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.     

Nitrogen compound emission from biomass burning in tropical African savanna FOS/DECAFE 1991 experiment (Lamto,Ivory Coast)

Gaseous nitrogen compounds (NO _x , NO _y , NH₃, N₂O) were measured at ground level in smoke plumes of prescribed savanna fires in Lamto, in the southern Ivory Coast, during the FOS/DECAFE experiment in January 1991. During the flaming phase, the linear regression between [NO _x ] and [CO₂] (differences in concentration between smoke plumes and atmosheric background) results volumic emission ratio [NO _x ]/[CO₂]=1.37×10^–3 with only slight differences between heading and backing fires. Nearly 90% of the nitrogen oxides are emitted as NO. Average emission ratios of other compounds are: 1.91, 0.047, and 0.145×10^–3 for NO _y , NH₃ and N₂O, respectively. The emission ratios obtained during this field experiment are compred with corresponding values measured during former experiments with the same plant species in combustion chambers. An accurate determination of both the biomass actually burned and of the plant nitrogen content, allows an assessment of emission fluxes of N-compounds from Guinean savanna burns. Preliminary results dealing with the influence of fire on biogenic emissions from soils are also reported.     

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     

Carbonyl sulfide emissions from biomass burning in the tropics

Carbonyl sulfide emissions from biomass burning have been studied during field experiments conducted both in an African savanna area (Ivory Coast) and rice fields, central highland pine forest and savanna areas in Viet-Nam. During these experiments CO₂, CO and C₂H₂ or CH₄ have also been also monitored. COS values range from 0.6 ppbv outside the fires to 73 ppbv in the plumes. Significant correlations have been observed between concentrations of COS and CO (R ²=0.92,n=25) and COS and C₂H₂ (R ²=0.79,n=26) indicating a COS production during the smoldering combustion. COS/CO₂ emission factors (COS/CO₂) during field experiments ranged from 1.2 to 61×10^–6 (11.4×10^–6 mean value). COS emission by biomass burning was estimated to be up to 0.05 Tg S/yr in tropics and up to 0.07 Tg S/yr on a global basis, contributing thus about 10% to the global COS flux. Based on the S/C ratio measured in the dry plant biomass and the COS/CO₂ emission factor, COS can account for only about 7% of the sulfur emitted in the atmosphere by biomass burning.     

A Generalized Structure-Activity Relationship for the Decomposition of (Substituted) Alkoxy Radicals

A novel and readily applicable Structure-Activity Relationship (SAR) for predicting the barrier height E_b to decomposition by C-C scission of (substituted) alkoxy radicals is presented. Alkoxy radicals are pivotal intermediates in the atmospheric oxidation of (biogenic) volatile organic compounds, and their fate is therefore of crucial importance to the understanding of atmospheric VOC degradation mechanisms. The SAR is based on available theoretical energy barriers and validated against barriers derived from experimental data. The SAR is expressed solely in terms of the number(s) N_i of alkyl-, hydroxy- and/or oxo-substituents on the - and -carbons of the breaking bond: E_b(kcal/mol) =17.5 – 2.1 × N(alk) – 3.1 ×N(alk) – 8.0 × N_,(OH) – 8.0 × N(O=) – 12 × N(O=). For barriers below 7 kcal/mol, an additional, second-order term accounts for the curvature. The SAR reproduces the available experimental and theoretical data within 0.5 to 1 kcal/mol. The SAR generally allows conclusive predictions as to the fate of alkoxy radicals; several examples concerning oxy radicals from prominent atmospheric VOC are presented. Specific limitations of the SAR are also discussed. Using the predicted barrier height E_b, the high-pressure rate coefficient for alkoxy decomposition k _diss (298 K) can be obtained from k _diss (298 K) = L ×1.8 × 10¹³ exp(–E_b/RT) s^–1, with L the reaction path degeneracy.     

A laboratory study of the mechanism of the oxygen airglow

Further laboratory studies of emission by O(¹ S) and by O₂ A ³ _u ⁺ ,A³ _u andc ¹ _u ^– in the oxygen afterglow lead to the conclusion that Barth's mechanism for the excitation of the auroral green line O ₂ ^* +O(³P=O₂+O(¹S)–(1) is correct and that levelsv=6 and 7 of O₂ A ³ _u ⁺ are Barth precursors. The value ofk ₁=7×10^–11 cm³ s^–1 deduced for these levels is shown to be in fair agreement with atmospheric measurements.     

