Impact of ozone mini-holes on the heterogeneous destruction of stratospheric ozone

A comprehensive study of ozone mini-holes over the mid-latitudes of both hemispheres is presented, based on model simulations with the coupled climate-chemistry model ECHAM4.L39(DLR)/CHEM representing atmospheric conditions in 1960, 1980, 1990 and 2015. Ozone mini-holes are synoptic-scale regions of strongly reduced total ozone, directly associated with tropospheric weather systems. Mini-holes are supposed to have chemical and dynamical impacts on ozone levels. Since ozone levels over northern mid-latitudes show a negative trend of approximately -4%/decade and since it exists a negative correlation between total column ozone and erythemally active solar UV-radiation reaching the surface it is important to understand and assess the processes leading to the observed ozone decline. The simulated mini-hole events are validated with a mini-hole climatology based on daily ozone measurements with the TOMS (total ozone mapping spectrometer) instrument on the satellite Nimbus-7 between 1979 and 1993. Furthermore, possible trends in the event frequency and intensity over the simulation period are assessed. In the northern hemisphere the number of mini-hole events in early winter decreases between 1960 and 1990 and increases towards 2015. In the southern hemisphere a positive trend in mini-hole event frequency is detected between 1960 and 2015 in spring associated with the increasing Antarctic Ozone Hole. Finally, the impact of mini-holes on the stratospheric heterogeneous ozone chemistry is investigated. For this purpose, a computer-based detection routine for mini-holes was developed for the use in ECHAM4.L39(DLR)/CHEM. This method prevents polar stratospheric cloud formation and therefore heterogeneous ozone depletion inside mini-holes. Heterogeneous processes inside mini-holes amount to one third of heterogeneous ozone destruction in general over northern mid- and high-latitudes during winter (January-April) in the simulation.     

Climatic effect of observed changes in atmospheric trace gases at Antarctica

The seasonal decline in ozone in the Antarctic atmosphere has been termed the ‘Antarctic ozone hole’. Possibly this hole is caused by upper atmospheric wind, due to resumption of high solar activity after the polar night which produces large amounts of ozone-destroying nitric oxide or due to unusual chlorine chemistry at extreme cold temperatures and associated polar stratospheric clouds. Of particular concern is that the observed changes in ozone could be linked to the observed increases in the gases that affect ozone such as methane, nitrous oxide, etc. All these gases affect the climate of the Earth through their so-called ‘greenhouse’ action. We have examined the nature of the greenhouse effect on polar climate due to observed changes in atmospheric trace gases in Antarctica which are reported here.     

What is the lesson from the unprecedented event over antarctica in 2002

Varotsos (2002a,b), suggested that both the smaller-sized ozone hole over Antarctica and its splitting in two holes in September 2002 occurred due to an unprecedented major sudden stratospheric warming caused by very strong planetary waves propagated in the southern hemisphere. Subsequently, a NASA press release of December 6, 2002, also reported the prevalence of very strong planetary waves in Antarctica. The aim of this Letter is to further discuss the morphology of the Antarctic ozone hole, to detect the causes that allowed the Antarctic stratosphere to exhibit this exceptional warming and to examine what it denotes about its mechanisms. Concerning the morphology, among the principal findings is that the ozone hole split occurred not only in the stratosphere but extended in the lower altitudes (upper troposphere). As to the causes of the major sudden stratospheric warming of 2002, a comparison with the previous warmings in Antarctica since 1964 is made. The smaller-sized Antarctic ozone hole of 2002 is approximately equal to that of 1988 when a strong sudden stratospheric warming occurred. If only the destruction of ozone by chlorofluorocarbons resulted in the delayed sudden stratospheric warmings in Antarctica, then the early sudden stratospheric warmings of 1988 and 2002 would not have occurred, since chlorofluorocarbon loading of the stratosphere has remained relatively stable in recent years. Furthermore, it appears that the El Nino characteristics in 1988 and 2002 are not similar.     

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.     

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.     

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.     

