Surface NO and NO2 mixing ratios measured between 30° N and 30° S in the Atlantic region

Surface NO and NO₂ mixing ratios were measured aboard the research vessel Polarstern during the mission ANT VII/1 from 24 September to 5 October 1988. The measurements were taken along the meridian at 30° W in the Atlantic region covering latitudes between 30° N and 30° S. The average mixing ratios were about 12 pptv NO/30 pptv NO₂ in the Northern Hemisphere and about 7 pptv NO/22 pptv NO₂ in the Southern. Elevated mixing ratios of 20 pptv NO/70 pptv NO₂ were found at 12° N (probably due to air masses originating from the surface of West Africa) and in the region of the ITCZ between 8° N and 5° N. Because of probable contamination by the ship, the measured mixing ratios mostly represent upper limits.     

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.     

High atmospheric NO x levels and multiple photochemical steady states

Previous zero-dimensional photochemical calculations indicate that multiple tropospheric steady states may exist, in which different NO _x (NO+NO₂) levels could be supported by the same source of NO _x . To investigate this possibility more closely, a one-dimensional photochemical model has been used to estimate the rate of removal of atmospheric NO _x compounds at different NO _x levels. At low NO _x levels NO _x is photochemically converted to HNO₃, which is removed by either wet or dry deposition. At high NO _x levels formation of HNO₃ is inhibited, and NO _x is removed by a variety of other processes, including rainout of N₂O₄ and N₂O₅, surface deposition of NO and NO₂, and direct dissolution of NO and NO₂ in rainwater. Multiple steady states are possible if surface deposition of NO _x is relatively inefficient. The NO _x source required to trigger high atmospheric NO _x levels is approximately 10 to 15 times the present global emission rate-less than half the source strength predicted by the zero-dimensional model. NO _x mixing ratios in excess of 10^-7 would cause severe damage to the ozone layer and could result in either a climatic warming or cooling, depending upon the amount of NO₂ present.     

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.     

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.     

Intercomparison of remote measurements of stratospheric NO and NO2

During the 1982 and 1983 Balloon Intercomparison Campaigns, the vertical profile of stratospheric NO₂ was measured remotely by nine instruments and that of NO by two. Total overhead columns were measured by two more instruments. Between 30 and 35km, where measurements overlapped, agreement between NO profiles was within ±30%, which is better than the accuracies claimed by the experimenters. Between 35 and 40km there was similarly good agreement between NO₂ profiles, but below 30km, differences of greater than a factor three were found. In the second Campaign, NO₂ values from most instruments agreed within their quoted errors, except that the Oxford radiometer gave much lower values; but the first Campaign and the column measurements show a more uniform spread of results.These differences below 30km could not be resolved, but new laboratory measurements are planned which should do so.     

Stable Carbon Isotope Ratios and the Photochemical Age of Atmospheric Volatile Organic Compounds

Abstract

The dependence of ozone formation on the mixing ratios of volatile organic compounds (VOCs) and nitrogen oxides (NO_x) has been widely studied. In addition to the atmospheric levels of VOCs and NO_x, the extent of photochemical processing of VOCs has a strong impact on ozone levels. Although methods for measuring atmospheric mixing ratios of VOCs and NO_x are well established and results of those measurements are widely available, determination of the extent of photochemical processing of VOCs, known as photochemical age (PCA), is difficult. In this article a recently developed methodology for the determination of PCA for individual compounds based on the change in their stable carbon isotope composition is used to investigate the dependence between ozone and VOC or NO_x mixing ratios at a rural site in Ontario, Canada, during fall and winter. The results show that under these conditions the variability in VOC mixing ratios is predominantly a result of the varying impact of local emissions and not a result of changes in the extent of atmospheric processing. This explains why the mixing ratio of ozone shows no systematic dependence on the mixing ratios of VOCs or NO_x in this environment and at this time of the year.     

A modified profile method for determining the vertical fluxes of NO,NO2, ozone,and HNO3 in the atmospheric surface layer

A modified profile method for determining the vertical deposition (or/and exhalation) fluxes of NO, NO₂, ozone, and HNO₃ in the atmospheric surface layer is presented. This method is based on the generally accepted micrometeorological ideas of the transfer of momentum, sensible heat and matter near the Earth's surface and the chemical reactions among these trace gases. The analysis (aerodynamic profile method) includes a detailed determination of the micrometeorological quantities (such as the friction velocity, the fluxes of sensible and latent heat, the roughness length and the zero plane displacement), and of the height-invariant fluxes of the composed chemically conservative trace gases with group concentrations c ₁=[NO]+[NO₂]+[HNO₃], c ₂=[NO₂]+[O₃]+3/2·[HNO₃], and c ₃=[NO]–[O₃]–1/2·[HNO₃]. The fluxes of the individual species are finally determined by the numerical solution of a system of coupled nonlinear ordinary differential equations for the concentrations of ozone and HNO₃ (decoding method). The parameterization of the fluxes is based on the flux-gradient relationships in the turbulent region of the atmospheric surface layer. The model requires only the vertical profile data of wind velocity, temperature and humidity and concentrations of NO, NO₂, ozone, and HNO₃.The method has been applied to vertical profile data obtained at Jülich (September 1984) and collected in the BIATEX joint field experiment LOVENOX (Halvergate, U.K., September 1989).     

