Ozone production due to emissions from vegetation burning

Ozone has been observed in elevated concentrations by satellites over areas previously believed to be background. There is meteorological evidence, that these ozone plumes found over the Atlantic Ocean originate from vegetation fires on the African continent.In a previous study (DECAFE-88), we have investigated ozone and assumed precursor compounds over African tropical forest regions. Our measurements revealed large photosmog layers at altitudes from 1.5 to 4 km. Both chemical and meteorological evidence point to savanna fires up to several thousand km upwind as sources.Here we describe ozone mixing ratios observed over western Africa and compare ozone production ratios from different field measurement campaigns related to vegetation burning. We find that air masses containing photosmog ingredients require several days to develop their oxidation potential, similar to what is known from air polluted by emissions from fossil fuel burning. Finally, we estimate the global ozone production due to vegetation fires and conclude that this source is comparable in strength to the stratospheric input.     

Diffuse radiation,twilight, and photochemistry — I

A photochemical scheme which includes a detailed treatment of multiple scattering up to solar zenith angles of 96° (developed for use in a GCM) has been used to study partitioning within chemical families. Attention is drawn to the different zenith angle dependence of diffuse radiation for the two spectral regions <310 nm and >310 nm. The effect that this has on the so-called 40 km ozone problem is discussed. The importance of correctly including multiple scattering for polar ozone studies is emphasised.     

Relative optical mass functions for air, water vapour, ozone and nitrogen dioxide in atmospheric models presenting different latitudinal and seasonal conditions

Summary A study of the dependence features of the relative optical mass functions for air, water vapour, ozone and nitrogen dioxide on the apparent solar zenith angle was performed by calculating these optical parameters by means of the well-known computer code LOWTRAN 7 at several values of and for nine atmospheric models characterized by different latitudes and seasons. Moreover, other investigations were performed on the dependence features of (i) the relative optical air mass on the thermal characteristics of the low troposphere, (ii) the relative optical water vapour mass on the vertical distribution characteristics of absolute humidity in the troposphere, and (iii) the relative optical mass function for ozone and nitrogen dioxide on the shape characteristics of the vertical profiles of the two gaseous concentrations and the concentration peak altitudes. The results are compared with the values given by the two simple formulas proposed by Kasten (1966) for air and water vapour and the formulas defined by Young (1969) and Staehelin et al. (1995) for ozone and nitrogen dioxide. From this comparison, a wide set of correction factors were obtained which can be conveniently used in the analysis of multispectral sun-radiometric measurements for calculating, with a very high precision, the values of the four optical mass functions at all the angles in the 0° to 87° range, corresponding to the various latitudinal and seasonal conditions described by the nine atmospheric models.With 9 Figures     

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.     

Climatology of Ozone, PAN, CO, and NMHC in the Free Troposphere Over the Southern North Atlantic

Free tropospheric measurements of ozone, peroxyacetylnitrate andprecursors (CO, NMHC) that were made within the framework of the EUROTRACsub-project TOR (Tropospheric Ozone Research) between 1990 and 1995 at theGAW station Izana, Tenerife (28°18N, 16°30W) arediscussed. The average annual cycles reveal the importance of transport fromnorthern mid-latitudes and the role of photo-chemistry. According toair-mass trajectories, which were supplied to us from AEROCE(Atmosphere/Ocean Chemistry Experiment), transport from northernmid-latitudes is associated with high precursor concentrations in winter,whereas ozone concentrations in winter are not much influenced by transportpatterns, suggesting a rather uniform distribution over the northern part ofthe Northern Hemisphere around mean value of 43 ± 5 ppb. In summer,high ozone concentrations of up to 90 ppb are often encountered duringtransport from north, while the levels of precursors are much lower than inwinter, because of photochemical destruction. Trajectories from southerlylatitudes and the Sahara usually have the lowest ozone concentrationsassociated with them.     

Reactions of alkoxy radicals under atmospheric conditions: The relative importance of decomposition versus reaction with O2

The reactions of alkoxy radicals determine to a large extent the products formed during the atmospheric degradations of emitted organic compounds. Experimental data concerning the decompositions, 1,5-H shift isomerizations and reactions with O₂ of several classes of alkoxy radicals are inconsistent with literature estimations of their absolute or relative rate constants. An alternative, although empirical, method for assessing the relative importance under atmospheric conditions of the reactions of alkoxy radicals with O₂ versus decomposition was derived. This estimation method utilizes the differences in the heats of reaction, (H)=(H_{decomposition}–H_{O 2 reaction}), between these two reactions pathways. For (H)[22–0.5(H_{O 2 reaction})], alkoxy radical decomposition dominates over the reaction with O₂ at room temperature and atmospheric pressure of air, while for (H)[25-0.5(H_{O 2 reaction})], the O₂ reaction dominates over decomposition (where the units of H are in kcal mol^–1). The utility and shortcomings of this approach are discussed. It is concluded that further studies concerning the reactions of alkoxy radicals are needed.     

