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.     

Is the Arctic Surface Layer a Source and Sink of NOx in Winter/Spring?

Measurements of NO_x (NO +NO₂) and the sum of reactive nitrogenconstituents, NO_y, were made near the surface atAlert (82.5°N), Canada during March and April1998. In early March when solar insolation was absentor very low, NO_x mixing ratios were frequentlynear zero. After polar sunrise when the sun was abovethe horizon for much or all of the day a diurnalvariation in NO_x and NO_y was observed withamplitudes as large as 30–40 pptv. The source ofactive nitrogen is attributed to release from the snowsurface by a process that is apparently sensitized bysunlight. If the source from the snowpack is a largescale feature of the Arctic then the diurnal trendsalso require a competing process for removal to thesurface. From the diurnal change in the NO/NO₂ratio, mid-April mixing ratios for the sum of peroxyand halogen oxide radicals of 10 pptv werederived for periods when ozone mixing ratios were inthe normal range of 30–50 ppbv. Mid-day ozoneproduction and loss rates with the active nitrogensource were estimated to be 1–2 ppbv/day and in nearbalance. NO_y mixing ratios which averaged only295±66 pptv do not support a large accumulation inthe high Arctic surface layer in the winter and springof 1998. The small abundance of NO_y relative tothe elevated mixing ratios of other long-livedanthropogenic constituents requires that reactivenitrogen be removed to the surface during transport toor during residence within the high Arctic.     

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.     

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.     

Experiments On Buoyant Plume Dispersion In A Laboratory Convection Tank

Plume dispersion in the convective boundary layer (CBL) is investigated experimentally in a laboratory convection tank. The focusis on highly-buoyant plumes that loft near or become trapped in the CBL capping inversion and resistdownward mixing. Such plumes are defined by dimensionless buoyancy fluxes F_* 0.1, where F_* = F_b/(U w_* ² z_i), F_b is the stack buoyancy flux,U is the mean wind speed, w_* is the convective velocity scale, and z_i is the CBL depth. The aim is to obtain statistically-reliable mean (C) and root-mean-square (rms, _c) concentration fields as a function of F_* and the dimensionless distance X = w_*x/(U z_i), where x is the distance downstream of the source.The experiments reveal the following mainresults: (1) For 3 X 4and F_* 0.1, the crosswind-integrated concentration (CWIC) fields exhibit distinctly uniform profiles below z_i with a CWIC maximum aloft, in contrast to the nonuniform profiles obtained earlier by Willis and Deardorff. (2) The lateral dispersion (_y) variation with X is consistent with Taylor's theory for _* 0.1 and a buoyancy-enhanced dispersion, _y/z_i F_* ^1/3X^2/3, forF_* = 0.2 and 0.4. (3) The entrapment, the plume fraction above z_i, has a mean (E) that follows a systematic variationwith X and F_*, and a variability (_e/E) that is broad ( 0.3 to 2) near the source but subsides to 0.25 far downstream. (4) Vertical profiles of the concentration fluctuation intensity (c/C) are uniform for z < z_i and X > 1.5, but exhibit significant increases: (a) at the surface and close to the source (X 1.5), and(b) in the entrainment zone. (5) The cumulative distribution functions (CDFs) of the scaled concentration fluctuations (c/_c) separate into mixed-layer and entrainment-layer CDFs for X 2, with the mixed-layer group collapsing to a single distribution independent of z.These are the first experiments to obtain all components of the lateral and vertical dispersion parameters (rms meander, relative dispersion, total dispersion) for continuous buoyant releases in a convection tank. They also are the first tank experiments to demonstrate agreement with field observations of: (1) the scaled ground-level concentration along the plume centreline, and (2) the dimensionless lateral dispersion _y/z_i of buoyant plumes.     

