The stratospheric ozone layer-an overview

This paper summarises the knowledge on the properties of the stratospheric ozone layer. Dynamic, chemical, and microphysical aspects are reviewed with emphasis on chemistry. The questions addressed are as follows. Do we have a quantitative understanding of the Antarctic ozone hole? What lies behind the trend of slowly decreasing ozone columns over northern mid-latitudes? To what degree was chemistry responsible for the extremely low ozone levels over northern Europe in January 1992? The discovery of the ozone hole in 1985 exposed scientific neglect of the category of fast heterogeneous reactions taking place on particulate matter in the stratosphere. But even now after the wide acceptance of some heterogeneous reactions it is difficult to fully account for the rate at which Antarctic ozone is depleted each year in August. After reviewing the known heterogeneous reactions, possible hitherto unrecognised mechanisms are briefly outlined. The paper also includes a discussion of the chemical reactions which can occur even under relatively warm conditions on the ubiquitous, stratospheric aerosol particles and which could contribute to the observed mid-latitudinal ozone depletion. Finally, the paper underlines the importance of dynamic processes, that is, horizontal transport and vertical adiabatic motion, which appear to be the main cause of the anomalously low northern hemispheric ozone values during the 1991/1992 winter.     

Origin and variability of upper tropospheric nitrogen oxides and ozone at northern mid-latitudes

Year-long measurements of NO_x and ozone performed during the NOXAR project are compared to results from the ECHAM4.L39(DLR)/CHEM (E39/C) and GISS coupled chemistry–climate models. The measurements were taken on flights between Europe and the eastern United States and between Europe and the Far East in the latitude range 40–65°N. Our comparison concentrates on the upper troposphere and reveals strong longitudinal variations in seasonal mean NO_x of more than 200 pptv, which both models are able to reproduce qualitatively. Vertical profiles show maximum NO_x values 2–3 km below the tropopause (“E-shape”) with a strong seasonal cycle. E39/C simulates a maximum located at the tropopause and with a reasonable seasonal cycle. The GISS model reproduces the seasonal cycle but not the profile's shape due to its coarser vertical resolution. A comparison of NO_x frequency distributions reveals that both models are capable of reproducing the observed variability, except that E39/C shows no very high NO_x mixing ratios.Both models show that lightning and surface NO_x emissions contribute the most to the seasonal cycle of NO_x at tropopause altitudes. The impact of lightning in the upper troposphere does not vary strongly with altitude, whereas the impact of surface emissions decreases with altitude. Among all sources, lightning contributes the most to the variability of NO_x in the upper troposphere in northern mid-latitudes during summer.     

Closing Remarks

Considerable attention has been paid in recent years to photochemical smog pollution close to the earth's surface and to stratospheric ozone depletion. There is reason to suspect that the next round of scientific concern will be devoted to the perturbations in the “free troposphere.” Tropospheric ozone has been building up in many regions of the northern hemisphere. Ozone changes in the upper troposphere will exert a considerable impact on global warming. This could affect moisture levels, cloud amount and distribution, precipitation, and atmospheric dynamics on different scales.

This paper analyzes: (1) the physical and chemical processes contributing to changes in tropospheric ozone concentration; (2) the observational evidence of previous ozone change; and (3) results drawn from computer modelling of past and future radiative forcing caused by rising ozone concentrations in the upper troposphere.

The solar and longwave radiative model developed by Wang et al. (1991) was used for calculating the change in radiative forcing to the troposphere-surface system that can be ascribed to changing concentrations in ozone and other greenhouse gases. Nitric oxide emission from aircraft are a prime suspect for the observed increases in upper tropospheric ozone. The inference can be drawn that a radiative forcing of 0.2 to 0.35 Wm^-2 will result from a doubling of aircraft emissions over the next two decades. This will amount to 10 to 25 percent of the radiative forcing attributable to CO₂ alone for the same period. The effect of doubling aircraft emissions will increase as stratospheric ozone concentrations recover from the recent buildup of harmful chlorofluorocarbons. A large fraction of the radiative forcing that occurred during the 1970 to 1990 period can be attributed to increases in tropospheric ozone as opposed to increases in other greenhouse gases.     

