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.     

On the Role of Lightning NOx in the Formation of Tropospheric Ozone Plumes: A Global Model Perspective

A series of ozone transects measured each year from 1987 to 1990 over thewestern Pacific and eastern Indian oceans between mid-November andmid-Decembershows a prominent ozone maximum reaching 50–80 ppbv between 5 and 10 kmin the 20° S–40° S latitude band. This maximum contrasts with ozonemixing ratios lower than20 ppbv measured at the same altitudes in equatorial regions. Analyses witha globalchemical transport model suggest that these elevated ozone values are part ofa large-scale tropospheric ozone plume extending from Africa to the western Pacific acrosstheIndian ocean. These plumes occur several months after the peak in biomassburninginfluence and during a period of high lightning activity in the SouthernHemispheretropical belt. The composition and geographical extent of these plumes aresimilar to theozone layers previously encountered during the biomass burning season in thisregion.Our model results suggest that production of nitrogen oxides from lightningstrokes sustains the NO_x (= NO+NO₂) levels and the ozonephotochemical productionrequired in the upper troposphere to form these persistent elevated ozonelayers emanating from biomass burning regions.     

Downward transport and modification of tropospheric ozone through moist convection

This study estimated the largely unstudied downward transport and modification of tropospheric ozone associated with tropical moist convection using a coupled meteorology-chemistry model. High-resolution cloud resolving model simulations were conducted for deep moist convection events over West Africa during August 2006 to estimate vertical transport of ozone due to convection. Model simulations realistically reproduced the characteristics of deep convection as revealed by the estimated spatial distribution of temperature, moisture, cloud reflectivity, and vertical profiles of temperature and moisture. Also, results indicated that vertical transport reduced ozone by 50% (50 parts per billion by volume, ppbv) in the upper atmosphere (12–15 km) and enhanced ozone by 39% (10 ppbv) in the lower atmosphere (<2 km). Field observations confirmed model results and indicated that surface ozone levels abruptly increased by 10–30 ppbv in the area impacted by convection due to transport by downdrafts from the upper troposphere. Once in the lower troposphere, the lifetime of ozone decreased due to enhanced dry deposition and chemical sinks. Ozone removal via dry deposition increased by 100% compared to non-convective conditions. The redistribution of tropospheric ozone substantially changed hydroxyl radical formation in the continental tropical boundary layer. Therefore, an important conclusion of this study is that the redistribution of tropospheric ozone, due to deep convection in non-polluted tropical regions, can simultaneously reduce the atmospheric loading of ozone and substantially impact the oxidation capacity of the lower atmosphere via the enhanced formation of hydroxyl radicals.     

Variability of ozone in the marine boundary layer of the equatorial Pacific Ocean

This study examines the processes controlling the diurnal variability of ozone (O₃) in the marine boundary layer of the Kwajalein Atoll, Republic of the Marshall Islands (latitude 8° 43′ N, longitude 167° 44′ E), during July to September 1999. At the study site, situated in the equatorial Pacific Ocean, O₃ mixing ratios remained low, with an overall average of 9–10 parts per billion on a volume basis (ppbv) and a standard deviation of 2.5 ppbv. In the absence of convective storms, daily O₃ mixing ratios decreased after sunrise and reached minimum during the afternoon in response to photochemical reactions. The peak-to-peak amplitude of O₃ diurnal variation was approximately 1–3 ppbv. During the daytime, O₃ photolysis, hydroperoxyl radicals, hydroxyl radicals, and bromine atoms contributed to the destruction of O₃, which explained the observed minimum O₃ levels observed in the afternoon. The entrainment of O₃-richer air from the free troposphere to the local marine boundary layer provided a recovery mechanism of surface O₃ mixing ratio with a transport rate of 0.04 to 0.2 ppbv per hour during nighttime. In the presence of convection, downward transport of O₃-richer tropospheric air increased surface O₃ mixing ratios by 3–12 ppbv. The magnitude of O₃ increase due to moist convection was lower than that observed over the continent (as high as 20–30 ppbv). Differences were ascribed to the higher O₃ levels in the continental troposphere and weaker convection over the ocean. Present results suggest that moist convection plays a role in surface-level O₃ dynamics in the tropical marine boundary layer.     