A DFT study of the reactions of O3 with Hg° or Br

In the mid 1980s the study of ozone reactivity gained a significant interest with the discoveries of the stratospheric ozone hole (Farman et al., 1985) and of the ozone depletion events in the polar boundary layer (Oltmans et al., 1989). In the stratosphere, the mechanism involves heterogeneous reactions on polar stratospheric clouds that lead to chlorine activation (Solomon et al., 1986). In contrast, tropospheric ozone depletion occurring during polar springtime rather involves reactive bromine species. They are released during a series of photochemical and heterogeneous reactions often called the bromine explosion (see the review of Simpson et al., 2007). In this reaction sequence, an essential step is the generation of photolyzable Br₂, the precursor of two Br atoms, via the multiphasic reaction (1):

(1)

HOBr + Br⁻ + H⁺ → H₂O + Br₂

The production of reactive HOBr could occur with the oxidation of BrO by HO₂.     

A review of surface ozone in the polar regions

Surface ozone records from ten polar research stations were investigated for the dependencies of ozone on radiative processes, snow-photochemisty, and synoptic and stratospheric transport. A total of 146 annual data records for the Arctic sites Barrow, Alaska; Summit, Greenland; Alert, Canada; Zeppelinfjellet, Norway; and the Antarctic stations Halley, McMurdo, Neumayer, Sanae, Syowa, and South Pole were analyzed. Mean ozone at the Northern Hemisphere (NH) stations (excluding Summit) is ∼5 ppbv higher than in Antarctica. Statistical analysis yielded best estimates for the projected year 2005 median annual ozone mixing ratios, which for the Arctic stations were 33.5 ppbv at Alert, 28.6 ppbv at Barrow, 46.3 ppbv ppb at Summit and 33.7 ppbv at Zeppelinfjellet. For the Antarctic stations the corresponding ozone mixing ratios were 21.6 ppbv at Halley, 27.0 ppbv at McMurdo, 24.9 ppbv at Neumayer, 27.2 ppbv at Sanae, 29.4 ppbv at South Pole, and 25.8 ppbv at Syowa. At both Summit (3212 m asl) and South Pole (2830 m asl), annual mean ozone is higher than at the lower elevation and coastal stations. A trend analysis revealed that all sites in recent years have experienced low to moderate increases in surface ozone ranging from 0.02 to 0.26 ppbv yr⁻¹, albeit none of these changes were found to be statistically significant trends. A seasonal trend analysis showed above-average increases in ozone during the spring and early summer periods for both Arctic (Alert, Zeppelinfjellet) and Antarctic (McMurdo, Neumayer, South Pole) sites. In contrast, at Barrow, springtime ozone has been declining. All coastal stations experience springtime episodes with rapid depletion of ozone in the boundary layer, attributable to photochemically catalyzed ozone depletion from halogen chemistry. This effect is most obvious at Barrow, followed by Alert. Springtime depletion episodes are less pronounced at Antarctic stations. At South Pole, during the Antarctic spring and summer, photochemical ozone production yields frequent episodes with enhanced surface ozone. Other Antarctic stations show similar, though less frequent spring and summertime periods with enhanced ozone. The Antarctic data provide evidence that austral spring and summertime ozone production in Antarctica is widespread, respectively, affects all stations at least through transport events. This ozone production contributes to a several ppbv enhancement in the annual mean ozone over the Antarctic plateau; however, it is not the determining process in the Antarctic seasonal ozone cycle. Although Summit and South Pole have many similarities in their environmental conditions, this ozone production does not appear to be of equal importance at Summit. Amplitudes of diurnal, summertime ozone cycles at these polar sites are weaker than at lower latitude locations. Amplitudes of seasonal ozone changes are larger in the Southern Hemisphere (by ∼5 ppbv), most likely due to less summertime photochemical ozone loss and more transport of ozone-rich air to the Arctic during the NH spring and summer months.     

