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.     

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.     

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.     

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.     

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.     

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.     

High-Latitude Springtime Photochemistry. Part Ii: Sensitivity Studies of Ozone Production

A seven-year record of surface ozone measurements from Denali NationalPark, Alaska shows a persistent spring maximum. These data, combined withmeasurements of NO_x, hydrocarbons, O₃, and PANfrom a continental site in Alaska during the spring of 1995 are used as thebasis for a sensitivity study to explore tropospheric photochemistry in thisregion. Because of the relatively high concentrations of NO_x(mean of 116, median of 91 pptv), the net tendency was for photochemicalozone production. The range of net O₃ production for averageconditions measured at this site during spring is between 0.96–3.9ppbv/day depending on the assumptions used; in any case, this productionmust contribute to the observed springtime maximum in O₃.Model calculations showed that of the anthropogenic ozone precursors, onlyNO_x had a strong effect on the rate of ozone production; themeasured concentrations of anthropogenic hydrocarbons did not significantlyaffect the ozone budget. Naturally produced biogenic hydrocarbons, such asisoprene, may also have a significant effect on ozone production, even atconcentrations of a few 10's of pptv. An observed temperature-isoprenerelationship from a boreal site in Canada indicates that isoprene may bepresent during the Alaskan spring. Measurements of isoprene taken duringthe spring of 1996 suggest that reactive biogenic hydrocarbon emissionsbegin before the emergence of leaves on deciduous trees and that theconcentrations were sufficient to accelerate ozone production.     

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.     

Reactive Nitrogen Compounds at Spitsbergen in the Norwegian Arctic

Simultaneousindependent measurements of NO_y and NO_x(NO_x= NO + NO₂) by high-sensitivitychemiluminescence systems and of PAN (peroxyacetylnitrate) and PPN (peroxypropionyl nitrate) by GC-ECDwere made at Spitsbergen in the Norwegian Arcticduring the first half year of 1994. The average mixingratio of the sum of PAN and PPN (denoted PANs)increased from around 150 pptv in early winter to amaximum of around 500 pptv in late March, whereasepisodic peak values reached 800 pptv. This occurredsimultaneously with a maximum in ozone which increasedto 45–50 ppbv in March–April. The average NO_xmixing ratio was 27 pptv and did not show any cyclethrough the period. The NO_y mixing ratio showeda maximum in late March, while the difference betweenNO_y and PAN decreased during spring. This is anindication of the dominance of PAN in the NO_ybudget in the Arctic, but possible changes in theefficiency of the NO_y converter could alsocontribute to this. Although most PAN in theArctic is believed to be due to long range transport,the observations indicate local loss and formationrates of up to 1–2 pptv h^-1 in April–May.Measurements of carbonyl compounds suggest thatacetaldehyde was the dominant, local precursor ofPAN.Now at 1.     

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     

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.     

Aircraft measurements of oxides of nitrogen along the eastern rim of the Asian continent: Winter observations

Aircraft observations of oxides of nitrogen (NO _y ), measured with a ferrous sulfate converter, over the sea surrounding the Japanese islands (30–43° N, 131–141° E) were carried out in the winter of 1983 and 1984 at altitudes mostly between 3 and 8 km. NO _y defined here is the sum of NO, NO₂, and other unstable oxides of nitrogen that are converted to NO by ferrous sulfate. The main observations were:

1. Over the Pacific Ocean between the latitudes of 30–35° N, the observed NO _y mixing ratio between 3 and 8 km was a fairly constant 200 pptv. The NO mixing ratio increased with altitude from 15 pptv at 3 km to 35 pptv at 7 km.
2. Over the Sea of Japan, tropospheric NO _y mesured between 1 and 6 km started increasing with latitude North of 35° N and reached about 1000 pptv at 40° N.
3. NO _y was measured in an air mass transported from the stratosphere near a tropopause fold region. When the ozone mixing ratio was between 80 and 140 ppbv, the NO _y mixing ratio was about 200 pptv.

     

Measurements of Photolyzable Halogen Compounds and Bromine Radicals During the Polar Sunrise Experiment 1997

As part of the Polar Sunrise Experiment (PSE) 1997, concentrations of halogen species thought to be involved in ground level Arctic ozone depletion were made at Alert, NWT, Canada (82.5°N, 62.3°W) during the months of March and April, 1997. Measurements were made of photolyzable chlorine (Cl₂ and HOCl) and bromine (Br₂ and HOBr) using the Photoactive Halogen Detector (PHD), and bromine radicals (BrO_x) using a modified radical amplifier. During the sampling period between Julian Day 86 (March 27) and Day 102 (April 12), two ozone depletion episodes occurred, the most notable being on days 96-99, when ozone levels were below detectable limits (1 ppbv). Concentrations of BrO_x above the 4 pptv detection limit were found for a significant part of the study, both during and outside of depletion events. The highest BrO_x concentrations were observed at the end of the depletion event, when the concentration reached 15 pptv. We found substantial amounts of Br₂ in the absence of O₃, indicating that O₃ is not a necessary requirement for production of Br₂. There is also Br₂ present when winds are from the south, implying local scale (e.g. from the snowpack) production. During the principal O₃ depletion event, the HOBr concentration rose to 260 pptv, coincident with the BrO_x maximum. This implies a steady state HO₂ concentration of 6 pptv. During a partial O₃ depletion event, we estimate that the flux of Br₂ from the surface is about 10 times greater than that for Cl₂.     