Gaseous and Particulate Oxidation Products Analysis of a Mixture of α-pinene + β-pinene/O3/Air in the Absence of Light and α-pinene + β-pinene/NOx/Air in the Presence of Natural Sunlight

The gas and particle phase reaction products of a mixture of the atmospherically important terpenes -pinene and -pinene with the atmospheric oxidants O₃ and OH/NO_x were investigated using both gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC) for identification and quantification of reaction products. The nighttime oxidation of a mixture of -pinene and -pinene in the presence of O₃/air, and the daytime oxidation of a mixture of -pinene + -pinene with NO_x air in the presence of natural sunlight were carried out in the University of North Carolina's large outdoor smog chamber (190 m³) located in Chatham County, North Carolina. Mass balances for gaseous and aerosol reaction products are reported over the course of the reaction. More than twenty-nine products were identified and/or quantified in this study. On average, measured gas and particle phase products accounted for 74 to 80% of the reacted -pinen/-pinene mixture carbon. Measurements show that a number of reaction products were found in both O₃ and NO_x system [pinonaldehyde, pinic acid, pinonic acid, pinalic-3-acid, 4-hydroxypinalic-3-acid, 4-oxonopinone, 1-hydroxy-nopinone, 3-hydroxy-nopinone, and nopinone]. Pinonic acid, pinic acid, pinalic-3-acid, 4-hydroxypinalic-3-acid, and 10-hydroxypinonic acid were observed in the early stage in the aerosol phase and may play an important role in the early formation of secondary aerosols.     

A study of ozone in the Colorado mountains

The seasonal and diurnal variations of ozone mixing ratios have been observed at Niwot Ridge. Colorado. The ozone mixing ratios have been correlated with the NO _x (NO+NO₂) mixing ratios measured concurrently at the site. The seasonal and diurnal variations in O₃ can be reasonably well understood by considering photochemistry and transport. In the winter there is no apparent systematic diurnal variation in the O₃ mixing ratio because there is little diurnal change of transport and a slow photochemistry. In the summer, the O₃ levels at the site are suppressed at night due to the presence of a nocturnal inversion layer that isolated ozone near the surface, where it is destroyed. Ozone is observed to increase in the summer during the day. The increases in ozone correlate with increasing NO _x levels, as well as with the levels of other compounds of anthropogenic origin. We interpret this correlation as in-situ or in-transit photochemical production of ozone from these precursors that are transported to our site. The levels of ozone recorded approach 100 ppbv at NO _x mixing ratios of approximately 3 ppbv. Calculations made using a simple clean tropospheric chemical model are consistent with the NO _x -related trend observed for the daytime ozone mixing ratio. However, the chemistry, which does not include nonmethane hydrocarbon photochemistry, underestimates the observed O₃ production.     

Monoterpene concentrations in and above a forest of scots pine

Diurnal and vertical ambient air measurements of the monoterpenes have been made in and above a Scots pine (Pinus sylvestris) forest of central Sweden, within the boreal northern coniferous biome. Sampling was done with Tenax TA, and analysis by GC and ion trap detection. Daytime mixing ratios were on the order of tenths of a ppbv from the forest floor to the top of the forest, and a factor of 2 or 3 lower above the forest. Mixing ratios at night were at the ppbv level, highest near the forest floor and the crown, and decreased with height above the forest. The highest total concentration observed was 8 ppbv inside the forest at 3 am (GMT). The average terpene composition was 3-carene 32%, -pinene 29%, limonene 18%, -pinene 10%, -phellandrene 7%, camphene 5%, and sabinene at less than 2%. The 3-carene/-pinene ratio varied with wind direction and speed, relative humidity, and wet/dry vegetation, but not with ozone or NO₂ concentration, solar radiation, or temperature. Variations in the observed terpene composition at the sampling site are mainly caused by the influence of other vegetation in the vicinity of the site. It would seem that wet Scots pine emits more 3-carene relative to -pinene than does dry pine.     

Ozone production potential following convective redistribution of biomass burning emissions

