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.     

Measurement of the Diurnal Variation of the OH Radical Concentration and Analysis of the Data by Modelling

Daily variations of the hydroxyl radical concentration have been measured during a campaign at the Weybourne Atmospheric Observatory (WAO) in June 1995. These measurements are compared with box model calculations, based on a slightly modified, second generation Regional Acid Deposition Model (RADM2). Results from eight days of the comparison are presented. A detailed analysis and discussion of the different source and sink terms is given for two days: Julian Day (JD) 170 (19 June, and 178 (27 June). In both cases excellent agreement between the measurements and the calculation is obtained, indicating that the model describes the OH chemistry sufficiently well. Furthermore, the analysis of these days demonstrate that JD 170 is dominated by the NOx catalysed OH production, whereas JD 178 is influenced by OH formation via ozone photolysis.     

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.     

Atmospheric chemistry of alkanes

The reactions of the alkanes under atmospheric conditions and in the presence of oxides of nitrogen are reviewed and evaluated. Particular emphasis is placed upon their subsequent reactions after the initial OH radical reaction under conditions where the alkyl peroxy radicals produced react predominantly with NO, rather than with HO₂ and/or RO₂ radicals. Methods are discussed for estimating the overall OH radical rate constants, the number of molecules of NO consumed per alkane molecule reacted, and the products formed and their yields.     

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

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

The Measurement of Active Chlorine in the Atmosphere by Chemical Amplification

Chemical amplification, CA, a method commonly used for the detection of peroxy radicals, HO₂ and RO₂, was found to be sensitive towards ClOx (Cl+ClO+OClO) as well. ClOx is reduced by NO to Cl atoms which react with carbon monoxide in the presence of O₂. The reaction sequence thus initiated oxidizes CO to CO₂ and NO to NO₂, with a chain length of 300 ± 60. This allows the atmospheric ClOx content to be measured under ambient conditions with a detection limit of better than 1 ppt. In parallel peroxy radicals are indicated with a chain length of 160 ± 15. Chemical amplification is not specific and does not indicate which radical chain it is seeing. Identification relies solely on plausibility. During the ARCtic Tropospheric Ozone Chemistry (ARCTOC) campaign in spring 1995 and 1996 the CA technique was used at Ny-Ålesund. ClOx at mixing ratios of up to 2 ppt were found in the boundary layer under certain conditions. The low concentrations of ClOx indicate that the arctic boundary ozone depletion is mainly driven by bromine.     

High-Latitude Springtime Photochemistry. Part I: NOx, PAN and Ozone Relationships

Springtime measurements of NO_x, ozone, PAN,J(NO₂), and other compounds were made near Ny-Ålesund,Svalbard (78°54N, 11°53E), in 1994 and Poker Flat,Alaska (65°08N, 147°29W), in 1995. At Svalbard medianmixing ratios for PAN and NO_x of 237 and 23.7 pptv,respectively, were observed. The median mixing ratios at Poker Flat for PANand NO_x were 79.5 and 85.9 pptv, respectively. These data areused to estimate thermal PAN decomposition using several differentapproaches. At Svalbard PAN decomposition was very small, while at PokerFlat up to 30 pptv/h PAN decomposed. At both sites the NO_x/PANratio increased with temperature between –10 and 20°C implyingthat PAN decomposition is an important NO_x source. In-situozone production was calculated from the measured NO, NO₂,O₃, J(NO₂), and temperature data, using thesteady state assumption Median ozone production was 605 pptv/h at PokerFlat, and one order of magnitude smaller at Svalbard during the daytime.Only at Poker Flat could a direct influence on the diurnal ozone cycle beobserved from in-situ production. These results imply that PAN decompositionis a major source of NO_x in the high latitude troposphere, andthat this contributes to the observed spring maximum in surface ozone.     

Hydroxyl and Peroxy Radical Chemistry in a Rural Area of Central Pennsylvania: Observations and Model Comparisons