Numerical Investigation of the Influence of Mineral Dust on the Tropospheric Chemistry of East Asia

An investigation of the influence of mineral dust ontrace gas cycles in the troposphere is carried out inthis study. A 3D regional scale atmospheric chemistrymodel (STEM-III) which includes aerosol processes isused for the numerical simulations for May 1987.Heterogeneous interactions between gaseous species(SO₂, N₂O₅, HNO₃, HO₂andH₂O₂) and the dust particles are considered.Emissions of dust behind convective cold fronts aremodeled. The transport and distribution of mineraldust predicted from the model is compared withsatellite measurements (aerosol index from TOMS). Themodel is shown to capture the synoptic variability inthe observed aerosol index. Calculations show twomajor dust events in May 1987, during which thedust levels close to the source reach more than500 g/m³. The transport of dust is mostlyrestricted towards the north, with the net continentaloutflow of 6 Tg for the entire month. Results showthat the presence of mineral aerosol can greatlyimpact sulfate and nitrate distributions. Averagedover the month of May, the presence of dust isestimated to increase particulate sulfate and nitratelevels in east Asia by 40%. Furthermore, the sulfateand nitrate on the dust particles are predicted to beassociated with the coarse mode (3–5 m particlediameter), consistent with observations over Japan.The influence of mineral dust on the photochemicaloxidant cycle is also investigated. For the entiremonth, a5–10% decrease in boundary layer ozone ispredicted by the model closer to regions of higherdust levels. The ratio of nitric acid to NO_x overmarine regions is reduced by a factor between 1 and 2in the boundary layer to more than 2 in the freetroposphere as a result of aerosol processes.     

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.     

Measurements of Volatile Organic Compounds (VOC) During POPCORN 1994: Applying a New On-Line GC–MS-Technique

Atmospheric concentrations of ca. 250 C6–C15 hydrocarb on and C4–C12 oxygenated volatile organic compounds (VOC) including alkanes, benzene and alkyl benzenes, monoterpenes and aldehydes were measured in August 1994 during the POPCORN campaign (POPCORN = Photo-Oxidant formation by Plant emitted Compounds and OH Radicals in North-Eastern Germany). About 80 substances together contributed 90% of the atmospheric carbon in this range of molecular weight. During this field campaign VOC-emissions from several crop and tree species and the ambient concentrations of CO, C2–C7 non-methane hydrocarbons (NMHC), C1 and C2 aldehydes, nitrogen oxides, ozone and hydroxyl-radicals (OH) were also measured. These data were used to interpret the VOC measurements presented here. The on-line GC–MS used for the VOC measurements combines adsorptive sampling with thermal desorption and GC–MS analysis in an automated system. Internal standards were used to quantify the measurements. Ozone was destroyed prior to the sample preconcentration through the gas phase reaction with NO. Aromatic compounds like benzene, toluene and xylenes were the most abundant compound class among the measured substances, -pinene and 3-carene, most probably originating from pineforests ca. 1 km away from the measuring site, were the most abundant monoterpenes. The highest mixing ratios of most compounds were measured in nights with strong inversion situations. The toluene mixing ratios then reached 630 pptv; -pinene mixing ratios went up to 430 pptv. The median of all toluene and -pinene measurements during the campaign was 125 pptv or 22 pptv, respectively. These values are on the lower end of ambient measurements reported for continental sites. In most samples also n-pentanal, n-hexananl, n-nonanal and n-undecanal were present. Median mixing ratios were 9, 16, 14 and 8 pptv, respectively. Emission studies indicate that these highly reactive compounds are most probably emitted from maize. It is shown by a simple first order approach that the potential for ozone formation during the POPCORN campaign was roughly equal for anthropogenic and biogenic VOC. From measured concentrations of ozone, OH-radicals, methane, CO, C2–C15 nonmethane hydrocarbons (NMHC) and C5–C11 aldehydes a photochemical production of ozone in the order of 3.5 ppb/h can be estimated. Apart from formaldehyde and acetaldehyde, which are at least partly products of VOC oxidation, the substance group with the largest contribution to the VOC turnover are the monoterpenes. They contribute ca. 30%. However, the mechanism of terpene oxidation is very complex and presently only partly understood. Thus the actual contribution of monoterpenes to ozone formation is very uncertain. Other measured compound classes such as light alkenes, alkanes, aromatics, and C5–C11 aldehydes contribute each between 10% and 15% to ozone formation. The measuring site was not influenced directly from strong biogenic or anthropogenic sources, and the results obtained during the POPCORN campaign can be regarded as a typical picture of a remote rural central European environment.