FT-IR Study of the Kinetics and Products of the Reactions of Dimethylsulphide, Dimethylsulphoxide and Dimethylsulphone with Br and BrO

Kinetics and products of the gas-phase reactions of dimethylsulphide (DMS), dimethylsulphoxide (DMSO) and dimethylsulphone (DMSO₂) with Br atoms and BrO radicals in air have beeninvestigated using on-line Fourier Transform Infrared Spectroscopy (FT-IR) as analytical technique at 740 ± 5 Torr total pressure and at 296 ± 3 K in a480 L reaction chamber. Using a relative rate method for determining the rate constants; the following values (expressed in cm³molecule^–1 s^–1) were found: k_DMS+Br = (4.9 ±1.0) ×10^–14, k_DMSO + Br < 6 × 10^–14,k_{DMSO 2} + Br 1 × 10^–15,k_DMSO + BrO = (1.0 ± 0.3) × 10^–14 andk_{DMSO 2} + BrO 3 × 10^–15 (allvalues are given with one on the experimental data). DMSO, SO₂, COS, CH₃SBr andCH₃SO₂Br were identified as the main sulphur containing products of the oxidation of DMS by Br atoms. From the reaction between DMSO and Br atoms, DMSO₂and CH₃SO₂Br were the only sulphur containing products thatwere identified. DMSO, DMSO₂ and SO₂ were identified as themain sulphur containing products of the reaction between DMS and BrO.DMSO₂ was found to be the only product of the reaction between DMSO and BrO. For the reactions of DMSO₂ with Br and BrO no products were identified because the reactions were too slow.The implications of these results for atmospheric chemistry are discussed.     

The prediction of dust erosion by wind: An interactive model

We have devised a partial differential equation for the prediction of dust concentration in a thin layer near the ground. In this equation, erosion (detachment), transport, deposition and source are parameterised in terms of known quantities. The interaction between a wind prediction model in the boundary layer and this equation affects the evolution of the dust concentration at the top of the surface layer. Numerical integrations are carried out for various values of source strength, ambient wind and particle size. Comparison with available data shows that the results appear very reasonable and that the model should be subjected to further development and testing.Notation (x, y, z, t) space co-ordinates and time (cm,t) - u, v components of horizontal wind speed (cm s^–1) - u _g, v_g components of the geostrophic wind (cm s^–1) - V=(u²+v²)^1/2 (cm s^–1) - (û v)= 1/(h – k) _k ^h(u, v)dz(cm s^–1) - V _* friction velocity (cm s^–1) - z ₀ roughness length (cm) - k ₁ von Karman constant =0.4 - V _d deposition velocity (cm s^–1) - V _g gravitational settling velocity (cm s^–1) - h height of inversion (cm) - k height of surface layer (cm) - potential temperature (°K) - _gr potential temperature at ground (°K) - _K potential temperature at top of surface layer (°K) - P pressure (mb) - P ₀ sfc pressure (mb) - C _p/C_v - (t)= /z lapse rate of potential temperature (°K cm^–1) - A(z) variation of wind with height in transition layer - B(z) variation of wind with height in transition layer - Cd drag coefficient - C _HO transfer coefficient for sensible heat - C dust concentration (g m^–3) - C _K dust concentration at top of surface layer (g m^–3) - D(z) variation with height of dust concentration - u, v, w turbulent fluctuations of the three velocity components (cm s^–1) - A ₁ constant coefficient of proportionality for heat flux =0.2 - Ri Richardson number - g gravitational acceleration =980 cm s^–2 - Re Reynolds number = - D _s thickness of laminar sub-layer (cm) - v molecular kinematic viscosity of air - coefficient of proportionality in source term - dummy variable - t time step (sec) - n time index in numerical equations On sabbatical leave at University of Aberdeen, Department of Engineering, September 1989–February 1990.     