A Seasonal Comparison of the Ozone Photochemistry in Clean and Polluted Air Masses at Mace Head, Ireland

Measurements of the sum of peroxy radicals [HO₂ + RO₂],NO_x (NO + NO₂) and NO_y (the sum of oxidisednitrogen species) made at Mace Head, on the Atlantic coast of Ireland in summer 1996 and spring 1997 are presented. Together with a suite of ancillary measurements, including the photolysis frequencies of O₃ O(¹D)(j(O¹D)) and NO₂ (j(NO₂)), the measured peroxy radicals are used to calculate meandailyozone tendency (defined as the difference of the in-situphotochemical ozone production and loss rates); these values are compared with values derived from the photochemical stationary state (PSS) expression. Although the correlation between the two sets of values is good, the PSS values are found to be significantly larger than those derived from the peroxy radical measurements, on average, in line with previous published work. Possible sources of error in these calculations are discussed in detail. The data are further divided up into five wind sectors, according to the instantaneous wind direction measured at the research station. Calculation of mean ozone tendencies by wind sector shows that ozone productivity was higher during spring (April–May) 1997 than during summer (July–August) 1996across all airmasses, suggesting that tropospheric photochemistry plays an important role in the widely-reported spring ozone maximum in the Northern Hemisphere. Ozone tendencies were close to zero for the relatively unpolluted south-west, west and north-west wind sectors in the summer campaign, whereas ozone productivity was greatest in the polluted south-east sector for both campaigns. Daytime weighted average ozone tendencies were +(0.3± 0.1) ppbv h^–1 for summer 1996 and +(1.0± 0.5) ppbvh^–1 for spring 1997. These figures reflect the higher mixing ratios of ozone precursors in spring overall, as well as the higher proportion of polluted air masses from the south-east arriving at the site during the spring campaign. The ozone compensation point, where photochemical ozone destruction and production processes are in balance, is calculated to be ca. 14 pptv NO for both campaigns.     

Background ozone and anthropogenic ozone enhancement at niwot ridge,Colorado

The mixing ratios for ozone and NO_x (NO+NO₂) have been measured at a rural site in the United States. From the seasonal and diurnal trends in the ozone mixing ratio over a wide range of NO_x levels, we have drawn certain conclusions concerning the ozone level expected at this site in the absence of local photochemical production of ozone associated with NO_x from anthropogenic sources. In the summer (June 1 to September 1), the daily photochemical production of ozone is found to increase in a linear fashion with increasing NO_x mixing ratio. For NO_x mixing ratios less than 1 part per billion by volume (ppbv), the daily increase is found to be (17±3) [NO_x]. In contrast, the winter data (December 1 to March 1) indicate no significant increase in the afternoon ozone level, suggesting that the photochemical production of ozone during the day in winter approximately balances the chemical titration of ozone by NO and other pollutants in the air. The extrapolated intercept corresponding to [NO_x]=0 taken from the summer afternoon data is 13% less than that observed from the summer morning data, suggesting a daytime removal mechanism for O₃ in summer that is attributed to the effects of both chemistry and surface deposition. No significant difference is observed in the intercepts inferred from the morning and afternoon data taken during the winter.The results contained herein are used to deduce the background ozone level at the measurement site as a function of season. This background is equated with the natural ozone background during winter. However, the summer data suggest that the background ozone level at our site is elevated relative to expected natural ozone levels during the summer even at low NO_x levels. Finally, the monthly daytime ozone mixing ratios are reported for 0[NO_x]0.2 ppbv, 0.3 ppbv[NO_x]0.7 ppbv and 1 ppbv[NO_x]. These monthly ozone averages reflect the seasonal ozone dependence on the NO_x level.     

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.     

Carbonyl sulfide emissions from biomass burning in the tropics

Carbonyl sulfide emissions from biomass burning have been studied during field experiments conducted both in an African savanna area (Ivory Coast) and rice fields, central highland pine forest and savanna areas in Viet-Nam. During these experiments CO₂, CO and C₂H₂ or CH₄ have also been also monitored. COS values range from 0.6 ppbv outside the fires to 73 ppbv in the plumes. Significant correlations have been observed between concentrations of COS and CO (R ²=0.92,n=25) and COS and C₂H₂ (R ²=0.79,n=26) indicating a COS production during the smoldering combustion. COS/CO₂ emission factors (COS/CO₂) during field experiments ranged from 1.2 to 61×10^–6 (11.4×10^–6 mean value). COS emission by biomass burning was estimated to be up to 0.05 Tg S/yr in tropics and up to 0.07 Tg S/yr on a global basis, contributing thus about 10% to the global COS flux. Based on the S/C ratio measured in the dry plant biomass and the COS/CO₂ emission factor, COS can account for only about 7% of the sulfur emitted in the atmosphere by biomass burning.     