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 role of halogen species in the troposphere

While the role of reactive halogen species (e.g. Cl, Br) in the destruction of the stratospheric ozone layer is well known, their role in the troposphere was investigated only since their destructive effect on boundary layer ozone after polar sunrise became obvious. During these 'Polar Tropospheric Ozone Hole' events O(3) is completely destroyed in the lowest approximately 1000 m of the atmosphere on areas of several million square kilometres. Up to now it was assumed that these events were confined to the polar regions during springtime. However, during the last few years significant amounts of BrO and Cl-atoms were also found outside the Arctic and Antarctic boundary layer. Recently even higher BrO mixing ratios (up to 176 ppt) were detected by optical absorption spectroscopy (DOAS) in the Dead Sea basin during summer. In addition, evidence is accumulating that BrO (at levels around 1-2 ppt) is also occurring in the free troposphere at all latitudes.In contrast to the stratosphere, where halogens are released from species, which are very long lived in the troposphere, likely sources of boundary layer Br and Cl are autocatalytic oxidation of sea salt halides (the 'Bromine Explosion'), while precursors of free tropospheric BrO and coastal IO probably are short-lived organo-halogen species. At the levels suggested by the available measurements reactive halogen species have a profound effect on tropospheric chemistry: In the polar boundary layer during 'halogen events' ozone is usually completely lost within hours or days. In the free troposphere the effective O(3)-losses due to halogens could be comparable to the known photochemical O(3) destruction. Further interesting consequences include the increase of OH levels and (at low NO(X)) the decrease of the HO(2)/OH ratio in the free troposphere.     

A lagrangian approach to analyse the tropospheric ozone climatology in the tropics: Climatology of stratosphere–troposphere exchange at Reunion Island

Sixteen years of ozone measurements (1992–2006) at Reunion Island (21°S, 55.5°E) have been processed to detect stratospheric signatures on each single ozone profile.The characterisation method consists in the advection of the potential vorticity (PV) over two to ten days of backtrajectory with the lagrangian trajectory code LACYTRAJ. LACYTRAJ is a Trajectory-Reverse Domain Filling code using the ERA40 ECMWF database and allowing the reconstruction of high resolution advected PV profiles. Correlation between high values of ozone mixing ratio and high PV is interpreted as a stratospheric signature.A climatology of STE events at Reunion has been derived and reveals that STE events occur more frequently during spring (SON) and summer (DJF). The method is tested for a set of PV threshold values (i.e. 1 PVU, 1.5 PVU and 2 PVU) and for a set of duration of backtrajectories (i.e. 2 days, 5 days and 10 days). The number of detected STE is sensitive to PV threshold values and duration criterions. For instance, the number of stratospheric intrusions detected in October with a 1.5 PVU criterion ranges between 25% (2 days of backtrajectories) and 56% (10 days of backtrajectories). The vertical distributions of STE show intrusions covering the whole free troposphere (between 7 and 15 km) and mainly located in the upper troposphere.Finally, results show that an important number of stratospheric intrusions are detected during spring and in the upper troposphere what points at the contribution of the stratospheric source to the tropospheric ozone spring maximum which is strongly influenced by the biomass burning emissions from South Africa and Madagascar.     

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.     

Ozone recovery as seen in perspective of the Dobson spectrophotometer measurements at Belsk (52°N, 21°E) in the period 1963–2008

The total ozone monthly means derived from measurements by the Dobson spectrophotometer at Belsk (52°N, 21°E) and satellite observations over central and midlatitudinal Europe are analyzed for the long-term changes between 1995 and 2008. Standard explanatory variables representing physical and chemical processes known to influence the ozone distribution are considered. The potential proxies are: atmospheric loading by the ozone depleting substances characterized by the equivalent effective stratospheric chlorine (EESC) time series, various drivers of ozone dynamical variability including solar cycle, teleconnection patterns, temperature at 50 hPa, and pressure at the tropopause level. The multivariate adaptive regression splines (MARS) methodology is used to find optimal set of the explanatory variables and shape of the anthropogenic trend curve. Following options for the trend curve are examined: proportional to EESC, piecewise linear (with the turning points in 1980 and 1995), and selected from a smooth curve fit to the total ozone time series having “natural variations” removed. Statistical estimates and their uncertainties are calculated using block bootstrapping. The analyses indicate that ozone over Belsk, in central Europe, and in midlatitudinal Europe reaches at least first stage of recovery as defined by the World Meteorological Organization: a statistically significant reduction in the rate of decline. Model using the EESC time series as a proxy for the anthropogenic trend pattern yields even the second stage, i.e., a positive trend in time series that remains after removal dynamical signal from the analyzed data. Substantial seasonal dependent long-term ozone oscillations by the dynamical drivers are revealed causing estimation of the ozone recovery time even more uncertain.     