The southern hemisphere ozone hole split in 2002

Among the most important aspects of the atmospheric pollution problem are the anthropogenic impacts on the stratospheric ozone layer, the related trends of the total ozone content drop and the solar ultraviolet radiation enhancement at the Earth's surface level. During September 2002, the ozone hole over the Antarctic was much smaller than in the previous six years. It has split into two separate holes, due to the appearance of sudden stratospheric warming that has never been observed before in the southern hemisphere. The analysis of this unprecedented event is attempted, regarding both the meteorological and photochemical aspects, in terms of the unusual thermal field patterns and the induced polar vortex disturbances.     

Seasonal ozone behavior along an elevation gradient in the Colorado Front Range Mountains

Ambient surface ozone was monitored for one year at a series of seven sites along an elevation gradient from 1600 m to 3500 m above sea level (ASL) in Boulder County, Colorado. Spatial variability of ozone, quantified as the root mean squared deviation of hourly ozone per kilometer horizontal separation, decreased with elevation and distance from local sources, validating the assumption that (except at the City of Boulder (BO) site) the results of the study are representative of the Colorado Front Range. The northern hemisphere (NH) tropospheric spring ozone peak was clearly apparent in late April and early May and affected ozone at all elevations. Ozone consistently increased with elevation during winter, with a mean monthly rate of 1.5 ppbv per 100 m elevation. In summer, this monotonic increase in ozone with elevation was not observed; instead mean monthly ozone increased in two steps, by ～15 ppbv between 1610 m and 1940 m ASL and by ～10 ppbv between 3350 m and 3530 m ASL to a maximum of 60 ppbv. The amplitude of the diurnal ozone cycle decreased with increasing elevation. Average summertime diurnal swings in ozone concentration had a magnitude of 29 ppbv at 1610 m ASL, and 7–16 ppbv at the mid-elevation sites. In winter a diurnal cycle was observed only at the BO site, ozone concentrations at the remaining six locations changed on a multi-day timescale, indicating regional background behavior as the primary factor for wintertime ozone. Even the highest elevation site was influenced by transported urban air pollution in summer, indicated by the average 5 ppbv diurnal increase in ozone. Ozone exposure at the mid- to high-elevation sites in many instances approached and exceeded the 8-h National Ambient Air Quality Standard of 75 ppbv. The elevated ozone levels along this transect were interpreted to be caused by the confounding effects of the high elevation of these sites, increased ozone in long-range transported air, and anthropogenic ozone production in air transported from the nearby urban and suburban areas east of the Colorado Front Range Mountains.     

Surface ozone at the Swiss Alpine site Arosa: the hemispheric background and the influence of large-scale anthropogenic emissions

An innovative and effective method using isentropic trajectory analysis based on the residence time of air masses over the polluted region of Europe was successfully applied to categorize surface ozone amounts at Arosa, Switzerland during 1996–1997. The “European representative” background ozone seasonal cycle at Arosa is associated with long-range transport of North Atlantic air masses, and displays the spring maximum–summer minimum with an annual average of 35 ppb. The photochemical ozone production due to the intense large-scale anthropogenic emission over Europe is estimated as high as 20 ppb in summer, whereas it is insignificant in winter. European sources contribute an annual net ozone production of 9–12 ppb at Arosa. Comparison with the selected regional representative site in Western Europe shows similar results indicating that the categorized ozone data at Arosa by this technique could be regarded as a representative for northern hemispheric mid-latitudes.     

Evaluation of near surface ozone in air quality simulations forced by a regional climate model over Europe for the period 1991–2000

This study aims to evaluate near surface ozone simulated with the modelling system RegCM3/CAMx against ozone measurements from the EMEP database for the recent decade 1991–2000. The RegCM3/CAMx simulations were performed on a 50 km × 50 km grid over Europe driven either by ERA-40 reanalysis (hereafter referred as ERA simulation) or the global circulation model (GCM) ECHAM5 (hereafter referred as ECHAM simulation). A set of statistical metrics is used for the model evaluation, including temporal correlation coefficient, the ratio of the standard deviations and the bias of simulated versus observed values. Overall, a good agreement is found for both ERA and ECHAM simulations at the majority of the selected EMEP stations in all metrics throughout the year based either on monthly or daily ozone values. Based on these results, it is assessed that the modelling system RegCM3/CAMx is suitable to be used for present and future regional climate-air quality simulations with emphasis on near surface ozone. The ERA simulations reproduce more accurately the observed ozone values in comparison to ECHAM simulations because the meteorology of the ERA experiment is closer to real atmospheric conditions than the GCM based experiment. On a seasonal basis, both ERA and ECHAM simulations exhibit a seasonally dependent bias, with winter and spring ozone values being generally under-estimated by the model and summer and autumn values being slightly overestimated. This seasonally dependent bias is also evident from median and peak midday ozone values. However, the highest observed midday ozone peaks in summer, with values higher than 80 ppbv, could not be captured either by ERA or ECHAM simulations. An analysis of day-time and night-time ERA and ECHAM modelled ozone values shows that CAMx performs better during the day-time.     