Variability of Near-Ground Ozone Concentrations During Cold Front Passages – a Possible Effect of Tropopause Folding Events

The analysis of surface ozone variability requires besides chemicalstudies the consideration of meteorological conditions and dynamicprocesses. Our research focuses on the mechanisms in connection with coldfront passages. A statistical study and case studies of cold front passageswere carried out at six German ground-based sites during the year 1990.After the passage of cold fronts three typical developments of thenear-ground ozone concentrations could be identified. Usually the ozoneconcentrations decrease due to advection of clean air masses or due toenhanced cloudiness preventing the photochemical production of ozone,chemical destruction by nitrogenoxides, and heterogeneous chemistry. In somecases the concentrations increased by reason of downward mixing of ozoneenriched air intruded from the stratosphere into the troposphere bytropopause foldings. For a few cases no modification set in. The decreasewas mostly twice as strong as the increase. The latter was between 4 and 8ppb on the average. Special emphasis is given to the transport ofstratospheric ozone down to the ground. There is no direct evidence forstratospheric ozone at ground level, because it cant be distinguished fromthe tropospheric one, but from case studies circumstantial evidence is foundin favour of it. As an example of increasing ozone behind the passage ofcold fronts one case study typical of all other case studies is presented.It shows the characteristic properties of the corresponding fronts, whichare fast movement, a vertical split structure and strong convection.     

Enhancements of CO and O3 from burnings in sugar cane fields

The manual harvest of sugar cane requires the burning of its foliage. This burning has strongly increased in Brazil after the National Alcohol Program was started which substituted automobile gasoline engines for alcohol engines. Presently, the source strength per unit area of this rural pollution is comparable to the well-known biomass burning source in Amazonia. The observed concentrations of CO and O₃ in the rural area of the state of São Paulo during the 1988 burning season were twice as large as those reported from an aircraft experiment of 1985 for biomass burnings of the tropical rain forest. Results are reported from airplane measurements and from three fixed ground stations. Mixing ratios of ozone and carbon monoxide in the height range below 6 km are normally less than 40 and 100 ppbv, (parts per billion by volume), respectively, in the absence of burnings. A strong O₃ and CO layer was observed during the burning period with peak concentrations of 80 ppbv of ozone and 580 ppbv of CO at about 2 km. The concentrations of CH₄ and CO₂ were also large, 1756 ppbv and 409 ppmv, respectively, at 1500 m. During the dry season period of the experiment, the ground based O₃ average diurnal variations obtained at the rural sites were practically identical to the typical urban variation observed at São José dos Campos, with daytime ozone values between 45 and 60 ppbv. A second three-day airplane excursion to the surgar cane fields in the wet season of 1989 has produces results to be contrasted with the dry (burning) season of 1988 and 1989. Carbon monoxide concentrations were below 100 ppbv at all heights and ozone concentrations were around 30–40 ppbv. The maximum daytime concentrations at the ground station Bauru was 25 ppbv of O₃, and at Jaboticabal it was 35 ppbv of O₃, only one half of what was observed in the dry season.Universidade Estadual de São Paulo.     

Effects of tropical deforestation on global and regional atmospheric chemistry

A major portion of tropospheric photochemistry occurs in the tropics. Deforestation, colonization, and development of tropical rain forest areas could provoke significant changes in emissions of radiatively and photochemically active trace gases. A brief review of studies on trace-gas emissions in pristine and disturbed tropical habitats is followed by an effort to model regional tropospheric chemistry under undisturbed and polluted conditions. Model results suggest that changing emissions could stimulate photochemistry leading to enhanced ozone production and greater mineral acidity in rainfall in colonized agricultural regions. Model results agree with measurements made during the NASA ABLE missions. Under agricultural/pastoral development scenarios, tropical rain forest regions could export greater levels of N₂O, CH₄, CO, and photochemical precursors of NO _y and O₃ to the global atmosphere with implications for climatic warming.     