Atmospheric hydroxyl (OH), hydroperoxy (HO₂), total peroxy (HO₂ and organic peroxy radicals, RO₂) mixing ratios and OH reactivity (first order OH loss rate) were measured at a rural site in central Pennsylvania during May and June 2002. OH and HO₂ mixing ratios were measured with laser induced fluorescence (LIF); HO₂ + RO₂ mixing ratios were measured with chemical ionization mass spectrometry (CIMS). The daytime maximum mixing ratios were up to 0.6 parts per trillion by volume (pptv) for OH, 30 pptv for HO₂, and 45 pptv for HO₂ + RO₂. A parameterized RACM (Regional Atmospheric Chemistry Mechanism) box model was used to predict steady state OH, HO₂ and HO₂ + RO₂ concentrations by constraining the model to the measured OH reactivity and previously measured volatile organic compound (VOC) distributions. The averaged model calculations are generally in good agreement with the observations. For OH, the model matched the observations for day and night, with an average observed-to-modeled ratio of 0.80. In previous studies such as PROPHET98, nighttime NO was near 0 pptv and observed nighttime OH was significantly larger than modeled OH. In this study, nighttime observed and modeled OH agree to within measurement and model uncertainties because the main source of the nighttime OH was the reaction HO₂ + NO → OH + NO₂, with the NO being continually emitted from the surrounding fertilized corn field. The observed-to-modeled ratio for HO₂ is 1.0 on average, although daytime HO₂ is underpredicted by a factor of 1.2 and nighttime HO₂ is over-predicted by a factor of ∼2. The average measured and modeled HO₂ + RO₂ agree well during daytime, but the modeled value is about twice the measured value during nighttime. While measured HO₂ + RO₂ values agree with modeled values for NO mixing ratios less than a few parts per billion by volume (ppbv), it increases substantially above the expected value for NO greater than a few ppbv. This observation of the higher-than-expected HO₂ + RO₂ with the CIMS technique confirms the observed increase of HO₂ above expected values at higher NO mixing ratios in HO₂ measurements with the LIF technique. The maximum instantaneous O₃ production rate calculated from HO₂ and RO₂ reactions with NO was as high as 10–15 ppb h⁻¹ at midday; the total daily O₃ production varied from 13 to 113 ppbv d⁻¹ and was 48 ppbv d⁻¹ on average during this campaign.     

Tropospheric Box-Modelling and Analytical Studies of the Hydroxyl (OH) Radical and Related Species: Comparison with Observations

Calculated and observed hydroxyl (OH) fields are presented. Calculated OH was obtained in three ways using (1) a photochemical box-model (2) a simple OH steady state approach and (3) a variant on (2) – the multiple equation steady state approach which assumes steady state for OH, HO2 and RO2 and hence obtains three simultaneous, non linear, equations. All three methods used data collected in June 1995 during the Weybourne Atmospheric Observatory Summer Experiment (WAOSE'95). Julian Days 169, 178, 179 and 180 displayed especially good data capture and were consequently chosen for study. The two steady state methods are essentially driven purely by observations and derive OH from the ratio of the relevant source and sink terms. The box-model was constrained where possible to observations; remaining unmeasured volatile organic compounds (VOCs) were initialised to an arbitrary low value of 10 ppt. Agreement between theory and experiment was usually around 50% and often better than this value, especially on J169, though discrepancies of up to a factor of 3 were occasionally apparent. Despite the inherent scatter, neither the box-model nor the simple steady state method were found to consistently over-estimate OH (a common feature of many numerical approaches) although this did occur to a certain extent using the multiple equation steady state approach, probably due to breakdowns in the steady state approximation. More data spread was evident in the box-model approach compared with the other methods. An analysis of the major sources and sinks of OH is presented for the three methods of calculation. Calculated and observed peroxy radicals are also presented. Calculated peroxy radicals were generally lower than that observed at night yet higher, sometimes by up to a factor of 7, during the day. Possible explanations for this result are explored.     

Impact of Air Transport on Seasonal Variations and Trends of Surface Ozone at Kislovodsk High Mountain Station

The impact of air transport on the surface ozone variations is analyzed at Kislovodsk High Mountain Station for the period 1989–1996 on the basis of 2D back trajectories. It was shown that the contribution of photochemical and dynamical processes is different for the different seasons. In summer months the surface ozone concentration is governed by photochemical ozone production in semi polluted air from the regions of Northern Caspian, Southern Ural and Volga region. Time of the seasonal ozone maximum appearance is defined by joint influence of the processes of photochemical production and destruction in the eastern sectors and advection from Ukraine and Central Europe. The value of the seasonal minimum is determined by the processes of ozone destruction in the air coming from northeastern direction in the stable frontal zone. Distribution of sectors of the air transport changes from year to year and it can partly explain strong negative trend of the surface ozone concentration at the site.     

