Modelling chemistry in the nocturnal boundary layer above tropical rainforest and a generalised effective nocturnal ozone deposition velocity for sub-ppbv NOx conditions

Measurements of atmospheric composition have been made over a remote rainforest landscape. A box model has previously been demonstrated to model the observed daytime chemistry well. However the box model is unable to explain the nocturnal measurements of relatively high [NO] and [O₃], but relatively low observed [NO₂]. It is shown that a one-dimensional (1-D) column model with simple O₃-NO_x chemistry and a simple representation of vertical transport is able to explain the observed nocturnal concentrations and predict the likely vertical profiles of these species in the nocturnal boundary layer (NBL). Concentrations of tracers carried over from the end of the night can affect the atmospheric chemistry of the following day. To ascertain the anomaly introduced by using the box model to represent the NBL, vertically-averaged NBL concentrations at the end of the night are compared between the 1-D model and the box model. It is found that, under low to medium [NO_x] conditions (NO_x?<?1 ppbv), a simple parametrisation can be used to modify the box model deposition velocity of ozone, in order to achieve good agreement between the box and 1-D models for these end-of-night concentrations of NO_x and O₃. This parametrisation would could also be used in global climate-chemistry models with limited vertical resolution near the surface. Box-model results for the following day differ substantially if this effective nocturnal deposition velocity for ozone is implemented; for instance, there is a 9% increase in the following days peak ozone concentration. However under medium to high [NO_x] conditions (NO_x > 1 ppbv), the effect on the chemistry due to the vertical distribution of the species means no box model can adequately represent chemistry in the NBL without modifying reaction rate coefficients.     

NUMERICAL SIMULATION OF THE SEASONAL VARIATION OF TROPOSPHERIC OZONE OVER CHINA

An updated version of the Regional Acid Deposition Model(RADM)driven by meteorologicalfields derived from Chinese Regional Climate Model(CRegCM)is used to simulate seasonal variationof tropospheric ozone over the eastern China.The results show that:(1)Peak O_3 concentration moves from south China to north China responding to the changing ofsolar perpendicular incidence point from south to north.When solar perpendicular incidence pointmoves from north to south,so does the peak O_3 concentration.(2)In the eastern China.the highest O_3 month-average concentration appears in July.thelowest in January and the medium in April and October.The pattern mainly depends on the solarradiation,the concentration of O_3 precursors NO_x and NMHC and the ratio of NMHC/NO_x.(3)Daily variations of O_3 over the eastern China are clear.Namely,O_3 concentrations rise withthe sun rising and the maximums appear at noon.then O_3 concentrations decrease.The highest dailyvariation range of O_3 appears in summer(40×10~(-9) in volume fraction)and the lowest in winter(20×10~(-9) in volume fraction).(4)Daily variations of O_3 over the western China are not clear.The daily variation range of O_3 isless than 10×10~(-9) in volume fraction.     

Convective Redistribution of Ozone and Oxides of Nitrogen in the Troposphere over Europe in Summer and Fall

The fluxes of ozone and NO_x out of the atmospheric boundary layer (ABL) over Europe are calculated in a mesoscale chemical transport model (MCT) and compared with the net chemical production or destruction of ozone and the emissions of precursors within the ABL for two 10 days' periods which had quite different synoptic situations and levels of photochemical activity (1–10 July 1991 (JUL91) and 26 October–4 November 1994 (ON94)). Over the European continent, about 8% of the NO_x emissions were brought from the ABL to the free troposphere as NO_x, while about 15% of the NO_x emissions were brought to the free troposphere as NO_y–NO_x, i.e. as PAN or HNO₃. The convection dominates over the synoptic scale vertical advection as a transport mechanism both for NO_x and NO_y out of the boundary layer in the summertime high pressure situation (JUL91), while in the fall situation (ON94) the convective part was calculated to be the smallest. NO_x was almost completely transformed to NO_y–NO_x or removed within the ABL. Also for NO_y the major part of the atmospheric cycle is confined to the ABL both for JUL91 and ON94. The vertical transport time out of the ABL is of the order of 100h both for the total model domain and over the European continent. The net convective exchange of ozone from the ABL is not a dominant process for the amount of ozone in the ABL averaged over 10 days and the whole domain, but convection reduces the maximum ozone concentration in episodes significantly. The ozone producing efficiency of NO_x is calculated to increase with height to typically 15–20 in the upper half of the troposphere from around 5 in the ABL, but in the middle free troposphere the concentration of NO_x is often too low to cause net chemical formation of ozone there.     

