Natural and anthropogenic C2 to C6 hydrocarbons in the central-eastern Venezuelan atmosphere during the rainy season

The levels of low molecular weight hydrocarbons were measured at pristine sites and rural locations affected by hydrocarbon emissions from oil and gas producing fields in Venezuela. At the clean sites, lower concentrations of C₂ to C₆ alkanes were observed, whereas, in comparison with remotes sites, very much higher levels were measured at the polluted sites. Alkenes present relatively high concentrations, with isoprene being the most abundant, all over the study region. The main sources of alkenes are likely to be natural, mainly from vegetation. The levels of alkanes recorded at the clean sites and the alkene levels found everywhere in the region are in agreement with the values reported for other clean sites in the tropics. The increase of ozone production capacity due to the anthropogenic emissions of alkanes from oil and gas fields was estimated. Due to the presence in the atmosphere of important amounts of naturally emitted isoprene, ethene and propene, which makes a substantial contribution to the reactivity of the hydrocarbon mixture, a small increase (<5%) was estimated to occur in the capacity of the ozone production at a regional scale during the rainy season.     

Accuracy of ozonesonde measurements in the troposphere

Measurements of atmospheric ozone at concentrations typical of the free troposphere have been compared for ECC sondes and a UV-absorption photometer, using a Bendix chemiluminescent analyser as a transfer standard. Comparisons were conducted in the laboratory and in the tropospheric part of the atmosphere. It was found that the measurements agreed to within 4% provided that the background current for the ECC sonde was measured before exposure to ozone in the preparation procedure, and was assumed to be constant throughout the sonde flight. These results confirm those of earlier experiments and mean that the methods currently used to correct for the background current in the troposphere need to be revised.     

Collection and analysis of atmospheric ozone samples

Anomalies found in the isotope ratios of ozone are traceable to the ozone formation process. Metastable electronic states may be responsible for the preferred production of the heavy molecules. While laboratory isotope data and first tropospheric results agree well in the magnitude of isotope enrichments, stratospheric measurements show often higher values. Only through the collection of ozone samples can sufficiently large amounts of gas be obtained to analyze the three isotopes ⁴⁸O₃, ⁴⁹O₃, and ⁵⁰O₃. Collector systems have been developed and successfully operated in the troposphere and in the stratosphere. They will play in the future an important role in atmospheric oxygen isotope studies.     

Boundary-layer ozone depletion as seen in the Norwegian Arctic in spring

Several years of measurements of ozone, hydrocarbons, sulphate and meteorological parameters from Spitsbergen in the Norwegian Arctic are presented. Most of the measurements were taken on the Zeppelin Mountain at an altitude of 474 m a.s.l. The focus is the episodes of ozone depletion in the lower troposphere in spring, which are studied in a climatological way. Episodes of very low ozone concentrations are a common feature on the Zeppelin Mountain in spring. The low ozone episodes were observed from late March to the beginning of June. When the effect of transport direction was subtracted, the frequenty of the low ozone episodes was found to peak in the beginning of May, possibly reflecting the seasonal cycle in the actual depletion process. Analyses based on trajectory calculations show that most of the episodes occurred when the air masses were transported from W-N. Ozone soundings show that the ozone depletion may extend from the surface and up to 3–4 km altitude. The episodes were associated with a cold boundary layer beneath a thermally stable layer, suppressing mixing with the free troposphere. The concentration of several individual hydrocarbons was much lower during episodes of low ozone than for the average conditions. The change in concentration ratio between the hydrocarbons was in qualitative agreement with oxidation of hydrocarbons by Br and Cl atoms rather than by OH radicals.     

NO2 total column evolution during the 1989 spring at Antarctica Peninsula

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

A Eulerian air pollution model for Europe with nonlinear chemistry

A long-range transport model with nonlinear chemical reactions is described. The model contains 35 pollutants and 70 chemical reactions. This is a Eulerian model defined on a space domain containing the whole of Europe. The spherical space domain (corresponding to the Earth's surface covered by the model) is mapped into a square plane domain and discretized by using a 32×32 grid. The grid increments are equidistant (both along the Ox axis and along the Oy axis). The choice of values of the physical parameters involved in the model and the numerical treatment of the model are shortly discussed. The model is tested with meteorological data for 1985 and 1989. The numerical results are compared with measurements at stations located in different European countries. Extensive comparisons of ozone concentrations for July 1985 with measurements taken at 24 European stations are also carried out. Results concerning three episodes in July 1985 as well as results obtained in the study of the sensitivity of the ozone concentrations to variations of NO _x and/or anthropogenic VOC emissions are presented. The advantages and the limitations of such a model are discussed. The model is continuously improved by adding new modules to it. The plans for improvements in the near future are outlined.     