Peroxy Radical Concentrations Measured at a Forest Canopy in Nikko,Japan, in Summer 2002

Concentrations of peroxy radicals were measured by a chemical amplification technique at a remote forested site as part of the Program for Research on Oxidants in a Forested Region in Nikko (PROFRN). During the measurement period of 22–27 July 2002, the mixing ratios of peroxy radicals averaged for 3 min at midday ranged from 109 to 134 pptv at a height approximately 5 m above the forest canopy. Significant diurnal variation in concentrations of peroxy radicals was observed, with the maximum usually occurring around noon. Most of the variation was driven by changes in the intensity of solar radiation. However, it was found that the peroxy radical concentration reached its peak about 3-h later than that of solar radiation on 24 and 26 July. The origins of this delay are discussed based on an analysis of the total radical budget in that period. A transport of polluted air masses to the site was one of possible causes for the inconsistency. In addition, the measured peroxy radical concentrations were compared with those derived from the deviations of NO-NO₂-O₃ photo-stationary state (PSSD) for clear days. The estimated half-hour-average concentrations of peroxy radical were in agreement with the PERCA measured in the morning and late afternoon. However the two techniques differed by as much as a factor of two during the time of near midday.     

Modelling of the long-range transport of peroxyacetylnitrate to Scandinavia

Model calculations and field measurements have shown that when air masses accumulate emissions of hydrocarbons and nitrogen oxides from sources in continental Europe and then move towards Scandinavia without any synoptic scale break-up of the atmospheric boundary layer (e.g. frontal passages), elevated PAN concentrations in southern Norway or Sweden in the range 1–5 ppb may be caused by long-range transport. The model calculations showed that over sea, the persistence of PAN was comparable to that of ozone in an ageing air mass when the temperatures were fairly low (5–10°C). At higher temperatures the thermal decomposition of PAN made the compound less persistent than ozone. Over land, the situation may be different since the ground removal is typically three times more efficient for ozone than for PAN.According to the model, the concentration of PAN did not change very much when an ageing air mass was exposed to moderate emissions of hydrocarbons, nitrogen oxides, or both. The concentration of PAN decreased less than the concentration of ozone when an ageing air mass was exposed to high emissions of nitrogen oxides.     

Tropospheric ozone and oxides of nitrogen over the north-western Pacific in summer

In summer, atmospheric ozone was measured from an aircraft platform simultaneously with nitric oxide (NO), oxides of nitrogen (NO _y ), and water vapor over the Pacific Ocean in east Asia from 34° N to 19° N along the longitude of 138±3°E. NO _y was measured with the aid of a ferrous sulfate converter. The altitude covered was from 0.5 to 5 km. A good correlation in the smoothed meridional distributions between ozone and NO _y was seen. In particular, north of 25° N, ozone and NO _y mixing ratios were considerably higher than those observed in tropical marine air south of 25° N. NO _y and O₃ reached a minimum of 50 pptv and 4 ppbv respectively in the boundary layer at a latitude of 20° N. The NO concentration between 2 and 5 km at the same latitude was 30 pptv. The profiles of ozone and water vapor mixing ratios were highly anti-correlated between 25° N and 20° N. In contrast, it was much poorer at the latitude of 33° N, suggesting a net photochemical production of ozone there.     

Tropospheric Ozone in a Global-Scale Three-Dimensional Lagrangian Model and Its Response to NOX Emission Controls

A three-dimensional Lagrangian tropospheric chemistry modelis used toinvestigate the impact of human activities on the tropospheric distributionofozone and hydroxyl radicals. The model describes the behaviour of 50 speciesincluding methane, carbon monoxide, oxides of nitrogen, sulphur dioxide andnineorganic compounds emitted from human activities and a range of other sources.Thechemical mechanism involves about 100 chemical reactions of which 16 arephotochemical reactions whose diurnal dependence is treated in full. The modelutilises a five minute chemistry time step and a three hour advection timestepfor the 50,000 air parcels. Meteorological data for the winds, temperatures,clouds and so on are taken from the UK Meteorological Office global model for1994 onwards. The impacts of a 50% reduction in European NO_Xemissions onglobal ozone concentrations are assessed. Surface ozoneconcentrations decrease in summertime and rise in wintertime, but to differentextents.     

NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> change over China and its influences

A 3-D chemical transport model (OSLO CTM2) is used to investigate the impact of the increase of NOx emission over China. The model is capable to reproduce basically the seasonal variation of surface NOx and ozone over eastern China. NOx emission data and observations reveal that NOx over eastern China increases quite quickly with the economic development of China. Model results indicate that NOx concentration over eastern China increasingly rises with the increase of NOx emission over China, and accelerates to increase in winter. When the NOx emission increases from 1995 to its double, the ratio of NO2/NOx abruptly drops in winter over northern China. Ozone at the surface decreases in winter with the continual enhancement of the NOx level over eastern China, but increases over southern China in summertime. It is noticeable that peak ozone over northern China increases in summer although mean ozone changes little. In summer, ozone increases in the free troposphere dominantly below 500 hPa.Moreover, the increases of total ozone over eastern China are proportional to the increases of NOx emission.In a word, the model results suggest that the relationship between NOx and ozone at the surface would change with NOx increase.     