中美大气化学联合考察实验结果的初步分析与比较

根据临安区域本底站观测资料分析结果得出,中国中纬度地区秋、冬季O₃及其前体物NO_x等浓度偏高,可以对农作物和地表生态系统产生影响.观测结果表明:近地层大气O₃浓度主要决定于地面总辐射量控制下的光化学反应过程;O₃的生成受到前体物NO_x的控制,但O₃与NO_x存在着明显的非线性关系.从PEM-WESTA和B的实验及1995年的观测资料表明,O₃的生成效率随着NO_x浓度的增大而减小.尽管O₃的生成速率秋季比冬季的大,但由于秋季较高的NO_x抑制了过氧基的生成,因此冬季O₃的累积量几乎可以和秋季相比拟.在临安观测的NMHC和NO_x的比值比国外同纬度地区测值要大.这说明在临安本底站O₃的光化学生成中,NMHC不是控制物种.从而提示我们,在这些季节临安O₃光化学产物能够被NO_x浓度所控制.中美大气化学联合考察(PEM-WEST-B)实验期间,台湾省的卡盯站SO₂的平均浓度为0.29ppb,O₃的平均浓度为42.2ppb,可以认为此值为低纬度海岛的本底值.1994年PEM-WEST-B实验期间临安站的观测资料和台湾省的卡盯站资料相比,临安站SO₂的浓度约为卡盯站SO₂浓度的50倍左右,从而可以看出人类活动对大气本底的显着影响.     

Airborne measurements of turbulent trace gas fluxes and analysis of eddy structure in the convective boundary layer over complex terrain

Using the new high-frequency measurement equipment of the research aircraft DO 128, which is described in detail, turbulent vertical fluxes of ozone and nitric oxide have been calculated from data sampled during the ESCOMPTE program in the south of France. Based on airborne turbulence measurements, radiosonde data and surface energy balance measurements, the convective boundary layer (CBL) is examined under two different aspects. The analysis covers boundary-layer convection with respect to (i) the control of CBL depth by surface heating and synoptic scale influences, and (ii) the structure of convective plumes and their vertical transport of ozone and nitric oxides. The orographic structure of the terrain causes significant differences between planetary boundary layer (PBL) heights, which are found to exceed those of terrain height variations on average. A comparison of boundary-layer flux profiles as well as mean quantities over flat and complex terrain and also under different pollution situations and weather conditions shows relationships between vertical gradients and corresponding turbulent fluxes. Generally, NO_x transports are directed upward independent of the terrain, since primary emission sources are located near the ground. For ozone, negative fluxes are common in the lower CBL in accordance with the deposition of O₃ at the surface.The detailed structure of thermals, which largely carry out vertical transports in the boundary layer, are examined with a conditional sampling technique. Updrafts mostly contain warm, moist and NO_x loaded air, while the ozone transport by thermals alternates with the background ozone gradient. Evidence for handover processes of trace gases to the free atmosphere can be found in the case of existing gradients across the boundary-layer top. An analysis of the size of eddies suggests the possibility of some influence of the heterogeneous terrain in mountainous area on the length scales of eddies.     

NUMERICAL SIMULATION OF OZONE DISTRIBUTIONS AND ITS VARIATION MECHANISM*

A 2-D global chemistry-transport model is set up in this paper.The model simulates the atmospheric ozone distributions well with specified dynamical conditions.The analysis of ozone variation mechanism shows that ozone is chemically in quasi-equilibrium except for the polar night region where the variation of ozone concentration is under the control of dynamical processes,that the oxygen atoms which produce ozone are mainly provided by the photolysis of O₂ in the upper stratosphere and by the photolysis of NO₂ in the lower stratosphere and the troposphere.and that the ozone is destroyed mainly by NO_x:the reactions between NO_x and O₃ and the odd oxygen cycle contribute 80% to more than 90% of the ozone destruction.     