Volatile organic compounds at a rural site in western Senegal

The objectives of this study were to identify species and levels of volatile organic compounds (VOCs), and determine their oxidation capacity in the rural atmosphere of western Senegal. A field study was conducted to obtain air samples during September 14 and September 15, 2006 for analyses of VOCs. Methanol, acetone, and acetaldehyde were the most abundant detected chemical species and their maximum mixing ratios reached 6 parts per billion on a volume basis (ppbv). Local emission sources such as firewood and charcoal burning strongly influenced VOC concentrations. The VOC concentrations exhibited little temporal variations due to the low reactivity with hydroxyl radicals, with reactivity values ranging from 0.001 to 2.6 s⁻¹. The conditions in this rural site were rather clean. Low ambient NO _x levels limited ozone production. Nitrogen oxide (NO _x ) levels reached values less than 2 ppbv and maximum VOC/NO _x ratios reached 60 ppbvC/ppbv, with an overall average of 2.4 ± 4.5 ppbvC/ppbv. This indicates that the rural western Senegal region is NO _x limited in terms of oxidant formation potential. Therefore, during the study period photochemical ozone production became limited due to low ambient NO _x levels. The estimated ozone formation reactivity for VOCs was low and ranged between −5.5 mol of ozone/mol of benzaldehyde to 0.6 mol/mol of anthropogenic dienes.     

Simultaneous Measurements of Black Carbon, PM10, Ozone and NOx Variability at a Locally Polluted Island in the Southern Tropics

This paper shows a comparative study of particle and surface ozone concentration measurements undertaken simultaneously at two distinct semi-urban locations distant by 4 km at Saint-Denis, the main city of La Réunion island (21.5° S, 55.5° E) during austral autumn (May 2000). Black carbon (BC) particles measured at La Réunion University, the first site situated in the suburbs of Saint-Denis, show straight-forward anti-correlation with ozone, especially during pollution peaks ( 650 ng/m³ and 15 ppbv, for BC and ozone respectively) and at night-time (90 ng/m³ and 18.5 ppbv, for BC and ozone respectively). NO_x (NO and NO₂) and PM₁₀ particles were also measured in parallel with ozone at Lislet Geoffroy college, a second site situated closer to the city centre. NO_x and PM₁₀ particles are anti-correlated with ozone, with noticeable ozone destruction during peak hours (mean 6 and 9 ppbv at 7 a.m. and 8 p.m. respectively) when NO_x and PM₁₀ concentrations exhibit maximum values. We observe a net daytime ozone creation (19 ppbv, O₃ +4.5 ppbv), following both photochemical and dynamical processes. At night-time however, ozone recovers (mean 11 ppbv) when anthropogenic activities are lower ([BC] 100 ng/m³). BC and PM₁₀ concentration variation obtained during an experiment at the second site shows that the main origin of particles is anthropogenic emission (vehicles), which in turn influences directly ozone variability. Saint-Denis BC and ozone concentrations are also compared to measurements obtained during early autumn (March 2000) at Sainte-Rose (third site), a quite remote oceanic location. Contrarily to Saint-Denis observations, a net daytime ozone loss (14.5 ppbv at 4 p.m.) is noticed at Sainte-Rose while ozone recovers (17 ppbv) at night-time, with however a lower amplitude than at Saint-Denis. Preliminary results presented here are handful data sets for modelling and which may contribute to a better comprehension of ozone variability in relatively polluted areas.     

The Role of In Situ Photochemistry in the Control of Ozone during Spring at the Jungfraujoch (3,580 m asl) – Comparison of Model Results with Measurements