Comparison of Measured Ozone Production Efficiencies in the Marine Boundary Layer at Two European Coastal Sites under Different Pollution Regimes

Ozone production efficiencies (E_N), which can be defined as the netnumber of ozone molecules produced per molecule of NO_xoxidised, have been calculated from measurements taken during three intensive field campaigns (one in the spring, EASE 96, and two in the summer, EASE 97 and TIGER 95), at two European coastal sites (Mace Head, Ireland (EASE) and Weybourne, Norfolk (TIGER)) impacted by polluted air masses originating from both the U.K. and continental Europe, as well as relatively clean oceanic air masses from the Arctic and Atlantic. From a detailed wind sector analysis of the EASE 96 and 97 data it is clear that two general types of pollution regime were encountered at Mace Head. The calculated ozone production efficiency in clean oceanic air masses was approximately 65, which contrasted to more polluted air, from the U.K. and the continental European plume, where the efficiency decreased to between 4 and 6. The latter values of E_Nagree well with literature measurements conducted downwind of various urban centres in the U.S. and Europe, which are summarised in a wide-ranging review table. The E_N value calculated for clean oceanic air is effectivelyan upper limit, owing to the relatively rapid deposition of HNO₃ tothe ocean. Consideration of the variation of E_N with NO_x forthe three campaigns suggests that ozone production efficiency is relatively insensitive to both geographical location and season. The measuredE_N values are also compared with values derived from steady-state expressions. An observed anti-correlation between E_N and measured ozone tendencyis briefly discussed.     

Surface Trace Gases at a Rural Site between the Megacities of Beijing and Tianjin

The North China Plain （NCP） has recently faced serious air quality problems as a result of enhanced gas pollutant emissions due to the process of urbanization and rapid economic growth. To explore regional air pollu- tion in the NCP, measurements of surface ozone （O3）, nitrogen oxides （NOx）, and sulfur dioxide （SO2） were car- ried out from May to November 2013 at a rural site （Xianghe） between the twin megacities of Beijing and Tianjin. The highest hourly ozone average was close to 240 ppbv in May, followed by around 160 ppbv in June and July. High ozone episodes were more notable than in 2005 and were mainly associated with air parcels from the city cluster in the hinterland of the polluted NCP to the southwest of the site. For NOx, an important ozone precur- sor, the concentrations ranged from several ppbv to nearly 180 ppbv in the summer and over 400 ppbv in the fall. The occurrence of high NOx concentrations under calm condi- tions indicated that local emissions were dominant in Xianghe. The double-peak diurnal pattern found in NOx concentrations and NO/NOx ratios was probably shaped by local emissions, photochemical removal, and dilution re- sulting from diurnal variations of surface wind speed and the boundary layer height. A pronounced SO2 daytime peak was noted and attributed to downward mixing from an SO2-rich layer above, while the SO2-polluted air mass transported from possible emission sources, which differed between the non-heating （September and October） and heating （November） periods, was thought to be responsible for night-time high concentrations.     

Observations of the Nitrate Radical in the Marine Boundary Layer

A study of the nitrate radical (NO3) has been conducted through a series of campaigns held at the Weybourne Atmospheric Observatory, located on the coast of north Norfolk, England. The NO3 concentration was measured in the lower boundary layer by the technique of differential optical absorption spectroscopy (DOAS). Although the set of observations is limited, seasonal patterns are apparent. In winter, the NO3 concentration in semi-polluted continental air masses was found to be of the order of 10 ppt, with an average turnover lifetime of 2.4 minutes. During summer in clean northerly air flows, the concentration was about 6 ppt with a lifetime of 7.2 minutes. The major loss mechanisms for the radical were investigated in some detail by employing a chemical box model, constrained by a suite of ancillary measurements. The model indicates that during the semi-polluted conditions experienced in winter, the major loss of NO3 occurred indirectly through reactions of N2O5, either in the gas-phase with H2O, or through uptake on aerosols. The most important direct loss was via reactions of NO3 with a number of unsaturated nonmethane hydrocarbons. The cleaner air masses observed during the summer were of marine origin and contained elevated concentrations of dimethyl sulfide (DMS), which provided the major loss route for NO3. The box model was then used to investigate the conditions in the remote marine boundary layer under which DMS will be oxidised more rapidly at night (by NO3) than during the day (by OH). This should occur if the concentration of NO2 is more than about 60% that of DMS.