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.     

Impact of Non-Methane Hydrocarbons on Tropospheric Chemistry and the Oxidizing Power of the Global Troposphere: 3-Dimensional Modelling Results

The impact of natural and anthropogenicnon-methane hydrocarbons (NMHC) on troposphericchemistry is investigated with the global,three-dimensional chemistry-transport model MOGUNTIA.This meteorologically simplified model allows theinclusion of a rather detailed scheme to describeNMHC oxidation chemistry. Comparing model resultscalculated with and without NMHC oxidation chemistryindicates that NMHC oxidation adds 40–60% to surfacecarbon monoxide (CO) levels over the continents andslightly less over the oceans. Free tropospheric COlevels increase by 30–60%. The overall yield of COfrom the NMHC mixture considered is calculated to beabout 0.4 CO per C atom. Organic nitrate formationduring NMHC oxidation, and their transport anddecomposition affect the global distribution of NO _x and thereby O₃ production. The impact of theshort-lived NMHC extends over the entire tropospheredue to the formation of longer-lived intermediateslike CO, and various carbonyl and carboxyl compounds.NMHC oxidation almost doubles the net photochemicalproduction of O₃ in the troposphere and leads to20–80% higher O₃ concentration inNO _x -rich boundarylayers, with highest increases over and downwind ofthe industrial and biomass burning regions. Anincrease by 20–30% is calculated for the remotemarine atmosphere. At higher altitudes, smaller, butstill significant increases, in O₃ concentrationsbetween 10 and 60% are calculated, maximizing in thetropics. NO from lightning also enhances the netchemical production of O₃ by about 30%, leading to asimilar increase in the global mean OH radicalconcentration. NMHC oxidation decreases the OH radicalconcentrations in the continental boundary layer withlarge NMHC emissions by up to 20–60%. In the marineboundary layer (MBL) OH levels can increase in someregions by 10–20% depending on season and NO _x levels.However, in most of the MBL OH will decrease by10–20% due to the increase in CO levels by NMHCoxidation chemistry. The large decreases especiallyover the continents strongly reduce the markedcontrasts in OHconcentrations between land and oceanwhich are calculated when only the backgroundchemistry is considered. In the middle troposphere, OHconcentrations are reduced by about 15%, although dueto the growth in CO. The overall effect of thesechanges on the tropospheric lifetime of CH₄ is a 15%increase from 6.5 to 7.4 years. Biogenic hydrocarbonsdominate the impact of NMHC on global troposphericchemistry. Convection of hydrocarbon oxidationproducts: hydrogen peroxides and carbonyl compounds,especially acetone, is the main source of HO _x in theupper troposphere. Convective transport and additionof NO from lightning are important for the O₃ budgetin the free troposphere.     

Photochemistry in the Arctic Free Troposphere: Ozone Budget and Its Dependence on Nitrogen Oxides and the Production Rate of Free Radicals

Local ozone production and loss rates for the arctic free troposphere (58–85° N, 1–6 km, February–May) during the TroposphericOzone Production about the Spring Equinox (TOPSE) campaign were calculated using a constrained photochemical box model. Estimates were made to assess the importance of local photochemical ozone production relative to transport in accounting for the springtime maximum in arctic free tropospheric ozone. Ozone production and loss rates from our diel steady-state box model constrained by median observations were first compared to two point box models, one run to instantaneous steady-state and the other run to diel steady-state. A consistent picture of local ozone photochemistry was derived by all three box models suggesting that differences between the approaches were not critical. Our model-derived ozone production rates increased by a factor of 28 in the 1–3 km layer and a factor of 7 in the 3–6 kmlayer between February and May. The arctic ozone budget required net import of ozone into the arctic free troposphere throughout the campaign; however, the transport term exceeded the photochemical production only in the lower free troposphere (1–3 km) between February and March. Gross ozone production rates were calculated to increase linearly with NO_x mixing ratiosup to 300 pptv in February and for NO_x mixing ratios up to 500 pptv in May. These NO_x limits are an order of magnitude higher thanmedian NO_x levels observed, illustrating the strong dependence ofgross ozone production rates on NO_x mixing ratios for the majority of theobservations. The threshold NO_x mixing ratio needed for netpositive ozone production was also calculated to increase from NO_x 10pptv in February to 25 pptv in May, suggesting that the NO_x levels needed to sustain net ozone production are lower in winter than spring. This lower NO_x threshold explains how wintertime photochemical ozone production can impact the build-up of ozone over winter and early spring. There is also an altitude dependence as the threshold NO_x neededto produce net ozone shifts to higher values at lower altitudes. This partly explains the calculation of net ozone destruction for the 1–3 km layerand net ozone production for the 3–6 km layer throughout the campaign.     