Size-Resolved Characterisation of Soluble Ions in the Particles in the Tropospheric Plume of Masaya Volcano, Nicaragua: Origins and Plume Processing

We present the first application of a multi-stage impactor to study volcanic particle emissions to the troposphere from Masaya volcano, Nicaragua. Concentrations of soluble SO₄ ^2–,Cl^–, F^–, NO₃ ^–, K⁺, Na⁺,NH₄ ⁺, Ca²⁺ and Mg²⁺ were determined in 11 size bins from 0.07 m to >25.5 m. The near-source size distributions showed major modes at 0.5m (SO₄ ^2–, H⁺,NH₄ ⁺); 0.2 m and 5.0 m (Cl^–) and 2.0–5.0 m(F^–). K⁺ and Na⁺ mirrored the SO₄ ^2– size-resolvedconcentrations closely, suggesting that these were transported primarily asK₂SO₄ and Na₂SO₄ in acidic solution, while Mg²⁺ andCa²⁺ presented modes in both <1 m and >1 m particles. Changes in relative humidity were studied by comparing daytime (transparent plume) and night-time (condensed plume) results. Enhanced particle growth rates were observed in the night-time plume as well as preferential scavenging of soluble gases, such as HCl, by condensed water. Neutralisation of the acidic aerosol by background ammonia was observed at the crater rim and to a greater extent approximately 15 km downwind of the active crater. We report measurements of re-suspended near-source volcanic dust, which may form a component of the plume downwind. Elevated levels ofSO₄ ^2–, Cl^–, F^–,H⁺, Na⁺, K⁺ and Mg²⁺ were observed around the 10 m particle diameter in this dust. The volcanic SO₄ ^2– flux leaving the craterwas 0.07 kg s^–1.     

Henry's law coefficients of formic and acetic acids

The Henry's law constants, K _H, of dilute aqueous formic and acetic acids were determined experimentally as a function of concentration and temperature using a new counterflow packed-column technique. K _H was found to be (8.9±1.3)×10³ and (4.1±0.4)×10³ M atm^-1 at 25°C for HCOOH and CH₃COOH, respectively. The reaction enthalpies, H, were found to be –51±2 kJ mol^-1 and –52±1 kJ mol^-1 for formic and acetic acid, respectively. These are in good agreement with calculated thermochemical values.Whereas the K _H values are in reasonably good agreement with certain other experimentally determined values, K _H (HCOOH) is two to three times higher than calculated thermochemical values while K _H (CH₃COOH) is lower than the two calculated values.The best experimental values appear to be (11±2)×10³ M atm^-1 and (7±3)×10³ M atm^-1 for HCOOH and CH₃COOH, respectively.     

Microwave vegetation optical depth and inverse modelling of soil emissivity using Nimbus/SMMR satellite observations

Summary A radiative transfer model has been used to determine the large scale effective 6.6 GHz and 37 GHz optical depths of the vegetation cover. Knowledge of the vegetation optical depth is important for satellite-based large scale soil moisture monitoring using microwave radiometry. The study is based on actual observed large scale surface soil moisture data and observed dual polarization 6.6 and 37 GHz Nimbus/SMMR brightness temperatures over a 3-year period. The derived optical depths have been compared with microwave polarization differences and polarization ratios in both frequencies and with Normalized Difference Vegetation Index (NDVI) values from NOAA/AVHRR. A synergistic approach to derive surface soil emissivity from satellite observed brightness temperatures by inverse modelling is described. This approach improves the relationship between satellite derived surface emissivity and large scale top soil moisture fromR ²=0.45 (no correction for vegetation) toR ²=0.72 (after correction for vegetation). This study also confirms the relationship between the microwave-based MPDI and NDVI earlier described and explained in the literature.List of Symbols f frequency [Hz] - f _i(p) fractional absorption at polarizationp - h surface roughness - h h cos² - H horizontal polarization - n _i complex index of refraction - p polarization (H orV) - R _s microwave surface reflectivity - T _B(p) brightness temperature at polarizationp - T ^* normalized brightness temperature - T polarization difference (T _v-T _H) - T _s temperature of soil surface - T _c temperature of canopy - T _max daily maximum air temperature - T _min daily minimum air temperature - V vertical polarization - soil moisture distribution factor; also used for the constant to partition the influence of bound and free water components to the dielectric constant of the mixture - empirical complex constant related to soil texture - microwave transmissivity of vegetation (=e ^–) - ^* effective transmissivity of vegetation (assuming =0) - microwave emissivity - _s emissivity of smooth soil surface - _rs emissivity of rough soil surface - _vs emissivity of vegetated surface - soil moisture content (% vol.) - K dielectric constant [F·m^–1] - K _fw dielectric constant of free water [F·m^–1] - K _ss dielectric constant of soil solids [F·m^–1] - K _m dielectric constant of mixture [F·m^–1] - K _o permittivity of free space [8.854·10^–12 F·m^–1] - high frequency limit ofK _wf [F·m^–1] - wavelength [m] - incidence angle [degrees from nadir] - polarization ratio (T _H/T _V) - b soil bulk density [gr·cm^–3] - s soil particle density [gr·cm^–3] - R surface reflectivity in red portion of spectrum - NIR surface reflectivity in near infrared portion of spectrum - _eff effective conductivity of soil extract [mS·cm^–1] - vegetation optical depth - _6.6 vegetation optical depth at 6.6 GHz - ₃₇ vegetation optical depth at 37 GHz - ^* effective vegetation optical depth (assuming =0) - single scattering albedo of vegetation With 12 Figures     

