosol mass, particulate ²¹⁰Pb and⁷Be and precipitation ²¹⁰Pb were made at an atmosphericcollection station located in a near remote area of northcentral Wisconsin,U.S.A. (46°10N, 89°50W) during the summers of 1993, 1994and 1995. Total Hg and ²¹⁰Pb were observed to correlate strongly(slope = 0.06 ± 0.03 ng mBq^-1; r ² =0.72) in rainwater. Mercury to ²¹⁰Pb ratios in particulate matter(0.03 ± 0.02 ng mBq^-1; r ² = 0.06) wereconsistent with the ratio in rain. Enrichment of the Hg/mass ratio (approx.5–50×) relative to soil and primary pollutant aerosols indicatedthat gas-to-particle conversion had taken place during transport. Comparisonof these results with models for the incorporation of Hg into precipitationindicates that atmospheric particles deliver more Hg to precipitation than canbe explained by the presence of soot. A lack of correlation between totalgas-phase Hg (TGM) and a ⁷Be/²¹⁰Pb function suggests novertical concentration gradient within the troposphere, and allows an estimateof TGM residence time of 1.5 ± 0.6 yr be made based on surface airsamples.