Responses of the tropospheric ozone and odd hydrogen radicals to column ozone change

The response of tropospheric ozone to a change in solar UV penetration due to perturbation on column ozone depends critically on the tropospheric NO _x (NO+NO₂) concentration. At high NO _x or a polluted area where there is net ozone production, a decrease in column ozone will increase the solar UV penetration to the troposphere and thus increase the tropospheric ozone concentration. However, the opposite will occur, for example, at a remote oceanic area where NO _x is so low that there is net ozone destruction. This finding may have important implication on the interpretation of the long term trend of tropospheric ozone. A change in column ozone will also induce change in tropospheric OH, HO₂, and H₂O₂ concentrations which are major oxidants in the troposphere. Thus, the oxidation capacity and, in turn, the abundances of many reduced gases will be perturbed. Our model calculations show that the change in OH, HO₂, and H₂O₂ concentrations are essentially independent of the NO _x concentration.     

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).     

A one-dimensional photochemical model of the troposphere with planetary boundary-layer parameterization

The results from a one-dimensional photochemical model of the troposphere representative of summertime conditions at Northern Hemisphere mid-latitudes are presented. A parameterization of mixing processes within the planetary boundary layer (PBL) has been incorporated into the model for both the daytime convective PBL and the formation of the nocturnal PBL. One result of the parameterized PBL is that the concentrations of some trace species in the free troposphere are 20–30% higher than when mixing processes are described by a vertical eddy diffusion coefficient which is held constant with respect to height and time.The calculations indicate that the lifetime of the oxides of nitrogen (NO _x =NO+NO₂) against photochemical conversion to nitric acid (HNO₃) during summertime conditions is on the order of 6 h. This lifetime is short enough to deplete most of the NO _x in the PBL, resulting in the finding that other reactive nitrogen species (HNO₃ and peroxyacetyl nitrate) are more abundant than NO _x throughout the free troposphere, even though NO _x is the most abundant reactive nitrogen species at the surface. The effects of the inclusion of anthropogenic nonmethane hydrocarbon (NMHC) chemistry are also discussed. The inclusion of NMHC chemistry has a pronounced effect on the photochemistry of tropospheric oxone and increases thein situ column production by more than 30%.     

Profiles and simulated exchange of H2O,O3, NO2 between the atmosphere and the HartX Scots pine plantation

Summary Vertical profiles of H₂O, CO₂, O₃, NO and NO₂ were measured during the Hartheim Experiment (HartX) to develop and calibrate a multi-layer resistance model to estimate deposition and emission of the cited gaseous species. The meteorological and gas concentration data were obtained with a 30 m high telescopic mast with 7 gas inlets located at 5 m intervals and meteorological sensors at 5, 15 and 30 m above ground; a complete gas profile was obtained every 9 min 20 s. Measured profiles were influenced by several exchange processes, namely evapotranspiration, dewfall, assimilation of CO₂ in the tree crowns, soil respiration, deposition of NO₂ and O₃ to the soil and advection of NO_x from the nearby highway. Surprisingly, no decrease in O₃ concentration was observed in the crown layer during daytime, probably due to the relatively low density of foliage elements and strong turbulent mixing.The advantage of measuring in-canopy profiles is that turbulent exchange coefficients need not be estimated as a prerequisite to obtaining vertical flux estimates. In recent years, flux-gradient relationships in canopies have been subject to many criticisms. If fluxes are calculated at several heights considering only the transfers between the turbulent air and the interacting surfaces at a certain height, and those fluxes are then integrated vertically in a subsequent step, then exchange estimates (deposition or emission) can be obtained independent of turbulent exchange conditions.Typical estimated deposition velocities calculated for a 3-day period are between 4 and 10 mm/s for NO₂ and about 4–9 mm/s for O₃ (day and night values respectively). This leads to deposition rates of about 20–40 ng N/m²s for NO₂ and about 30–40 mg O₃/m² deposited daily under the conditions encountered during HartX. Sensitivity tests done with the best available and most realistic values for model parametrization have shown that sensitivity is large with respect to the soil and cuticula resistances as well as for gas-phase ozone destruction and that more research is required to describe the effectiveness of cuticula and soil in modifying sink characteristics for NO₂ and O₃.With 12 Figures     