The effects of deep convection on the potential for forming ozone (ozone production potential) in the free troposphere have been simulated for regions where the trace gas composition is influenced by biomass burning. Cloud dynamical and photochemical simulations based on observations in 1980 and 1985 Brazilian campaigns form the basis of a sensitivity study of the ozone production potential under differing conditions. The photochemical fate of pollutants actually entrained in a cumulus event of August 1985 during NASA/GTE/ABLE 2A (Case 1) is compared to photochemical ozone production that could have occurred if the same storm had been located closer to regions of savanna burning (Case 2) and forest burning (Case 3). In each case studied, the ozone production potential is calculated for a 24-hour period following convective redistribution of ozone precursors and compared to ozone production in the absence of convection. In all cases there is considerably more ozone formed in the middle and upper troposphere when convection has redistributed NO_x, hydrocarbons and CO compared to the case of no convection.In the August 1985 ABLE 2A event, entrainment of a layer polluted with biomass burning into a convective squall line changes the free tropospheric cloud outflow column (5–13 km) ozone production potential from net destruction to net production. If it is assumed that the same cloud dynamics occur directly over regions of savanna burning, ozone production rates in the middle and upper troposphere are much greater. Diurnally averaged ozone production following convection may reach 7 ppbv/day averaged over the layer from 5–13 km-compared to typical free tropospheric concentrations of 25–30 ppbv O₃ during nonpolluted conditions in ABLE 2A. Convection over a forested region where isoprene as well as hydrocarbons from combustion can be transported into the free troposphere leads to yet higher amounts of ozone production.     

Field measurements of NO and NO2 emissions from fertilized and unfertilized soils

Field measurements of NO and NO₂ emissions from soils have been performed in Finthen near Mainz (F.R.G.) and in Utrera near Seville (Spain). The applied method employed a flow box coupled with a chemiluminescent NO _x detector allowing the determination of minimum flux rates of 2 g N m^-2 h^-1 for NO and 3 g m^-2 h^-1 for NO₂.The NO and NO₂ flux rates were found to be strongly dependent on soil surface temperatures and showed strong daily variations with maximum values during the early afternoon and minimum values during the early morning. Between the daily variation patterns of NO and NO₂, there was a time lag of about 2 h which seem to be due to the different physico-chemical properties of NO and NO₂. The apparent activation energy of NO emission calculated from the Arrhenius equation ranged between 44 and 103 kJ per mole. The NO and NO₂ emission rates were positively correlated with soil moisture in the upper soil layer.The measurements carried out in August in Finthen clearly indicate the establishment of NO and NO₂ equilibrium mixing ratios which appeared to be on the order of 20 ppbv for NO and 10 ppbv for NO₂. The soil acted as a net sink for ambient air NO and NO₂ mixing ratios higher than the equilibrium values and a net source for NO and NO₂ mixing ratios lower than the equilibrium values. This behaviour as well as the observation of equilibrium mixing ratios clearly indicate that NO and NO₂ are formed and destroyed concurrently in the soil.Average flux rates measured on bare unfertilized soils were about 10 g N m^-2 h^-1 for NO₂ and 8 g N m^-2 h^-1 for NO. The NO and NO₂ flux rates were significantly reduced on plant covered soil plots. In some cases, the flux rates of both gases became negative indicating that the vegetation may act as a sink for atmospheric NO and NO₂.Application of mineral fertilizers increased the NO and NO₂ emission rates. Highest emission rates were observed for urea followed by NH₄Cl, NH₄NO₃ and NaNO₃. The fertilizer loss rates ranged from 0.1% for NaNO₃ to 5.4% for urea. Vegetation cover substantially reduced the fertilizer loss rate.The total NO _x emission from soil is estimated to be 11 Tg N yr^-1. This figure is an upper limit and includes the emission of 7 Tg N yr^-1 from natural unfertilized soils, 2 Tg N yr^-1 from fertilized soils as well as 2 Tg N yr^-1 from animal excreta. Despite its speculative character, this estimation indicates that NO _x emission by soil is important for tropospheric chemistry especially in remote areas where the NO _x production by other sources is comparatively small.     

Charakteristische Zirkulationstypen in mittleren Breiten der nördlichen Hemisphäre