Averaging Intervals For Spectral Analysis Of Nonstationary Turbulence

We formulate a method for determining the smallest time interval Tover which a turbulence time series can be averaged to decompose it intoinstantaneous mean and random components. From the random part the method defines the optimal interval (or averaging window) AW over which this part should be averaged to obtain the instantaneous spectrum. Both T and AW vary randomly with time and depend on physical properties of the turbulence. T also depends on the accuracy of the measurements and is thus independent of AW. Interesting features of the method are its real-time capability and the non-equality between AW and T.     

Nitrate in the atmospheric boundary layer of the tropical South Pacific: Implications regarding sources and transport

Weekly bulk aerosol samples collected at Funafuti, Tuvalu (8°30S, 179°12E), American Samoa (14°15S, 170°35W), and Rarotonga (21°15S, 159°45W), from 1983 through most of 1987 have been analyzed for nitrate and other constituents. The mean nitrate concentration is about 0.11 g m^–3 at each of these stations: 0.107±0.011 g m^–3 at Funafuti; 0.116±0.008 at American Samoa; and 0.117±0.010 at Rarotonga. Previous measurements of mineral aerosol and trace metal concentrations at American Samoa are among the lowest ever recorded for the near-surface troposphere and indicate that this region is minimally affected by transport of soil material and pollutants from the continents. Consequently, the nitrate concentration of 0.11 g m^–3 can be regarded as the natural level for the remote marine boundary layer of the tropical South Pacific Ocean. In contrast, over the tropical North Pacific which is significantly impacted by the transport of material from Asia and North America, the mean nitrate concentrations are about three times higher, 0.29 and 0.36 g m^–3 at Midway and Oahu, respectively. The major sources of the nitrate over the tropical South Pacific are still very uncertain. A very significant correlation between the nitrate concentrations at American Samoa and the concentrations of ²¹⁰Pb suggests that transport from continental sources might be important. This continental source could be lightning, which occurs most frequently over the tropical continents. A near-zero correlation with ⁷Be indicates that the stratosphere and upper troposphere are probably not the major sources. A significant biogenic source would be consistent with the higher mean nitrate concentrations, 0.16 to 0.17 g m^–3, found over the equatorial Pacific at Fanning Island (3°55N, 159°20W) and Nauru (0°32S, 166°57E). The lack of correlation between nitrate and nss sulfate at American Samoa does not necessarily preclude an important role for marine biogenic sources.     

Effects of heat and water vapor transport on eddy covariance measurement of CO2 fluxes

Flux densities of carbon dioxide were measured over an arid, vegetation-free surface by eddy covariance techniques and by a heat budget-profile method, in which CO₂ concentration gradients were specified in terms of mixing ratios. This method showed negligible fluxes of CO₂, consistent with the bareness of the experimental site, whereas the eddy covariance measurements indicated large downward fluxes of CO₂. These apparently conflicting observations are in quantitative agreement with the results of a recent theory which predicts that whenever there are vertical fluxes of sensible or latent heat, a mean vertical velocity is developed. This velocity causes a mean vertical convective mass flux (= _cw for CO₂, in standard notation). The eddy covariance technique neglects this mean convective flux and measures only the turbulent flux _c w. Thus, when the net flux of CO₂ is zero, the eddy covariance method indicates an apparent flux which is equal and opposite to the mean convective flux, i.e., _c w = – _c w. Corrections for the mean convective flux are particularly significant for CO₂ because _cw and _c w are often of similar magnitude. The correct measurement of the net CO₂ flux by eddy covariance techniques requires that the fluxes of sensible and latent heat be measured as well.     

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.     

Measurements of solar radiation and estimation of optical depth in the high Andes of Peru

Summary During an expedition to the high Andes of Southern Peru in June–July 1977, measurements of direct solar radiation in four spectral bands (0.270–0.530–0.630–0.695–2.900 ) were conducted at six sites in elevations ranging from sea level to 5645 m. These measurements were evaluated in Langley plots to determine total optical depths () and irradiances at the top of the atmosphere. In addition, water vapor optical depths (_wv) were calculated from the mean radiosounding over Lima during the expedition, and Rayleigh (_ray) and ozone (_oz) optical depths were obtained from published tabulations. Subtracting _ray, _oz, and _wv from yielded estimates of aerosol optical depth _aer. The components _ray and _oz decrease from the shorter towards the longer wavelength bands and from the lower towards the higher elevation sites; _aer also decreases towards the higher elevations. Particularly pronounced is the decrease of _aer and from the lowlands of the Pacific coast to the highlands of the interior, reflecting the effect of a persistent lower-tropospheric inversion and the contrast from the marine boundary layer to the clear atmosphere of the high Andes.With 4 Figures     

