The role of clouds in tropospheric photochemistry

We show that photochemical processes in the lower half of the troposphere are strongly affected by the presence of liquid water clouds. Especially CH₂O, an important intermediate of CH₄ (and of other hydrocarbon) oxidation, is subject to enhanced breakdown in the aqueous phase. This reduces the formation of HO _x -radicals via photodissociation of CH₂O in the gas phase. In the droplets, the hydrated form of CH₂O, its oxidation product HCO₂ ^–, and H₂O₂ recycle O₂ ^– radicals which, in turn, react with ozone. We show that the latter reaction is a significant sink for O₃. Further O₃ concentrations are reduced as a result of decreased formation of O₃ during periods with clouds. Additionally, NO _x , which acts as a catalyst in the photochemical formation of O₃, is depleted by clouds during the night via scavenging of N₂O₅. This significantly reduces NO _x -concentrations during subsequent daylight hours, so that less NO _x is available for O₃ production. Clouds thus directly reduce the concentrations of O₃, CH₂O, NO _x , and HO _x . Indirectly, this also affects the budgets of other trace gases, such as H₂O₂, CO, and H₂.     

Extremely low temperatures in the stratosphore and very low total ozone amount above northern and central Europe during winter 1989

On 1 February 1989, -83.5°C was recorded in 27.8 hPa over Hohenpeißenberg, the lowest temperature in the 22-year series. This was measured together with a very low total ozone amount of 266 DU. This may be compared with nearly twice this amount on 27 February 1989. The situation was very unusual: following an extremely cold winter in the Arctic stratosphere, the stratospheric cold pole was located over southern Scandinavia on 1 February in a very southerly position. The analyzed temperatures of -92 °C in 30 hPa were also unusual. Even though the low ozone amounts over Hohenpeißenberg were probably dynamically caused, an additional very small ozone decrease due to heterogeneous reactions in altitudes from 23–28 km, where the temperatures lie below -80 °C, cannot be ruled out. Extinction measurements by the orbitting SAGE II instrument indeed show polar stratospheric clouds over Europe near 50° N during the period 31 January–2 February. Also, polar stratospheric clouds were previously observed over Kiruna at similarly low temperatures and signs of a corresponding small ozone decrease were noted there.     

气象因子对近地面臭氧污染影响的研究

本文通过对１９９３年春季和春夏之交的O3浓度逐日变化、日变化和气象因子关系的分析，提出了影响O3浓度的主导气象因子和不同情况下形成高浓度O3的主要因子，提出了大风速对逐日变化中O3浓度特高及浓度日变化峰值的重要作用，并指出高温、低湿、小风并不是在所有情况都是促成高浓度O3的因子。另外，雾也可以成为近地面O3浓度增值的因素，主要原因是雾内湍流发展将高浓度O3大量输向下方。     

Performance of the electrochemical ozone sonde OSR

Summary The accuracy of the electrochemical ozone sonde, type OSR, has been estimated by analysing tandem ozone soundings of the balloon-borne electrochemical ozone sonde OSR at the Lindenberg Observatory from May to November 1982. A negative bias, though not significant, has been observed above about 28 km for soundings having high single correction factors. Random errors are at their minimum just above the level of the maximum of ozone partial pressure, and reach their maximum in the troposphere. Except at heights above about 28 km the random error of ozone sondes is a factor 2 to 3 times less than the error of the short Umkehr method. Provided that soundings with too high correction factors are neglected, the ozone sonde OSR has an accuracy comparable to that of other Brewer type sondes.The maximum amount of information on the vertical ozone distribution can be drawn from sonde measurements in the lower stratosphere. A study is underway to improve the sensitivity of the sonde OSR and thus to further enhance its reliability.     

The latitudinal distribution of carbon monoxide across the pacific from California to Antarctica

The results of a research study of the carbon monoxide concentration from California to 90° S, Antarctica are presented. The data both extend and support other research studies of the latitudinal distribution of carbon monoxide in that higher concentrations are evident over the Northern Hemisphere than over the Southern Hemisphere. Carbon monoxide concentrations range between 50 to 60 ppb with a few peaks into the 60s in the latitudinal area south of the ITCZ and values of 80 ppb or higher at latitudes north of Hawaii. A comparison is also made of carbon monoxide and ozone concentrations along the flight tract between California and Antarctica, over the Ellsworth Mountains of Antarctica, and between 78° S and the South Pole. These ozone-carbon monoxide data show statistically significant negative correlations in the upper troposphere and lower stratosphere over Antarctica. It is believed that this is a good indication of mixing across the tropopause.     