Zusammenfassung In der vorliegenden Arbeit werden neue Klassifikationsprinzipien für Großwetterlagen entwickelt. Bisher wurde bei Wetterlagenklassifikationen das Druckfeld zugrunde gelegt, wobei quasistationären Druckzentren eine nicht berechtigte Vorrangstellung eingeräumt wurde. In der hier versuchten Klassifikation wird vom Strömungsfeld ausgegangen, das in elementare Formen zerlegt wird. Eine zu diesem Zweck durchgeführte statistische Untersuchung ergab, daß alle im Strömungsfeld auftretenden Zirkulationstypen auf drei Grundformen zurückgeführt werden können. Diese Grundformen sind:Driften, Wellen undWirbel.Die Untersuchung ergab im einzelnen, daß in mittleren Breiten der nördlichen Hemisphäre bei 49% aller untersuchten Fälle Driften, bei 23% Wellen und bei 28% Wirbel auftraten.In der hier durchgeführten Klassifikation wird das Druckfeld durch das Strömungsfeld und der Begriff Großwetterlage durch den umfassenderen Begriff des Zirkulationstyps ersetzt. Damit wird der unberechtigte Vorrang der Druckformen bei der Wetterlagenklassifikation aufgegeben. Die Klassifizierung der Zirkulationstypen ergibt sich schließlich durch Kombination der drei Zirkulationselemente: Drift, Welle und Wirbel.

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Summary New principles of classification for large-scale weather situations are outlined in this paper. Hitherto the pressure-field has been taken as a basis for such classifications by conceding a precedence of an unjustified position to semi-permanent centres of pressure. The new classification starts from the field of large-scale motions, which is dissected in elementary models. A statistical test yielded the possibility to reduce all types of atmospheric circulations in the following three elementary models:drifts, waves andeddies.In detail it was found out, that drifts occur in 49%, waves in 23% and eddies in 28% of all cases investigated.In the new classification the term pressure-field is substituted by field of motion and the expression large-scale weather situation by the more comprehensive conception type of circulation. By that the unjustified priority of pressure-centers in classifying weather situations is abolished. At last the classification of the types of circulation follows from a combination of the three elementary models: drift, wave and eddy.

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résumé La présente étude développe de nouveaux principes de classification des situations météorologiques. Alors que jusqu'ici on s'est fondé sur le champ de pression ce qui conduisait à attribuer aux centres d'action quasi stationnaires un rôle trop important, l'auteur part ici du champ de mouvement décomposé en formes élémentaires. Un examen statistique lui a montré que tous les types de circulation peuvent se ramener à trois formes fondamentales:courants, ondulations ettourbillons.Aux latitudes moyennes de l'hémisphère Nord les courants représentent le 49%, les ondulations le 23% et les tourbillons le 28%.Au champ de pression se substitue donc le champ de courant, et les situations météorologiques se groupent en types de circulation ce qui supprime le rôle prépondérant des formes isobariques. Le classement final des types de circulation résulte de la combinaison des trois types mentionnés:courants, ondulations ettourbillons.

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Mit 15 Textabbildungen     

Characteristics of the ozone decline in the northern polar and middle latitudes during the winter-spring

Summary The total ozone decline during the past twenty years, especially strong during the winter-spring season poleward from 50° N, is well established with known average trends of 5–7% per decade. This study presents a number of additional characteristics such as ozone-mass deficiency (O₃MD) from the pre- 1976 base average, and areal extent with negative deviations greater than2 and3. Gridded satellite data combined with ground-based total ozone maps, permit calculations of daily and regional ozone deficiencies from the anthropogenically undisturbed average ozone levels of the 1960s and early 1970s. Then the quantity of the O₃MD and the changes in surface area, with deficiencies larger than-10 and-15% are integrated for the 1 January to 15 April period for each of the last 20 years, and compared. In addition, the polar vortex extent during the last 10 years is determined using the PV at 475°K. The quantity of the O₃MD within the sunlit part of the vortex is shown to contribute from15 to 35% of the overall ozone deficiency within the-10% contours over the area 35–90°N. The ozone deficiency, integrated for the first 105 days of each year, has increased dramatically from 2,800Mt in the early 1980s to7,800Mt in the 1990s, exceeded 12,000Mt in the winter-springs of 1993 and 1995. The latter quantity is comparable with the average O₃MD over the same Southern latitudes in the last ten austral springs. During the 1990s over the 35–90° latitudes the average ozone deficiency in the Southern hemisphere belt is less than over the Northern hemisphere belt by40%. It is known that the main ozone decline is observed in the lower stratosphere and the ozone loss over the Arctic is very sensitive to decreasing stratospheric temperatures; negative 50hPa monthly anomalies greater than 4°C have occurred during 7 of the springs in the last decade, thus possibly facilitating doubling the area with negative ozone deviations greater than-10% in the 1990s to5,000.10⁶km² and nearly tripling the O₃MD as stated above. The changes in total eddy heat fluxes as a proxy indicator of the long wave perturbations are positively correlated with the ozone deficiency in the 45–75°N. The strong anticorrelation between the ozone deficiency in the region>55° N. versus the 35–50° N belt is discussed in relation to possible transport of air masses with low ozone from the sub-tropics, which in some years are the dominant reason for the observed ozone deficiency.With 11 Figures     