A Simple Model for the Vertical Transport of Reactive Species in the Convective Atmospheric Boundary Layer

We have developed a simple, steady-state, one-dimensional second-order closure model to obtain continuous profiles of turbulent fluxes and mean concentrations of non-conserved scalars in a convective boundary layer without shear. As a basic tool we first set up a model for conserved species with standard parameterizations. This leads to formulations for profiles of the turbulent diffusivity and the ratio of temperature-scalar covariance to the flux of the passive scalar. The model is then extended to solving, in terms of profiles of mean concentrations and fluxes, the NO _x –O₃ triad problem. The chemical reactions involve one first-order reaction, the destruction of NO₂ with decay time τ, and one second-order reaction, the destruction of NO and O₃ with the reaction constant k. Since the fluxes of the sum concentrations of NO _x = NO + NO₂ and O₃ + NO₂ turn out to be constant throughout the boundary layer, the problem reduces to solving two differential equations for the concentration and the flux of NO₂. The boundary conditions are the three surface fluxes and the fluxes at the top of the boundary layer, the last obtained from the entrainment velocity, and the concentration differences between the free troposphere and the top of the boundary layer. The equations are solved in a dimensionless form by using 1/(kτ) as the concentration unit, the depth h of the boundary layer as the length unit, the convective velocity scale w _* as the velocity unit, and the surface temperature flux divided by w _* as the temperature unit. Special care has been devoted to the inclusion of the scalar–scalar covariance between the concentrations of O₃ and NO. Sample calculations show that the fluxes of the reactive species deviate significantly from those of non-reactive species. Further, the diffusivities, defined by minus the flux divided by the concentration gradient may become negative for reactive species in contrast to those of non-reactive species, which in the present model are never negative.     

Emission characteristic of ozone related trace gases at a semi-urban site in the Indo-Gangetic plain using inter-correlations

Measurements of surface O₃, CO, NO_x and light NMHCs were made during December 2004 at Hissar, a semi-urban site in the state of Haryana in north-west region of the Indo-Gangetic Plain (IGP). The night-time O₃ values were higher when levels of CO, NO and NO₂ were lower but almost zero values were observed during the episodes of elevated mixing ratios of CO (above 2000 ppbv) and NO_x (above 50 ppbv). Slopes derived from linear fits of O₃ versus CO and O₃ versus NO_x scatter plots were also negative. However, elevated levels of O₃ were observed when CO and NO_x were in the range of 200–300 ppbv and 20–30 ppbv, respectively. Slope of CO-NO_x of about 33 ppbv/ppbv is much larger than that observed in the US and Europe indicating significant impact of incomplete combustion processes emitting higher CO and lesser NO_x. Correlations and ratios of these trace gases including NMHCs show dominance of recently emitted pollutants mostly from biomass burning at this site.     