On the Response of the Greenland Ice Sheet to Greenhouse Climate Change

Numerical computations are performed with the three-dimensional polythermal ice-sheet model SICOPOLIS in order to investigate the possible impact of a greenhouse-gas-induced climate change on the Greenland ice sheet. The assumed increase of the mean annual air temperature above the ice covers a range from T = 1°C to 12°C, and several parameterizations for the snowfall and the surface melting are considered. The simulated shrinking of the ice sheet is a smooth function of the temperature rise, indications for the existence of critical thresholds of the climate input are not found. Within 1000 model years, the ice-volume decrease is limited to 10% of the present volume for T 3°C, whereas the most extreme scenario, T = 12°C, leads to an almost entire disintegration, which corresponds to a sea-level equivalent of 7 m. The different snowfall and melting parameterizations yield an uncertainty range of up to 20% of the present ice volume after 1000 model years.     

Estimating product yields of carbon-containing products from the atmospheric photooxidation of ambient air alkenes

The yields of products have been calculated for the reactions of hydroxyl radicals and ozone with 19 of the two-through-six carbon anthropogenic alkenes. Based on their rate of reaction, mechanisms of reactions and the ambient air distribution for these alkenes their seasonal ambient air yields have been estimated.Aldehydes predominate as products irrespective of season, with smaller yields of several ketones. Other minor products include carboxylic acids, carbon monoxide, carbon dioxide, and alkenes. About a two-fold increase is estimated in the yields of hot biradicals and their products from summer to winter.One sensitivity analysis was made by recomputing yields at a different OH radical to O₃ concentration than assumed most likely in the calculations discussed above. In addition, the sensitivity of product yields to an estimated range of seasonally averaged sunset-to-sunrise NO₃ radical concentrations was calculated. The effects of free radical reactions are discussed, but these are believed to make a relatively minor contribution within the NO _x -rich atmospheres that contain anthropogenic alkenes.The uncertainties in product yields associated with the range of NO₃ radical concentrations assumed present is relatively small for aldehydes, as is the decrease in yield of the one carbon hot biradical. Larger uncertainties occur for ketones. Significant decreases in yields occur for larger hot biradicals, especially the branched-chain hot radicals in the presence of NO₃ radicals.     

Stable boundary layers: Observations,models and variability part I: Modelling and measurements

Selected field measurements of evening stable boundary layers are presented in detail comparable with published Large Eddy Simulation results. Such models appear to match idealized theories more closely than do some boundary-layer observations. Any attempt to compare detailed observations with idealized models therefore highlights the variability of the real boundary layer.Here direct turbulence measurements across the stable boundary layer from a heterogeneous and an ideal site are contrasted. Recommendations are made for the information needed to distinguish heterogeneous and ideal cases.The companion paper (Part II) discusses further the issues of data, analysis in the presence of variability, and the effects of averaging over heterogeneous terrain.Part of UK Meteorological Office Atmospheric Process Research Division.     

AN E – ε – ℓ TURBULENCE CLOSURE SCHEME FOR PLANETARY BOUNDARY-LAYER MODELS: THE NEUTRALLY STRATIFIED CASE

The standard E – model generates aplanetary boundary layerthat appears to be much too deep. The cause of theproblem is traced to the equation for the dissipationrate () of turbulent kinetic energy (E), specifically theparameterization of dissipation production anddestruction. In the context of atmosphericboundary-layer modelling, we argue that a part of thedissipation production should be modelled as the inputto the spectral cascade from the energy-containingpart of the spectrum, with a characteristic length , while the equilibrium imbalancebetween local production and destruction ofdissipation is modelled as proportional toE2/E, as in the standard model. Wepropose an E – – turbulence closurescheme, in which both the mixing length, m, and are prescribed. The importance ofthe equation is diminished, though itstill determines the dissipation rate in the Eequation.     

Scavenging Efficiency of ‘Aerosol Carbon’ and Sulfate in Supercooled Clouds at Mt. Sonnblick (3106 m a.s.l., Austria)

Cloud water and interstitial aerosol samples collected at Mt. Sonnblick (SBO) were analyzed for sulfate and aerosol carbon to calculate in-cloud scavenging efficiencies. Scavenging efficiencies for sulfate (_SO) ranged from 0.52 to 0.99 with an average of 0.80. Aerosol carbon was scavenged less efficiently with an average value (_AC) of 0.45 and minimum and maximum values of 0.14 and 0.81, respectively. Both _SO and _AC showed a marked, but slightly different, dependence on the liquid water content (LWC) of the cloud. At low LWC, _SO increased with rising LWC until it reached a relatively constant value of 0.83 above an LWC of 0.3 g/m³. In the case of aerosol carbon, we obtained a more gradual increase of _AC up to an LWC of 0.5 g/m³. At higher LWCs, _{_} remained relatively constant at 0.60. As the differences between _SO and _A varied across the LWC range observed at SBO, we assume that part of the aerosol carbon was incorporated into the cloud droplets independently from sulfate. This hypothesis is supported by size classified aerosol measurements. The differences in the size distributions of sulfate and total carbon point to a partially external mixture. Thus, the different chemical nature and the differences in the size and mixing state of the aerosol particles are the most likely candidates for the differences in the scavenging behavior.     