Effects of Temperature and Humidity upon the Entrainment of Sedimentary Particles by Wind

Aeolian transport of sedimentary particles is a well-recognized phenomenon in cold regions, but the effect of low temperature (T) and specific humidity (q) upon particle entrainment has not previously been investigated. This study reports on wind-tunnel experiments (-12 °C T 32 °C, and 1 g kg^-1 q 10 g kg^-1) that suggest the aerodynamic drag required to entrain sand sized particles can be 30% lower in cold or high latitude settings, as compared to hot deserts. For any given regional wind velocity, this effect will increase the wind strength index and thereby the proportion of time a surface is active at low temperature.The influence of air temperature and humidity upon the threshold for particle motion is determined by three physical processes: (1) The effect of air viscosity and density on the fluid drag force acting to dislodge sedimentary particles; (2) the effect of viscosity on the turbulent wake shed from these particles, and the frequency and magnitude of burst-sweep events; and (3) the development of inter-particle cohesion via adsorbed water. This study considers the relative importance of each of these processes. The threshold friction velocity model of Shao and Lu is revised to incorporate the inter-particle force associated with hygroscopic water. It is found to perform well when tested against the experimental data obtained for this study.     

The conductance of a maize crop and the underlying soil to ozone under various environmental conditions

Flux measurements of ozone and water vapour employing the eddy correlation technique were used to determine the surface conductance and canopy conductance to ozone. In the surface conductance to ozone, all surfaces at which ozone is destroyed and the transport process to these surfaces are included. The canopy conductance to ozone represents the ozone uptake of transpiring plant parts. The surface conductance to ozone of the maize crop and the underlying soil was generally larger than the canopy conductance to ozone. This means that beside the uptake by stomata, there was another important ozone sink. Under wet soil surface conditions, the surface conductance and the canopy conductance to ozone coincided. This indicates that the resistance of wet soil and the remaining plant parts (cuticle) to ozone was much larger than the stomatal or soil resistance. On the other hand, under dry soil conditions the conductances differ, largely caused by a variation in the transport process to the soil. The transport of ozone to soil increased with increasing friction velocity (u _*) and decreased with increasing atmospheric stability, leaf area index (LAI) or crop height (h). These effects for midday (unstable) conditions were parameterized with an in-crop aerodynamic resistance,r _inc in a very straightforward way;r _inc=13.9 LAIh/u _*+67 (cc.=0.77). If the ozone flux in air pollution models is described with a simple resistance model (Big Leaf model), the extra destruction at the soil should be modelled using an in-crop aerodynamic resistance. For these measurements the ozone flux to the soil was 0–65% of the total ozone flux measured above the crop. Under wet soil conditions, this was less than 20%; under dry soil conditions, this was 30–65%.     

Toward an improved global network for determination of tropospheric ozone climatology and trends

An examination of typical tropospheric ozone variability on daily, monthly, annual and interannual timescales and instrumental precision indicates that the current ozonesonde network is insufficient to detect a trend in tropospheric ozone of 1% per year at the 2 level even at stations with records a decade in length. From a trend prediction analysis we conclude that in order to detect a 1% per year trend in a decade or less it will be necessary to decrease the time between observations from its present value of 3–7 days to 1 day or less. The spatial distribution of the current ozonesonde stations is also inadequate for determining the global climatology of ozone. We present a quantitative theory taking into account photochemistry, surface deposition, and wind climatology to define the effectively sampled region for an observing station which, used in conjunction with the instrumental precision and the above prediction analysis, forms the basis for defining a suitable global network for determining regional and global ozone climatology and trends. At least a doubling of the present number of stations is necessary, and the oceans, most of Asia, Africa, and South America are areas where more stations are most needed. Differential absorption lidar ozone instruments have the potential for far more frequent measurements of ozone vertical profiles and hence potentially more accurate climatology and trend determinations than feasible with ozonesondes but may produce a (fair weather) biased data set above the cloud base. A strategy for cloudy regions in which either each station utilizes both lidars and sondes or each station is in fact a doublet comprised of a near-sea-level lidar and a proximal-mountain-top lidar could serve to minimize this bias.     