Using a reduced Common Representative Intermediates (CRIv2-R5) mechanism to simulate tropospheric ozone in a 3-D Lagrangian chemistry transport model

A reduced chemical scheme (CRIv2-R5) which describes ozone formation from the tropospheric degradation of methane and 22 emitted non-methane hydrocarbons and oxygenated volatile organic compounds has been applied in a global-3D chemistry transport model (STOCHEM). The scheme, which contains 220 species in 609 reactions, has been used to simulate ozone and its precursors for the meteorological year of 1998 and the results have been compared with those from STOCHEM runs with its original chemistry. Compared with the original chemistry scheme, the degradation of a larger number of more reactive VOCs in the CRI scheme results in the formation (and their consequent transportation) of more NO_x active reservoirs thus leading to formation of more ozone away from land-based sources. Conversely, the more reactive VOCs also lead to greater removal of OH in continental areas and greater formation of OH in marine environments. STOCHEM run with the CRI scheme simulates more ozone (by up to 10 ppb), which results in better agreement with observed vertical ozone profiles. The CRI scheme transforms the globally and annually integrated ozone budget for the considered year in STOCHEM from a net loss of ?55 Tg yr^?1 to a net gain of +50 Tg yr^?1.     

Stratospheric ozone depletion, UV-B radiation and crop disease

Ultraviolet-B radiation (UV-B: 290-315 nm) is expected to increase as the result of stratospheric ozone depletion. Within the environmental range, UV-B effects on host plants appear to be largely a function of photomorphogenic responses, while effects on fungal pathogens may include both photomorphogenesis and damage. The effects of increased UV-B on plant-pathogen interactions has been studied in only a few pathosystems, and have used a wide range of techniques, making generalisations difficult. Increased UV-B after inoculation tends to reduce disease, perhaps due to direct damage to the pathogen, although responses vary markedly between and within pathogen species. Using Septoria tritici infection of wheat as a model system, it is suggested that even in a species that is inherently sensitive to UV-B, the effects of ozone depletion in the field are likely to be small compared with the effects of variation in UV-B due to season and varying cloud. Increased UV-B before inoculation causes a range of effects in different systems, but an increase in subsequent disease is a common response, perhaps due to changes in host surface properties or chemical composition. Although it seems unlikely that most crop diseases will be greatly affected by stratospheric ozone depletion within the limits currently expected, the lack of a detailed understanding of the mechanisms by which UV-B influences plant-pathogen interactions in most pathosystems is a significant limit to such predictions.     

The ozone formation potential of 1-bromo-propane

1-Bromo-propane (1-BP) is a replacement for high-end chlorofluorocarbon (HCFC) solvents. Its reaction rate constant with the OH radical is, on a weight basis, significantly less than that of ethane. However, the overall smog formation chemistry of 1-BP appears to be very unusual compared with typical volatile organic compounds (VOCs) and relatively complex because of the presence of bromine. In smog chamber experiments, 1-BP initially shows a faster ozone build-up than what would be expected from ethane, but the secondary products containing bromine tend to destroy ozone such that 1-BP can have a net overall negative reactivity. Alternative sets of reactions are offered to explain this unusual behavior. Follow-up studies are suggested to resolve the chemistry. Using one set of bromine-related reactions in a photochemical grid model shows that 1-BP would be less reactive toward peak ozone formation than ethane with a trend toward even lower ozone impacts in the future.     

An isoprene mechanism intercomparison

The chemical mechanisms describing the photo-oxidation of isoprene in current Chemistry Transport Models (CTMs) have been intercompared in a series of box model experiments. The mechanisms ranged in size and complexity from ～600 reactions to ～25 reactions. The box model experiments covered two isoprene emission strengths over a broad range of NO emissions to assess the performances of the mechanisms over the spectrum of atmospherically relevant conditions. There was some variability in the simulated oxidation rates of isoprene and formation rates of ozone. The variability in performance is a consequence of the details of the underlying chemistry as represented in the mechanisms, and of the different assumptions and approximations made in mechanism reduction. These differences are illustrated and discussed for a series of species involved in the degradation of isoprene and the ozone formation mechanism, namely: HO_x radicals; organic peroxy radicals (RO₂); hydroperoxides; oxidised organic nitrogen compounds; and major carbonyl products. The results also confirm that all the considered isoprene mechanisms are unable to generate/recycle HO_x at the rates needed to match recently reported observations at locations characterized by low levels of NO_x.     