The extraordinary events of the major,sudden stratospheric warming,the diminutive antarctic ozone hole,and its split in 2002

GOAL, SCOPE AND BACKGROUND: Great interest in the unprecedented events of the major, sudden stratospheric warming and the ozone hole split over Antarctica in September 25, 2002 motivates a necessity to analyze the current understanding on the dynamics, chemistry and climate impacts that are associated with both events. METHODS: Significant progress in the analysis of the observational data obtained, as well as successful development and application of dynamical modeling, which have been achieved very recently, create a basis for the first survey on the role of the major, sudden stratospheric warming observed in the southern hemisphere and its relationship to the diminutive Antarctic ozone hole and its break up into two parts. RESULTS AND DISCUSSION: Special attention has been paid to assessments of the causes of the major warming event and the future expectations concerning the stratospheric ozone depletion effect. Among the principal results is the fact that, as the polar vortex elongated, it became hydrodynamically unstable, and this insta-, bility affected the upper troposphere and stratosphere. During the major, sudden stratospheric warming, the middle stratospheric vortex split into two pieces; one piece rapidly mixed with extra vortex air, while the other returned to the pole as a much weaker and smaller vortex. The polar night jet was considerably weaker than normal, and was displaced more poleward than has been observed in previous winters, resulting from a series of wave events (propagated from the troposphere) that took place over the course of the winter. Finally, the relative ozone decrease (increase) in the eastern Antarctic is tightly associated with westerly (easterly) zonal wind anomalies near the southern tip of South America, and the unusual behavior of the ozone hole in 2002 therefore appears to be caused by great easterlies in this region. CONCLUSIONS: The main conclusion is that the southern polar vortex and the diminutive ozone hole split into two parts in September 2002, due to the prevalence of very strong planetary waves, led to the appearance of a major, sudden stratospheric warming. Although there is evidence that sea surface temperature anomalies contributed to the excitation of the quite strong planetary waves over Antarctica in 2002, there is not yet a widely approved mechanism supporting that. RECOMMENDATIONS AND OUTLOOK:The appearance of the near-record size of the 2003 ozone hole confirmed that the 'no-ozone-hole' episode observed in the year 2002 does not denote a recovery of the ozone layer. Despite the current successful attempts to get a sufficient understanding for the genesis of both extraordinary events, more observations and further modeling efforts are necessary to more reliably assess the contribution of various dynamic mechanisms to the recently observed tropo-stratospheric surprises.     

Validation of leaf ozone symptoms in natural vegetation using microscopical methods

Ozone injury to natural vegetation is being increasingly surveyed throughout the northern hemisphere. There exists a growing list of species showing visible 'ozone-like' symptoms which needs to be validated. This study presents the results from a test survey of ozone injury to forest vegetation in the light exposed sites of five Swiss level II plots, for the new ICP-Forests protocol. With AOT40 from 14 to 28 ppm-h in 2000, ten out of 49 woody plant species displayed typical symptoms, and four showed untypical symptoms. Symptom origin was investigated in nine and validated in seven species, using morphological, histological and cellular markers of oxidative stress and ozone-induced plant response. Independent of taxonomic position, ozone effects were characterized by the induction of oxidative stress in the mesophyll resulting in discrete and light-dependent hypersensitive-like responses and in accelerated cell senescence. The presented combination of cellular and morphological markers allows differential diagnosis of visible ozone injury.     

What is causing high ozone at Summit,Greenland?