Numerical integration errors in calculated tropospheric photodissociation rate coefficients

Tropospheric photodissociation rate coefficients (J values) were calculated for NO₂, O₃, HNO₂, CH₂O, and CH₃CHO using high spectral resolution (0.1 mm wavelength increments), and compared to the J values obtained with numerically degraded resolution (=1, 2, 4, 6, 8, and 10 nm, and several commonly used nonuniform grids). Depending on the molecule, substantial errors can be introduced by the larger increments. Thus for =10 nm, errors are less than 1% for NO₂, less than 2% for HNO₂, +6.5% to -16% for CH₂O, -6.9% to +24% for CH₃CHO, and -24% to +110% for O₃. The errors for CH₂O arise from the fine structure of its absorption spectrum, and are prevalently negative (underestimate of J). The errors for O₃, and to a lesser extent for CH₃CHO, arise mainly from under-resolving the overlap of the molecular action spectrum and the tropospheric actinic flux in the wavelength region of stratospheric ozone attenuation. The sign of those errors depends on whether the actinic flux is averaged onto the grid before or after the radiative transfer calculation. In all cases studied, grids with 2 nm produced errors no larger than 5%.     

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.     

Carbonyl products of the gas phase reaction of ozone with 1,1-disubstituted alkenes

Carbonyl products have been identified and their formation yields measured in experiments involving the gas phase reaction of ozone with 1,1-disubstituted alkenes at ambient T and p=1 atm. of air. Sufficient cyclohexane was added to scavenge the hydroxyl radical in order to minimize OH-alkene and OH-carbonyl reactions. Formation yields (carbonyl formed/ozone reacted) of primary carbonyls were close to the value of 1.0 that is consistent with the mechanism: O₃+R₁R₂C=CH₂ (HCHO+R₁R₂COO)+(1–)(R₁COR₂+H₂COO) where formaldehyde and the ketone R₁ COR₂ are the primary carbonyls and R₁R₂COO and H₂COO are the corresponding biradicals. Measured values of were 0.58–0.82 and indicate modest preferential formation of formaldehyde and the disubstituted biradical as compared to the ketone and the biradical H₂COO. Carbonyls other than the primary carbonyls were identified. Their formation is discussed in terms of subsequent reactions of the disubstituted biradicals R₁R₂COO. Similarities and differences between disubstituted and monosubstituted biradicals are outlined.     

Preliminary modelling results of an urban air quality model verifying the prediction of nitrogen dioxide, sulfur dioxide and ozone over the Sydney basin

Summary The air quality modelling system (HIRES-AIRCHEM) of The University of New South Wales is tested with regard to forecast distributions of sulfur dioxide (SO₂), nitrogen dioxide (NO₂) and ozone (O₃) over the Sydney basin and surrounding area. This is achieved by assimilating the emissions inventory of the New South Wales State Environment Protection Authority. This inventory contains both road and non-road sources. The HIRES-AIRCHEM system was run over the greater Sydney metropolitan area for a four day period in February 1998. During this period O₃ readings, in particular, exceeded the EPAs threshold maximum of 80ppb. The model forecasts of the NO₂-, SO₂- and O₃-distributions verify well with the EPAs monitored readings. Diurnal concentrations are greatest in the late afternoon, as expected, when photochemical processes are most active. Furthermore, the forecast spatial distribution of NO₂ and SO₂ shows maximum values radiating out along major roads from the Sydney CBD and other population centres. This is consistent with NO₂ and SO₂ being major pollutants associated with vehicular traffic. These promising results have significant implications for possible future use of the system as a tool for routinely assessing air quality.