Impact of vertical transport processes on the tropospheric ozone layering above Europe.: Part II: Climatological analysis of the past 30 years

Using the set of multivariate criteria described in a companion paper, ozone-rich layers detected in tropospheric soundings are clustered according to their stratospheric or boundary layer origin. An additional class for aged tropospheric air masses is also considered. This analysis is exclusively based on the measured physical properties of the layers. The database includes 27,000 ozone profiles collected above 11 European stations—two of which provide measurements since 1970. The seasonal cycle of the tropospheric ozone stratification exhibits a clear summer maximum. This increase is due to aged tropospheric air masses that are more frequently detected, suggesting an enhanced lifetime of layers in summer. In terms of ozone content, the relative impact of stratospheric ozone compared to the other sources is highest in winter while export from the boundary layer presents a uniform seasonal cycle. Altitude and thickness distributions of the layers are consistent with the dynamical processes involved in the layering. Northernmost and southernmost stations are more exposed to stratospheric air intrusions into the free troposphere. Long-term trends show that transport from the tropopause region has increased since the mid 1980s. This trend being concomitant with lower ozone content of such layers, a moderate trend of the transport efficiency from the stratosphere on total tropospheric ozone is observed. The increase of ozone detected in tropospheric layers since the mid 1980s cannot be attributed to any recent export process from either the stratosphere or the boundary layer but rather to enhanced photochemical production in aged air masses or to an increase in the lifetime of the layers.     

Simulation of aerosols and gas-phase species over Europe with the Polyphemus system. Part II: Model sensitivity analysis for 2001

This paper presents a multi-pollutant sensitivity study of an air quality model over Europe with a focus on aerosols. Following the evaluation presented in the companion paper, the aim here is to study the sensitivity of the model to input data, mathematical parameterizations and numerical approximations. To that end, 30 configurations are derived from a reference configuration of the model by changing one input data set, one parameterization or one numerical approximation at a time. Each of these configurations is compared to the same reference simulation over two time periods of the year 2001, one in summer and one in winter. The sensitivity of the model to the different configurations is evaluated through a statistical comparison between the simulation results and through comparisons to available measurements. The species studied are ozone (O₃), nitrogen dioxide (NO₂), sulfur dioxide (SO₂), ammonia (NH₃), coarse and fine aerosol particles (PM_c and PM_2.5), sulfate, nitrate, ammonium, chloride and sodium.For all species, the modeled concentrations are very sensitive to the parameterization used for vertical turbulent diffusion and to the number of vertical levels. For the other configurations considered in this work, the sensitivity of the modeled concentration to configuration choice varies with the species and the period of the year. O₃ is impacted by options related to boundary conditions. PM_c is sensitive to sea-salt related options, to options influencing deposition and to options related to mass transfer between gas and particulate phases. PM_2.5 is sensitive to a larger number of options than PM_c: sea-salt, boundary conditions, heterogeneous reactions, aqueous chemistry and gas/particle mass transfer. NO₂ is strongly influenced by heterogeneous reactions. Nitrate shows the highest variability of all species studied. As with NO₂, nitrate is strongly sensitive to heterogeneous reactions but also to mass transfer, thermodynamic related options, aqueous chemistry and computation of the wet particle diameter. While SO₂ is mostly sensitive to aqueous chemistry, sulfate is also sensitive to boundary conditions and, to a lesser extent, to heterogeneous reactions. As with nitrate, ammonium is largely impacted by the different configuration choices, although the sensitivity is slightly lower than for nitrate. NH₃ is sensitive to aqueous chemistry, mass transfer and heterogeneous reactions. Chloride and sodium are impacted by sea-salt related options, by options influencing deposition and by options concerning the aqueous-phase module.