A photochemical box model has been used to model themeasured diurnal ozone cycle in spring at Jungfraujochin the Swiss Alps. The comparison of the modelleddiurnal ozone cycle with the mean measured diurnalozone cycle in spring, over the period 1988–1996,shows a good agreement both with regard to the shapeand amplitude. Ozone concentrations increase duringthe daytime and reach a maximum at about 16:00–17:00(GMT) in both the modelled and the mean observed ozonecycle, indicative of net ozone production during thedaytime at Jungfraujoch in spring. The agreement isbetter when the modelled ozone cycle is compared withthe mean measured diurnal cycle (1988–1996) filteredfor north-westerly winds >5 m/s (representative ofregional background conditions at Jungfraujoch). Inaddition to ozone, the modelled diurnal cycle of[HO₂] + [CH₃O₂] also shows rather goodagreement with the mean diurnal cycle of the peroxyradicals measured during FREETEX '96, a FREETropopsheric Experiment at Jungfraujoch in April/May1996. Furthermore, this mean diurnal cycle of the sumof the peroxy radicals measured during FREETEX '96 isused to calculate, using steady-state expressions, therespective diurnal cycle of the OH radical. Thecomparison of the OH diurnal cycle, calculated fromthe peroxy radical measurements during FREETEX '96,with the modelled one, reveals also good agreement.The net ozone production rate during the day-time is0.27 ppbv h^-1 from the model, and 0.13 ppbvh^-1 from the observations during FREETEX '96. Theobservations and model results both suggest that thediurnal ozone variation in spring at Jungfraujoch isprimarily of photochemical origin. Furthermore, theobserved and modelled positive net ozone productionrates imply that tropospheric in situphotochemistry contributes significantly to theobserved high spring ozone values in the observedbroad spring-summer ozone maximum at Jungfraujoch.     

Chlorine-hydrocarbon photochemistry in the marine troposphere and lower stratosphere

A one-dimensional photochemical model was used to explore the role of chlorine atoms in oxidizing methane and other nonmethane hydrocarbons (NMHCs) in the marine troposphere and lower stratosphere. Where appropriate, the model predictions were compared with available measurements. Cl atoms are predicted to be present in the marine troposphere at concentrations of approximately 10³ cm^-3, mostly as a consequence of the reaction of OH with HCl released from sea spray. Despite this low abundance, our results indicate that 20 to 40% of NMHC oxidation in the troposphere (0–10 km) and 40 to 90% of NMHC oxidation in the lower stratosphere (10–20 km) is caused by Cl atoms. At 15 km, NMHC-Cl reactions account for nearly 80% of the PAN produced.The model was also used to test the longstanding hypothesis that NOCl is an intermediate to HCl formation from sea salt aerosols. It was found that the NOCl concentration required (10 ppt) would be incompatible with field observations of reactive nitrogen and ozone abundance. Chlorine nitrate (ClONO₂) and methyl nitrate (CH₃ONO₂) were shown to be minor components of the total NO _y abundance. Heterogeneous reactions that might enhance photolysis of halocarbons or convert ClONO₂ to HOCl or Cl₂ were determined to be relatively unimportant sources of Cl atoms. Specific and reliable measurements of HCl and other reactive chlorine species are needed to better assess their role in tropospheric chemistry.     

Estimates of the Chemical Budget for Ozone at Waliguan Observatory

Waliguan Observatory (WO) is an in-land Global Atmosphere Watch (GAW) baseline station on the Tibetan plateau. In addition to the routine GAW measurement program at WO, measurements of trace gases, especially ozone precursors, were made for some periods from 1994 to 1996. The ozone chemical budget at WO was estimated using a box model constrained by these measured trace gas concentrations and meteorological variables. Air masses at WO are usually affected by the boundary layer (BL) in the daytime associated with an upslope flow, while it is affected by the free troposphere (FT) at night associated with a downslope flow. An anti-relationship between ozone and water vapor concentrations at WO is found by investigating the average diurnal cycle pattern of ozone and water vapor under clear sky conditions. This relationship implies that air masses at WO have both the FT and BL characteristics. Model simulations were carried out for clear sky conditions in January and July of 1996, respectively. The chemical characteristics of mixed air masses (MC) and of free tropospheric air masses (FT) at WO were investigated. The effects of the variation in NO_x and water vapor concentrations on the chemical budget of ozone at WO were evaluated for the considered periods of time. It was shown that ozone was net produced in January and net destroyed in July for both FT and MC conditions at WO. The estimated net ozone production rate at WO was –0.1 to 0.4 ppbv day^–1 in FT air of January, 0.0 to 1.0 ppbv day^–1 in MC air of January, –4.9 to –0.2 ppbv day^–1 in FT air of July, and –5.1 to 2.1 ppbv day^–1 in MC air of July.     