The role of precursor emissions on ground level ozone concentration during summer season in Poland

Three online coupled chemical transport model simulations were analyzed for three summer months of 2015 in Poland. One of them was run with default emission inventory, the other two with NO_x and VOC emissions reduced by 30%, respectively. Obtained ozone concentrations were evaluated with data from air quality measurement stations and ozone sensitivity to precursor emissions was estimated by ozone concentration differences between simulations and with the use of indicator ratios. They were calculated based on modeled mixing ratios of ozone, total reactive nitrogen and its components, nitric acid and hydrogen peroxide. The results show that the model overestimates ozone concentrations with the largest errors in the morning and evening, which is primarily related to the way vertical mixing is resolved by the model. Better model performance for ozone is achieved in rural than urban environment, as PBL and mixing mechanisms play more significant role in urban areas. Modeled ozone shows mixed sensitivity to precursor concentrations, similarly to other European regions, but indicator ratios have different values than are found in literature, particularly H₂O₂/HNO₃ is larger than in southern Europe. However, indicator ratios often differ between locations and transition values need to be established individually for a given region.     

Evaluation of a catalytic reduction technique for the measurement of total reactive odd-nitrogen NO y in the atmosphere

A catalytic reduction technique for the measurement of total reactive odd-nitrogen NO _y in the atmosphere was evaluated in laboratory and field tests. NO _y component species include NO, NO₂, NO₃, HNO₃, N₂O₅, CH₃COO₂NO₂(PAN), and particulate nitrate. The technique utilizes the reduction of the higher oxides to NO in reaction with CO on a metal catalyst and the subsequent detection of NO by chemiluminescence produced in reaction with O₃. The efficiency and linearity of the conversion of the principal NO _y species were examined for mixing ratios in the range of 0.1 to 100 parts per billion by volume (ppbv). Results of tests with Au, Ni, and stainless steel as the catalyst in the temperature range of 25–500°C showed Au to be the preferred catalyst. NH₃, HCN, N₂O, CH₄, and various chlorine and sulfur compounds were checked as possible sources of NO _y interference with the Au catalyst. The effects of pressure, O₃, and H₂O on NO _y conversion were also examined. The results of the checks and tests in the laboratory showed the technique to be suitable for initial NO _y measurements in the atmosphere. The technique was subsequently tested in ambient air at a remote ground-based field site located near Niwot Ridge, Colorado. The results of conversion and inlet tests made in the field and a summary of the NO _y data are included in the discussion.     

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.     

Solar eclipse-induced variations in solar flux, j(NO2) and surface ozone at Kannur, India

Surface ozone is mainly produced by the photodissociation of nitrogen dioxide (NO₂) by solar UV radiation. Subsequently, solar eclipses provide one of the unique occasions to explore the variations in the photolysis rate of NO₂ and their significant impact on the production of ozone at a location. This study aims to examine the diurnal variations in the photodissociation rate coefficient of NO₂, (j(NO₂*)), and mixing ratios of surface ozone and NO _X * (NO?+?NO₂*) during the solar eclipse that occurred on 15 January 2010 at Kannur (11.9°N, 75.4°E, 5?m amsl), a tropical coastal site on the Arabian Sea in South India. This investigation was carried out on the basis of the ground level observations of surface ozone and its prominent precursor NO₂*. The j(NO₂*) values were estimated from the observed solar UV-A flux data. A sharp decline in j(NO₂*) and surface ozone was observed during the eclipse phase because of the decreased efficiency of the ozone formation from NO₂. The NO₂* levels were found to increase during this episode, whereas the NO levels remained unchanged. The surface ozone concentration was reduced by 57.5%, whereas, on the other hand, that of NO _X * increased by 62.5% during the solar eclipse. Subsequently a reduction of *% in the magnitude of j(NO₂*) was found here during the maximum obscuration. Reductions in solar insolation, air temperature and wind speed were also observed during the solar eclipse event. The relative humidity showed a 6.4% decrease during the eclipse phase, which was a unique observation at this site.     