Satellite Measurements of Tropospheric Column O<Subscript>3</Subscript> and NO<Subscript>2</Subscript> in Eastern and Southeastern Asia: Comparison with a Global Model (MOZART-2)

Satellite measurements of tropospheric column O₃ and NO₂ in eastern and southeastern Asia are analyzed to study the spatial and seasonal characteristics of pollution in these regions. Tropospheric column O₃ is derived from differential measurements of total column ozone from Total Ozone Mapping Spectrometer (TOMS), and stratospheric column ozone from the Microwave Limb Sounder (MLS) instrument on the Upper Atmosphere Research Satellite (UARS). The tropospheric column NO₂ is measured by Global Ozone Monitoring Experiment (GOME). A global chemical and transport model (Model of Ozone and Related Chemical Tracers, version 2; MOZART-2) is applied to analyze and interpret the satellite measurements. The study, which is based on spring, summer, and fall months of 1997 shows generally good agreement between the model and satellite data with respect to seasonal and spatial characteristics of O₃ and NO₂ fields. The analysis of the model results show that the industrial emission of NO_x (NO + NO₂) contributes about 50%–80% to tropospheric column NO₂ in eastern Asia and about 20%–50% in southeastern Asia. The contribution of industrial emission of NO_x to tropospheric column O₃ ranges from 10% to 30% in eastern Asia. Biomass burning and lightning NO_x emissions have a small effect on tropospheric O₃ in central and eastern Asia, but they have a significant impact in southeastern Asia. The varying effects of NO_x on tropospheric column ozone are attributed to differences in relative abundance of volatile organic compounds (VOCs) with respect to total nitrogen in the two regions.     

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.     

Active Nitrogen in Surface Ozone Depletion Events at Alert during Spring 1998

Measurements of NO_x,y were made at Alert, Nunavut, Canada (82.5° N, 62.3° W) during surface layer ozone depletion events. In spring 1998, depletion events were rare and occurred under variable actinic flux, ice fog, and snowfall conditions. NO_y changed by less than 10% between normal, partially depleted, and nearly completely depleted ozone air masses. The observation of a diurnal variation in NO_x under continuous sunlight supports a source from the snowpack but with rapid conversion to nitrogen reservoirs that are primarily deposited to the surface or airborne ice crystals. It was unclear whether NO_x was reduced or enhanced in different stages of the ozone depletion chemistry because of variations in solar and ambient conditions. Because ozone was depleted from 15–20 ppbv to less than 1 ppbv in just over a day in one event it is apparent that the surface source of NO_x did not grossly inhibit the removal of ozone. In another case ozone was shown to be destroyed to less than the 0.5 ppbv detection limit of the instrument. However, simple model calculations show that the rate of depletion of ozone and its final steady-state abundance depend sensitively on the strength of the surface source of NO_x due to competition from ozone production involving NO_x and peroxy radicals. The behavior of the NO/NO₂ ratio was qualitatively consistent with enhanced BrO during the period of active ozone destruction. The model is also used to emphasize that the diurnal partitioning of BrO_x during ozone depletion events is sensitive to even sub ppbv variations in O₃.     

Concentration of trace gases in the lower troposphere,simultaneously recorded at neighboring mountain stations Part II: Ozone

Summary Long-term ozone recordings at different altitude levels, conducted in remote areas, can make a valuable contribution to an understanding of the background level of ozone, its periodical variations and possible long-term trends.The measuring stations (three high mountain stations between 740 and nearly 3000 m a.s.l. with small horizontal distance) are described together with recording and calibration procedures. Information is provided on the time history of all recordings since 1978, considering not only the annual means but also the monthly and 10-day means as a function of height. An analysis is presented of the annual variations which differ considerably in the respective height levels and—in three-dimensional diagrams—the correlation between daily and annual variation is shown as a function of height. Then follows a careful parameterization: analysis of the frequency distribution of the ozone concentration, correlation with relative humidity, relative sunshine duration, and temperature. It can be seen that the correlations are very different and partly inverse, depending on the altitude level.Many ozone profiles obtained between valley level and nearly 3000 m a.s.l. (cable car O₃ radiosonde) give a picture of the typical ozone profile for different meteorological situations and for the case of stratospheric intrusions of ozone into the troposphere. The stratospheric contribution of ozone to the tropospheric ozone budget is discussed.Since obviously a very high photochemical production rate can be established for ozone in the lowest layer above ground (correlation of O₃ with the daily variation of the sunshine duration) it was examined if this O₃ variation might be caused only by horizontal transport of ozone from remote areas with high anthropogenic activity by the daily quasiperiodical currents near the ground. But this is not the case.The correlation between ozone concentration, other trace gases such as nitrogen-oxygen compounds and hydrocarbons is shown.With 29 Figures