Assessment of the Uncertainties in the NO2 and O3 Measurements by Visible Spectrometers

The column amounts of nitrogen dioxide (NO2) and ozone (O3) were measured using a visible spectrometer based on the twilight zenith-sky technique at two observatories located at similar latitudes in the northern part of Japan separated by a distance of 150 km. The measurements began in April 1991 at the Moshiri Observatory (44.4°N, 142.3°E) and in April 1994 at the Rikubetsu Observatory (43.5°N, 143.8°E). Since weather conditions and the possible influence from tropospheric pollution were not always identical at these two observatories, the overall accuracy of the measurements was studied comparing these data sets. The first year data obtained at a solar zenith angle of 90 degrees indicated that the NO2 slant column values at sunrise and sunset agreed within 0.36 and 0.54 × 1016 cm-2, respectively, corresponding to 5 % (June) and to 12 % (December) of the columns. The O3 values agreed within 0.76 × 1019 cm-2, corresponding to 4 % (March) 6 % (August) of the columns, although a part of the difference was systematic. The O3 column amounts were also compared to those obtained by the Dobson spectrometer at Sapporo (43.5°N, 143.8°E), whose latitude is similar to these observatories. When an air mass factor of 17.5 was used, the two-year Moshiri vertical column values agreed with the Dobson direct sun values to within 15 Dobson Units, or 3 6 % of the column. The difference between the two values was found to be due partly to the change in the air mass factor caused by seasonal and day-to-day changes in the shape of the O3 vertical profiles. These results confirm the reliability of the NO2 and O3 measurements by visible spectrometers at these sites for the Network for the Detection of Stratospheric Change (NDSC).     

The possible influences of the increasing anthropogenic emissions in India on tropospheric ozone and OH

A 3-D chemical transport model (OSLO CTM2) is used to investigate the influences of the increasing anthropogenic emission in India. The model is capable of reproducing the observational results of the INDOEX experiment and the measurements in summer over India well. The model results show that when NOx and CO emissions in India are doubled, ozone concentration increases, and global average OH decreases a little. Under the effects of the Indian summer monsoon, NOx and CO in India are efficiently transported into the middle and upper troposphere by the upward current and the convective activities so that the NOx, CO, and ozone in the middle and upper troposphere significantly increase with the increasing NOx and CO emissions. These increases extensively influence a part of Asia, Africa, and Europe, and persist from June to September.     

Parameterization of the non-local thermodynamic equilibrium source function with chemical production by an equivalent two-level model

The classic two-level or equivalent two-level model that includes only the statistical equilibriumof radiative and thermal processes of excitation and quenching between two vibrational energy levelsis extended by adding chemical production to the rate equations. The modifications to the non-localthermodynamic equilibrium source function and cooling rate are parameterized by φc, which characterizesthe ratio of chemical production to collisional quenching. For applications of broadband emission of O3 at9.6 μm, the non-LTE effect of chemical production on the cooling rate and limb emission is proportionalto the ratio of O to O3. For a typical [O]/[O3], the maximum enhancements of limb radiance and coolingrate are about 15%-30% and 0.03-0.05 K day-1, respectively, both occurring near the mesopause regions.This suggests that the broadband limb radiance above ～80 km is sensitive to O3 density but not sensitiveto the direct cooling rate along the line-of-sight, which makes O3 retrieval feasible but the direct coolingrate retrieval difficult by using the O3 9.6 μm band limb emission.     

Product study of the reaction of OH radicals with isoprene in the atmosphere simulation chamber SAPHIR

Atmospheric oxidation of isoprene and its oxidation products methacrolein (MACR) and methyl vinyl ketone (MVK) have an important impact on the photochemical activity in the boundary layer, in particular in forested areas. The oxidation of isoprene by OH radicals was investigated in chamber experiments conducted under tropospheric conditions in the atmosphere simulation chamber SAPHIR at the Research Center Jülich. The aim was to determine the product yield of MVK and MACR in the OH-induced isoprene oxidation and the rate constant of their reaction with OH under real atmospheric conditions. The recently published updated degradation scheme for isoprene from Geiger et al. (2003) was used to determine rate constants and product yields. The fractional yields in the isoprene peroxy radical reaction with NO were found to be 0.41±0.03 for MVK and 0.27±0.03 for MACR. The rate coefficient for MACR with OH was found to be in very good agreement with the recommended value of IUPAC Atkinson (Atkinson et al., 2005). while the rate coefficient for MVK with OH was 27% lower.