In Situ Trace Gas and Particle Measurements in the Summer Lower Stratosphere during STREAM II: Implications for O3 Production

In situ aircraft measurements of O₃, CO,HNO₃, and aerosol particles are presented,performed over the North Sea region in the summerlower stratosphere during the STREAM II campaign(Stratosphere Troposphere Experiments by AircraftMeasurements) in July 1994. Occasionally, high COconcentrations of 200-300 pbbv were measured in thelowermost stratosphere, together with relatively highHNO₃ concentrations up to 1.6 ppbv. The particlenumber concentration (at standard pressure andtemperature) between 0.018-1 m decreased acrossthe tropopause, from >1000 cm^-3 in the uppertroposphere to <500 cm^-3 in the lowermoststratosphere. Since the CO sources are found in thetroposphere, the elevated CO mixing ratios areattributed to mixing of polluted tropospheric air intothe lowermost extratropical stratosphere. Further wehave used a chemical model to illustrate that nitrogenoxide reservoir species (mainly HNO₃) determinethe availability of NO_x (=NO + NO₂) andtherefore largely control the total net O₃production in the lower kilometers of thestratosphere. Model simulations, applying additionalNO_x perturbations from aircraft, show that theO₃ production efficiency of NO_x is smallerthan previously assumed, under conditions withrelatively high HNO₃ mixing ratios, as observedduring STREAM II. The model simulations furthersuggest a relatively high O₃ productionefficiency from CO oxidation, as a result of therelatively high ambient HNO₃ and NO_xconcentrations, implying that upward transport of COrich air enhances O₃ production in the lowermoststratosphere. Analysis of the measurements and themodel calculations suggest that the lowermoststratosphere is a transition region in which thechemistry deviates from both the upper troposphere andlower stratosphere.     

Study of Ozone and NO2 over Gadanki – a rural site in South India

We have studied long-term changes in tropospheric NO₂ over South India using ground-based observations, and GOME and OMI satellite data. We have found that unlike urban regions, the region between Eastern and Western Ghat mountain ranges experiences statistically significant decreasing trend. There are few ground-based observatories to verify satellite based trends for rural regions. However, using a past study and recent measurements we show a statistically significant decrease in NO_X and O₃ mixing ratio over a rural location (Gadanki; 13.48° N, 79.18° E) in South India. In the ground-based records of surface NO_X, the concentration during 2010–11 is found to be lower by 0.9 ppbv which is nearly 60 % of the values observed during 1994–95. Small but statistically significant decrease in noon-time peak ozone concentration is also observed. Noon-time peak ozone concentration has decreased from 34?±?13 ppbv during 1993–96 to 30?±?15 ppbv during 2010–11. NO_X mixing ratios are very low over Gadanki. In spite of low NO_X values (0.5 to 2 ppbv during 2010–11), ozone mixing ratios are not significantly low compared to many cities with high NO_X. The monthly mean ozone mixing ratio varies from 9 ppbv to 37 ppbv with high values during Spring and low values during late Summer. Using a box-model, we show that presence of VOCs is also very important in addition to NO_X in determining ozone levels in rural environment and to explain its seasonal cycle.     

The equilibrium constant of NO2 with N2O4 and the temperature dependence of the visible spectrum of NO2: A critical review and the implications for measurements of NO2 in the polar stratosphere

Measurements of stratospheric NO₂ by ground-based visible spectrometers rely on laboratory measurements of absorption cross-sections. We review low-temperature laboratory measurements, which disagree by amounts claimed to be significant. Our recalculation of their errors shows that in general disagreements are not significant and that errors in the ratios of cross-sections at low to room temperature are between ±3% and ±8.8%. Of these errors, up to ±3.5% was contributed by errors in the equilibrium constant,K _p, in those measurements where the pressure was above 0.1 mbar.We review measurements and calculations ofK _p, which were accurate to ±5% from 300 to 233 K. Each method was potentially flawed. For example, infrared measurements of the partial pressure of NO₂ ignored the dependence of absorption on total pressure. From thermodynamic theory, formulae forK _pcan be derived from expressions for the variation of heat capacity with temperature. Contrary to common belief, coefficients in the formulae used by spectroscopists were not derived from the thermodynamic quantities. Rather, they were fitted to measurements or to calculations. Hence, they are empirical and it is dangerous to extrapolate below 233 K, the lowest temperature of the measurements.There are no measurements of NO₂ cross-sections below 230 K. Extrapolation of these cross-sections to analysis of measurements of NO₂ at the low temperatures of the Arctic and Antarctic stratosphere is also dangerous. For satisfactory analysis of polar spectra, the NO₂ cross-sections should be measured at temperatures down to 190 K with a relative accuracy of ±1%. This difficult experiment would need a cell of minimum length 32 m whose length can be adjusted. Because their effects are circular, many errors cannot be removed simply. Although circular errors also arise in the measurements ofK _pand of the infrared spectrum, their weights differ from those in the visible spectrum. The optimum experiment might therefore simultaneously measure the visible and infrared spectra andK _p.     

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.     