Causes for the unusually high and seasonally anomalous ozone concentrations at Summit, Greenland were investigated. Surface data from continuous monitoring, ozone sonde data, tethered balloon vertical profiling data, correlation of ozone with the radionuclide tracers ⁷Be and ²¹⁰Pb, and synoptic transport analysis were used to identify processes that contribute to sources and sinks of ozone at Summit. Northern Hemisphere (NH) lower free troposphere ozone mixing ratios in the polar regions are ∼20 ppbv higher than in Antarctica. Ozone at Summit, which is at 3212 m above sea level, reflects its altitude location in the lower free troposphere. Transport events that bring high ozone and dry air, likely from lower stratospheric/higher tropospheric origin, were observed ∼40% of time during June 2000. Comparison of ozone enhancements with radionuclide tracer records shows a year-round correlation of ozone with the stratospheric tracer ⁷Be. Summit lacks the episodic, sunrise ozone depletion events, which were found to reduce the annual, median ozone at NH coastal sites by up to ∼3 ppbv. Synoptic trajectory analyses indicated that, under selected conditions, Summit encounters polluted continental air with increased ozone from central and western Europe. Low ozone surface deposition fluxes over long distances upwind of Summit reduce ozone deposition losses in comparison to other NH sites, particularly during the summer months. Surface-layer photochemical ozone production does not appear to have a noticeable influence on Summit's ozone levels.     

Increasing risk for negative ozone impacts on vegetation in northern Sweden

Trends were found for increasing surface ozone concentrations during April-September in northern Sweden over the period 1990-2006 as well as for an earlier onset of vegetation growing season. The highest ozone concentrations in northern Sweden occurred in April and the ozone concentrations in April showed a strong increasing trend. A model simulation of ozone flux for Norway spruce indicated that the provisional ozone flux based critical level for forests in Europe is exceeded in northern Sweden. Future climate change would have counteracting effects on the stomatal conductance and needle ozone uptake, mediated on the one hand by direct effect of increasing air temperatures and on the other through increasing water vapour pressure difference between the needles and air. Thus, there is a substantial and increasing risk for negative impacts of ozone on vegetation in northern Sweden, related mainly to increasing ozone concentrations and an earlier onset of the growing season.     

Depletion of stratospheric ozone over the Antarctic and Arctic: responses of plants of polar terrestrial ecosystems to enhanced UV-B, an overview

Depletion of stratospheric ozone over the Antarctic has been re-occurring yearly since 1974, leading to enhanced UV-B radiation. Arctic ozone depletion has been observed since 1990. Ozone recovery has been predicted by 2050, but no signs of recovery occur. Here we review responses of polar plants to experimentally varied UV-B through supplementation or exclusion. In supplementation studies comparing ambient and above ambient UV-B, no effect on growth occurred. UV-B-induced DNA damage, as measured in polar bryophytes, is repaired overnight by photoreactivation. With UV exclusion, growth at near ambient may be less than at below ambient UV-B levels, which relates to the UV response curve of polar plants. UV-B screening foils also alter PAR, humidity, and temperature and interactions of UV with environmental factors may occur. Plant phenolics induced by solar UV-B, as in pollen, spores and lignin, may serve as a climate proxy for past UV. Since the Antarctic and Arctic terrestrial ecosystems differ essentially, (e.g. higher species diversity and more trophic interactions in the Arctic), generalization of polar plant responses to UV-B needs caution.     

Reduction of stem growth and site dependency of leaf injury in Massachusetts black cherries exhibiting ozone symptoms

Leaf ozone symptoms in natural ecosystems are increasingly reported but ozone effects on tree growth and the mediation of site conditions are still little documented. This study tests two hypotheses: (1) leaf injury in black cherry is associated with decline in radial growth, (2) symptoms are more prevalent on mesic sites. On sites supporting black cherry across Massachusetts, tree growth and leaf ozone injury were surveyed in 1996 using a randomized plot network established in the 1960s. Forty-seven percent of 120 trees sampled for ozone symptoms were symptomatic with generally low levels of injury. Over a 31-year period symptomatic trees had 28% lower stem growth rates than asymptomatic trees. Ozone symptom expression was enhanced in well growing stands on moister, cooler and more elevated sites. Ozone appeared to increase environmental stress and had a more pronounced effect on growth in better growing black cherry stands. This complicates management decisions as thinning increases growth and moisture availability.     

Changes in seasonal and diurnal cycles of ozone and temperature in the eastern U.S.