A Possible Photochemical Link Between Stratospheric and Near-Surface Ozone on Swiss Mountain Sites in Late Winter

Record high near-surface ozone concentrations at two elevated sites (Chaumont, 1140 m asl, and Rigi, 1030 m asl) in Switzerland were observed simultaneously with extremely low total ozone during a fair weather period in mid-February 1993. An analysis of ozone, temperature, humidity, and wind profiles suggests that the surface ozone peaks were most possibly generated within the region in a layer between about 1000 and 1500 m asl. Mean diurnal cycles of ozone concentration during the period shows a strong increase from late morning to late afternoon at Chaumont and at the same time a decrease at the high alpine site Jungfraujoch (3580 m asl). The different diurnal ozone cycles can both be explained photochemically by taking into account the large difference in NOx concentrations (about two orders of magnitude) between the sites. Photochemical processes are also indicated by the diurnal cycles of NO2 and NO concentration. As a strong photochemical activity is not expected in mid-February at 47°N, we hypothesize that the extremely low total ozone played a role. Total ozone controls the amount of UV-B radiation reaching the troposphere and thus influences photochemical processes. Using a radiation model, we calculated an increase in ozone photolysis at Chaumont and Jungfraujoch of 73% and 83%, respectively, on the day with the lowest total ozone (243 DU) compared to average February conditions (335 DU). It is suggested that total ozone changes have the potential to stimulate photochemistry sufficiently to produce the observed surface ozone peaks at Chaumont and Rigi of 61 and 64 ppbv, respectively. A fog layer just below Chaumont during these days probably also influenced photochemistry, but on a smaller spatial scale. Our empirical results on the influence of changing UV radiation on tropospheric photochemistry are in close agreement with model studies of other groups. Although this case study represents unique conditions, a distinct anticorrelation between near-surface ozone at Chaumont and total ozone also appears in other years (1992–1997) when selecting fair weather days in mid-February. However, other influences cannot be excluded. The selected days provide evidence of a significant photochemical source of ozone in the mid-latitude lower troposphere in late winter.     

Tropospheric Ozone at the Swedish Mountain Site Åreskutan: Budget and Trends

Ozone measurements, performed since 1987, at the Swedish TOR/EUROTRACstation Åreskutan (lat. 63.4° N, long. 13.1° E, 1250 m abovesea level) are analyzed. The annual average ozone concentration at the sitehas increased by about 0.4 ppbv (1%) per year during the period1987–1994. The corresponding trends for individual months show adecrease during April–September and an increase during the rest of theyear. The ozone budget at Åreskutan has been investigated using backtrajectories of the air parcels, and the cosmogenic radionuclide⁷Be as a tracer of stratospheric air. From a simple diagnosticmodel, it is estimated that the contribution of stratospheric ozone to theconcentrations measured at Åreskutan is 5 ppbv (or 14% of themeasured values) on average, reaching a maximum of 23 ppbv (50%),during the episodes of direct stratospheric influence. In spring, thestratospheric contribution to ozone budget at Åreskutan is at itsmaximum, and approximately equal to the net photochemical ozone productionin the air mass affecting the site, whereas in winter, it is compensated byozone chemical sink during the transport of air masses from pollutedEuropean regions, to Scandinavia.     

A model investigation of the impact of increases in anthropogenic NO x emissions between 1967 and 1980 on tropospheric ozone

Recent observations suggest that the abundance of ozone between 2 and 8 km in the Northern Hemisphere mid-latitudes has increased by about 12% during the period from 1970 to 1981. Earlier estimates were somewhat more conservative suggesting increases at the rate of 7% per decade since the start of regular observations in 1967. Previous photochemical model studies have indicated that tropospheric ozone concentrations would increase with increases in emissions of CO, CH₄ and NO _x . This paper presents an analysis of tropospheric ozone which suggests that a significant portion of its increase may be attributed to the increase in global anthropogenic NO _x emissions during this period while the contribution of CH₄ to the increase is quite small. Two statistical models are presented for estimating annual global anthropogenic emissions of NO _x and are used to derive the trend in the emissions for the years 1966–1980. These show steady increase in the emissions during this interval except for brief periods of leveling off after 1973 and 1978. The impact of this increase in emissions on ozone is estimated by calculations with a onedimensional (latitudinal) model which includes coupled tropospheric photochemistry and diffusive meridional transport. Steady-state photochemical calculations with prescribed NO _x emissions appropriate for 1966 and 1980 indicate an ozone increase of 8–11% in the Northern Hemisphere, a result which is compatible with the rise in ozone suggested by the observations.