Flux between soil and atmosphere, vertical concentration profiles in soil, and turnover of nitric oxide: 2. Experiments with naturally layered soil cores

Intact soils cores were taken with a stainless steel corer from a sandy podzol and a loamy luvisol, and used to measure the flux (J) of NO between soil and atmosphere and the vertical profile of the NO mixing ratios (m) in the soil atmosphere, both as function of the NO mixing ratio (m _a) in the atmosphere of the headspace. These measurements were repeated after stepwise excavation of the soil column from the top, e.g. by removing the upper 2 cm soil layer. The gaseous diffusion coefficients of NO in the soil cores were either computed from soil porosity or were determined from experiments using SF6. The NO fluxes (J) that were actually measured at the soil surface were compared to the fluxes which were calculated either from the vertical NO profiles (J _c ) or from the NO production and uptake rates (J _m ) determined in the excavated soil samples. In the podzol, the actually measured (J) and the calculated (J _m , J_m) NO fluxes agreed within a factor of 2. In the luvisol, the measured NO fluxes (J) and those calculated from the vertical NO profiles (J _c ) also agreed well, but in the upper 6 cm soil layer the NO fluxes (J _m ) calculated from NO production and uptake rates were up to 7 times higher than the measured NO fluxes. This poor agreement was probably due to the inhomogeneous distribution of NO production and consumption processes and the change of diffusivities within the top layers of the luvisol. Indeed, the luvisol showed a pronounced maximum of the NO mixing ratios at about 6 cm depth, whereas the podzol column exhibited a steady and exponential decrease of the NO mixing ratios with depth. The inhomogeneities in the luvisol were confirmed by incubation of the soil cores under anoxic conditions. This treatment resulted in production of NO at several depths indicating a zonation of increased potential activities within the luvisol profile which may have biased the modelling of the NO surface flux from turnover measurements in soil samples. Inhomogeneities could be achieved even in homogenized soil by fertilization with nitrate solution.     

Verification of the Contribution of Vehicular Traffic to the Total NMVOC Emissions in Germany and the Importance of the NO3 Chemistry in the City Air

In 1997 and 1998 several field campaigns for monitoring non-methane volatile organic compounds (NMVOCs) and nitrogen oxides (NO_x) were carried out in a road traffic tunnel and in the city center of Wuppertal, Germany. C₂–C₁₀ aliphatic and aromatic hydrocarbons were monitored using a compact GC instrument. DOAS White and long path systems were used to measure aromatic hydrocarbons and oxygenated aromatic compounds. A formaldehyde monitor was used to measure formaldehyde. Chemiluminescence NO analysers with NO₂ converter were used for measuring NO and NO₂. The high mixing ratios of the NMVOCs observed in the road traffic tunnel, especially 2.9 ppbv phenol, 1.5ppbv para-cresol and 4.4 ppbv benzaldehyde, in comparison with themeasured background concentration clearly indicate that these compounds were directly emitted from road traffic. Para-Cresol was for the first timeselectively detected as primary pollutant from traffic. From the measured data a NMVOC profile of the tunnel air and the city air, normalised to benzene (ppbC/ppbC), was derived. For most compounds the observed city air NMVOC profile is almost identical with that obtained in the traffic tunnel. Since benzene originates mainly from road traffic emission, the comparison of the normalised emission ratios indicate that the road traffic emissions in Wuppertal have still the largest impact on the city air composition, which is in contrast to the German emission inventory. In both NMVOC profiles, aromatic compounds have remarkably large contributions of more than 40 ppbC%. In addtion, total NMVOC/NO_x ratios from 0.6 up to 3.0ppbC/ppb in the traffic tunnel air and 3.4± 0.5 in the city air of Wuppertal were obtained. From the observed para-cresol/toluene and ortho-cresol/toluene ratios in the city air, evidence was found thatalso during daytime NO₃ radical reactions play an important role in urban air.     

An analytic formulation for NO and NO2 flux profiles in the atmospheric surface layer

The chemical reactivity of NO and NO₂ is so rapid that their fluxes and concentrations can be considerably modified from that expected for conserved variables in the atmospheric surface layer, even as low as a meter above the surface. Fitzjarrald and Lenschow (1983) have calculated flux and mean concentration profiles for NO, NO₂ and O₃ in the surface layer using numerical techniques. However, their solutions do not approach the photostationary state at large heights. Here we solve a simpler set of equations analytically (i.e. we assume a constant O₃ concentration and neutral hydrodynamic stability), and are able to show how the flux profiles behave at large heights assuming that the concentrations approach their photostationary values. We find, for example, that at large heights the ratio of the flux of NO to that of NO₂ is equal to the ratio of their concentrations. These results are relevant to estimating surface fluxes of NO and NO₂, and are most applicable to nonurban environments where NO and NO₂ concentrations are usually much less than O₃ concentration.The National Center for Atmospheric Research is sponsored by the National Science Foundation.     

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.