The pollutant tropospheric ozone causes human health problems, and environmental degradation and acts as a potent greenhouse gas. Using long-term hourly observations at five US air quality monitoring surface stations we studied the seasonal and diel cycles of ozone concentrations and surface air temperature to examine the temporal evolution over the past two decades. Such an approach allows visualizing the impact of natural and anthropogenic processes on ozone; nocturnal inversion development, photochemistry, and stratospheric intrusion. Analysis of the result provides an option for determining the duration for a regulatory ozone season. The application of the method provides independent confirmation of observed changes and trends in the ozone and temperature data records as reported elsewhere. The results provide further evidence supporting the assertion that ozone reductions can be attributed to emission reductions as opposed to weather variation. Despite a (～0.5 °C decade^?1) daytime warming trend, ozone decreased by up to 6 ppb decade^?1 during times of maximum temperature in the most polluted locations. Ozone also decreased across the emission reduction threshold of 2002 by 6–10 ppb indicating that emission reductions have been effective where and when it is most needed. Longer time series, and coupling with other data sources, may allow for the direct investigation of climate change influence on regional ozone air pollution formation and destruction over annual and daily time scales.     

Monitoring of ozone in a marine environment in Tenerife (Canary Islands)

In the Aguere Valley (in the oceanic boundary layer at Tenerife, 28°N, 16°W, 580 m a.s.l.) the ozone levels were monitored for ambient air quality assessment. Although precursors are emitted in this area, the strong correlation between ozone levels and wind velocity indicates that ozone is transported into the valley from the ocean. The inland ozone supply along the valley is induced by an orographic channelling effect of the northern oceanic air masses. The highest ozone concentrations are mostly recorded during the nocturnal stage under the influence of fresh oceanic air masses, and during high wind speed events. The seasonal cycle is characterised by elevated ozone mixing ratios in the spring (nighttime levels >45 ppbv) and low mixing ratios in the summer (nighttime levels in the range 20–35 ppbv). Back-trajectory analysis shows that the ozone monitored in the Aguere Valley is associated with long-range transport processes. High ozone events in the spring are associated with transport from upper tropospheric levels, both over the North Atlantic-high latitudes (>45°N) and Europe. This downward transport was observed in the western edge of upper tropospheric cyclones, which suggests that the upper tropospheric/low stratospheric ozone sources play a significant role. In summer, ozone is mainly transported from the North Atlantic-high latitudes (>45°N) and from mid- to low-tropospheric levels. In autumn and winter, the high ozone concentrations are transported from sources located a few km above the North Atlantic-high latitudes (>45°N) and over Europe. The Central-North Atlantic (<45°N) and North Africa are not significant sources of ozone. The high spring and lower summer ozone events in the Aguere Valley agree with other North Atlantic ozone observation in the oceanic boundary layer. However, this behaviour contrasts with the high ozone events frequently recorded at Izaña BAPMoN station (located in the free troposphere in Tenerife) during the summer, which have been attributed in the literature to downward transport from upper levels. An intensification of the inversion layer that separates the oceanic boundary layer of the free troposphere during the summer in Canary Islands is interpreted as the cause of this different behaviour between ozone in the Aguere Valley and Izaña BAPMoN station.     

The effect of winter stress on Ilex aquifolium L.previously fumigated with ozone

European Holly (Ilex aquifolium) received either charcoal-filtered air (CFA) or CFA with 70 nl l(-1) ozone added for 7 h day(-1) over a 28 day period. Plants were then transferred into cooling incubators for hardening (4 degrees C day/2 degrees C night; day length 12 h) for 7 days and then to the frosting stage (2 degrees C day and -5, -10 or -15 degrees C night) for 4 days. The plants were then placed in ambient conditions. Treatment produced significant differences in chlorophyll fluorescence data. Stomatal conductance was significantly higher for the ozone treatments though both showed a general decline over all temperature regimes. Ozone also significantly increased electrolyte leakage and reduced winter survival. These results show that ambient concentrations of ozone can reduce the tolerance of I. aquifolium to freezing stress, which may have serious implications for its establishment and survival.     