Ultraviolet absorption spectra of some Br-containing haloalkanes

The ultraviolet absorption cross sections were measured for CF₃Br, CF₂ClBr, CF₂Br-CF₂Br, CF₂Br₂, CHF₂Br, CHFBr-CF₃, CH₂Br-CF₃, CHClBr-CF₃ in the wavelength range 190–320 nm at 295 K. The photolysis is concluded to be the minor atmospheric sink for CHF₂Br, CHFBr-CF₃, CH₂Br-CF₃, CHClBr-CF₃.     

Total ozone response to major geomagnetic storms and changes in meteorological situations

Summary The total ozone response to strong major geomagnetic storms (A_p≥60) in winter along the 50° N latitudinal circle is studied. The results add to the recent results of Laštovička et al. (1992) obtained for European middle latitudes (∼50°N) and to the results of Mlch (1994). A significant response of total ozone is only observed in winter under high solar activity/E-phase of QBO conditions (E-max) and seems to be caused by geomagnetic storm-induced changes of atmospheric dynamics. There are two sectors along latitude 50°N, which are sensitive to forcing by geomagnetic storms both in total ozone and the troposphere — north-eastern Atlantic-European and eastern Siberia-Aleutian sectors. The total ozone response under E-max conditions manifests itself mainly as a large decrease in the longitudinal variation of ozone after the storm, which means an increase of ozone in Europe. The observed effects in total ozone consist in redistribution, not production or loss of ozone.     

Low-latitude total ozone measurements in the Brazilian sector

Regular measurements of the atmospheric ozone in the Brazilian sector were started at Cachoeira Paulista (22.7°S, 45.0°W), and Natal (5.8°S, 35.2°W) in May 1974 and November 1978, respectively. The results of the total ozone measurements carried out at these two stations up to 1981 are presented in this communication and compared with other low-and mid-latitude stations. Although Natal is an equatorial station, it presents a prominent annual variation, and the average total ozone content is high compared to satellite measurements. During 1977–78, abnormally low values of total ozone were observed at Cachoeira Paulista. Some preliminary results about the QBO 9quasi-biennial oscillation) during 1974–81 are also presented.     

Ozone Production Efficiency in Savanna and Forested Areas during the EXPRESSO Experiment

NO, NO_x, NO_y and O₃ have been measuredduring the airborne EXPRESSO experiment, November 96,which took place near Bangui (Central Africa) at thebeginning of the dry season. This period correspondsto an intense burning activity. Chemical andphotochemical characteristics of the planetaryboundary layer, which corresponds most of the time tothe monsoon layer, and the Harmattan layer, which issituated above the latter, have been studied forsavanna as well as rain forest areas. These two layersare very different when considering the chemicalcomposition (especially for ozone and NO_z) andthe photochemical age.The relationship of photochemical ozone productionversus photochemical NO_x oxidation products hasbeen investigated. Results indicate an ozoneproduction efficiency (OPE) ranging from 6.3 to 14.8in the planetary boundary layer. Thus, this layer ischaracteristic of a photochemically young and activeair mass. In this layer, the ozone potentialproduction increases with the air mass photochemicalage. On the other hand, the Harmattan layer shows anOPE ranging from 4.6 to 7.4. These values arecharacteristic of photochemically well-aged airmasses. In this layer, the ozone potential productionseems to be exhausted with values around 4.0 (i.e., 4ozone molecules produced for each NO_x moleculeemitted).     

MEASUREMENTS AND MODEL SIMULATIONS OF SURFACE OZONE VARIATIONS AT DIFFERENT BACKGROUND CONCENTRATIONS OF THE PRECURSORS

Ozone photochemical production and loss in very different environments at Waliguan baselinestation and Lin'an background station were simulated by using the measurement data and photo-chemical box model.The results show that net ozone photochemical production rate is negative,about 0.5 ppb/d,at Waliguan baseline sation,because of very low precursor concentrations.Butat Lin'an background station,the net photochemical ozone production is positive,about 2—3 ppb/h.which is very closed with the measurement at Lin'an.That means ozone production was con-trolled by photochemical reactions at Lin'an background station,because of the higher precursorconcentrations.The net destruction rate,at Waliguan Mt.,is not large,so that future increase inanthropogenic emission of reactive nitrogen will lead to larger production rates of steady-state O_3concentration.