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.     

Recalibration of the hohenpeissenberg dobson spectrophotometer 104 presuming ‘effective absorption coefficients’

The well calibrated Brewer spectrophotometer 17 (Sci-Tec Instruments Inc., Canada) stayed at the Meteorological Observatory Hohenpeissenberg (MOHP) from August 27 until September 1, 1984, in order to check and recalibrate Brewer 10, which had some stability problems. Brewer 17 was initially calibrated in July 1983, the validity of this calibration was repeatedly verified before and after the stay at the MOHP (Kerr et al., 1985; Kerr, 1984). The instrument proved itself to be very stable and appropriate as travellings standard instrument.As Dobson 104 didn't seem to be well calibrated at that time, the occasion was taken to perform also a Dobson recalibration. The methods normally used were not satisfactory, but a different method, presuming Effective Absorption Coefficients (EAC), presented by Kerr et al. at the Quadrennial Ozone Symposium 1984 in Greece, yielded encouraging results. Before recalibration Dobson 104 showed a difference of 2–3% in comparison to Brewer 10-, Brewer 17- and TOMS- (on satellite Nimbus 7) measurements, whereas the agreement with the Brewers after EAC-calibration was good (X _rel < 1%). The different Dobson calibration methods are compared and the results of the Dobson 104 and Brewer 10 recalibrations are presented.

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Zusammenfassung Vom 27. August bis 1. September 1984 befand sich das Brewer Standard Spektrophotometer 17 (Sci-Tec Instruments Inc., Canada) am Meteorologischen Observatorium Hohenpeißenberg (MOHP), um den nicht sehr stabilen Brewer 10 zu überprüfen und neu zu kalibrieren. Der Brewer 17 wurde erstmals im Juli 1983 kalibriert, die Gültigkeit dieser Eichung wurde mehrfach vor und einmal nach dem Aufenthalt am MOHP bestätigt (Kerr et al., 1985; Kerr, 1984). Das Instrument erwies sich als sehr stabil und geeignet als transportables Standardinstrument.Da der Dobson 104 zum damaligen Zeipunkt ebenfalls nicht gut kalibriert schien, wurde die Gelegenheit einer Dobson-Neukalibrierung wahrgenommen. Die normalerweise benutzten Methoden waren nicht zufriedenstellend im Gegensatz zu einer Methode, die von Effektiven Absorption Coeffizienten (EAC) ausgeht. Diese von Kerr et al. auf dem Quadrennial Ozon Symposium 1984 in Griechenland vorgestellte Methode lieferte hier ermutigende Ergebnisse. Vor der Neueichung zeigte der Dobson 104 eine Differenz von etwa 2–3% im Vergleich mit Brewer 10-, Brewer 17- und TOMS- (auf dem Nimbus-7-Satelliten) Messungen, während die Übereinstimmung mit den Brewer-Geräten nach der EAC-Kalibrierung gut war (X _rel < 1%). Die verschiedenen Dobson-Kalibrierungsmethoden werden verglichen und Ergebnisse der Dobson 104- und Brewer 10-Neukalibrierungen werden vorgestellt.

     

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.     

In-water and remote measurements of ocean color

Spectral measurements of downwelling irradiance, E _d(), above the surface, and of upwelling irradiance just below the surface, E _u(), allow computation of spectral values of the diffuse reflectance R() = E _u()/E _d(); this yields full information about the true color and brightness of the ocean. Typical results are presented and interpreted for waters very different in turbidity and phytoplankton content. Conversely, the possibility of infering the water content from R() data at selected wavelengths is examined in terms of the respective number of equations and unknowns. The necessary use of assumptions and of empirical laws is emphasized.The magnitude of the useful signal emerging from the water, and the magnitude of the additional signals due to specular reflexion at the interface and to atmospheric scattering, are compared on the basis of spectroradiometric measurements performed within and above the sea, from different altitudes. These unwanted signals are dominant, causing a drastic change in the spectral composition of the light received by a remote sensor. The evaluation of the atmospheric effect must be very precise in order to recover the marine signal with a sufficient accuracy for a meaningful application of any kind of algorithm.This work was supported in part by the Centre National d'Exploitation des Océans (under contract CNEXO 77/1695) and in part by the Centre National de la Recherche Scientifique (RCP 247 & ERA 278).