Within season and carry-over effects following exposure of grassland species mixtures to increasing background ozone

Few studies have investigated effects of increased background ozone in the absence of episodic peaks, despite a predicted increase throughout the northern hemisphere over the coming decades. In this study Leontodon hispidus was grown with Anthoxanthum odoratum or Dactylis glomerata and exposed in the UK to one of eight background ozone concentrations for 20 weeks in solardomes. Seasonal mean ozone concentrations ranged from 21.4 to 102.5 ppb. Ozone-induced senescence of L. hispidus was enhanced when grown with the more open canopy of A. odoratum compared to the denser growing D. glomerata. There was increased cover with increasing ozone exposure for both A. odoratum and D. glomerata, which resulted in an increase in the grass:Leontodon cover ratio in both community types. Carry-over effects of the ozone exposure were observed, including delayed winter die-back of L. hispidus and acceleration in the progression from flowers to seed-heads in the year following ozone exposure.     

Modeling of ozone reactions on aircraft-related soot in the upper troposphere and lower stratosphere

Several studies in modeling atmospheric processes have suggested that heterogeneous chemistry on soot emitted from high altitude aircraft could affect stratospheric ozone depletion. However, these modeling studies were limited because they did not adequately consider the decrease in reaction probability with time as the surface of the soot becomes “poisoned” by its interactions with various gases. Here we extend UIUC's two-dimensional chemical-transport model to investigate possible effects of heterogeneous reactions of ozone on aircraft-generated carbon particles, including a treatment of soot poisoning in the model. We generally follow literature recommendations for ozone uptake probabilities and determine the available active sites on soot given partial pressures of the reactants, temperature, and time since soot emission in order to investigate ozone decrease. The regeneration of soot active sites is also taken into account in this study. We find that, even if active sites on soot surfaces are regenerated, upper troposphere and lower stratosphere ozone losses on aircraft emitted soot occurring through heterogeneous reactions are insignificant once poisoning effects are considered.     

Heterogeneous and homogeneous catalytic ozonation of benzothiazole promoted by activated carbon: kinetic approach

Ozone oxidation combined with activated carbon adsorption (O(3)/AC) has recently started to be developed as a single process for water and wastewater treatment. While a number of aspects of aqueous ozone decomposition are well understood, the importance and relationship between aqueous ozone decomposition and organic contaminant degradation in the presence of activated carbon is still not clear. This study focuses on determining the contribution of homogeneous and heterogeneous reactions to organic contaminants removal in O(3)/AC system. Benzothiazole (BT) was selected as a target organic pollutant due to its environmental concern. A reactor system based on a differential circular flow reactor composed by a 19 cm(3) activated carbon fixed bed column and 1 dm(3) storage tank was used. Ozone was produced from pure and dry oxygen using an Ozocav ozone generator rated at 5 g O(3)h(-1). Experimental results show that BT removal rate was proportional to activated carbon dosage. Activated carbon surface contribution to BT oxidation reactions with ozone, increased with pH in absence of radical scavengers. The radical reaction contribution within the pH range 2-11 accounted for 67-83% for BT removal in O(3)/AC simultaneous treatment. Results suggest that at pH higher than the pH of the point of zero charge of the activated carbon dissociated acid groups such as carboxylic acid anhydrides and carboxylic acids present on activated carbon surface could be responsible for the observed increase in the ozone decomposition reaction rate. A simplified mechanism and a kinetic scheme representing the contribution of homogeneous and heterogeneous reactions on BT ozonation in the presence of activated carbon is proposed.     

Dynamic-chemical coupling of the upper troposphere and lower stratosphere region

The importance of the interaction between chemistry and dynamics in the upper troposphere and lower stratosphere for chemical species like ozone is investigated using two chemistry-climate models and a Lagrangian trajectory model. Air parcels from the upper troposphere, i.e. regions of lightning and aircraft emissions, are able to be transported into the lowermost stratosphere (LMS). Trajectory calculations suggest that the main transport pathway runs via the inter tropical convergence zone, across the tropical tropopause and then to higher latitudes, i.e. into the LMS. NOx from aircraft emissions at mid-latitudes are unlikely to perturb the LMS since they are washed-out while still in the troposphere. In contrast, NOx from tropical lightning has the chance to accumulate in the LMS. Because of the longer residence times of NOx in the LMS, compared to the upper troposphere, this excess NOx from lightning has the potential to form ozone in the LMS, which then is transported back to the troposphere at mid-latitudes. In the models, around 10% of the ozone concentration and 50% of the NOx concentration in the northern hemisphere LMS is produced by lightning NOx At least 5% of the ozone concentration and 35% the NOx concentration at 150 hPa at mid-latitudes originates from tropical lightning in the climate-chemistry simulations.