Mass transfer at the air/water interface: Mass accommodation coefficients of SO2, HNO3, NO2 and NH3

We present here experimental determinations of mass accommodation coefficients using a low pressure tube reactor in which monodispersed droplets, generated by a vibrating orifice, are brought into contact with known amounts of trace gases. The uptake of the gases and the accommodation coefficient are determined by chemical analysis of the aqueous phase.We report in this article measurements of _exp=(6.0±0.8)×10^–2 at 298 K and with a total pressure of 38 Torr for SO₂, (5.0±1.0)×10^–2 at 297 K and total pressure of 52 Torr for HNO₃, (1.5±0.6)×10^–3 at 298 K and total pressure of 50 Torr for NO₂, (2.4±1.0)×10^–2 at 290 K and total pressure of 70 Torr for NH₃.These values are corrected for mass transport limitations in the gas phase leading to =(1.3±0.1)×10^–1 (298 K) for SO₂, (1.1±0.1)×10^–1 (298 K) for HNO₃, (9.7±0.9)×10^–2 (290 K) for NH₃, (1.5±0.8)×10^–3 (298 K) for NO₂ but this last value should not be considered as the true value of for NO₂ because of possible chemical interferences.Results are discussed in terms of experimental conditions which determine the presence of limitations on the mass transport rates of gaseous species into an aqueous phase, which permits the correction of the experimental values.     

The Henry's Law Constants of the Haloacetic Acids

Henry's law constants K_H (mol kg^-1 atm^-1) have been measured between 278.15 K and 308.15 K for the following organic acids: CH₂FCOOH (ln(K_H[298.15 K]) = 11.3 ± 0.2), CH₂ClCOOH (11.59 ± 0.14), CH₂BrCOOH (11.94 ± 0.21), CHF₂COOH (10.32 ± 0.10), CHCl₂COOH (11.69 ± 0.11), CHBr₂COOH (12.33 ± 0.29), CBr₃COOH (12.61 ± 0.21), and CClF₂COOH (10.11 ± 0.12). The variation of K_H with temperature was determined for all acids except CH₂FCOOH and CBr₃COOH, with _r H° for the dissolution reaction ranging from –85.2 ± 2.6 to –57.1 ± 2.5 kJ mol^-1, meaning that their solubility is generally more sensitive to temperature than is the case for the simple carboxylic acids. The Henry's law constants show consistent trends with halogen substitution and, together with their high solubility compared to the parent (acetic) acid (ln(K_H[298.15 K]) = 8.61), present a severe test of current predictive models based upon molecular structure. The solubility of haloacetic acids and strong dissociation at normal pH mean that they will partition almost entirely into cloud and fog in the atmosphere (0.05–1.0 g H₂O m^-3), but can reside in both phases for the liquid water contents typical of aerosols (10^-5-10^-4 g H₂O m^-3).     

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 Mechanism of Reactive NO3 Uptake on Dry NaX (X=Cl, Br)

A simple kinetic mechanism of nitrate radicals uptake on dry sea-salt NaCl, NaBr surfaces is proposed. The mechanism includes adsorption/desorption equilibrium and unimolecular decomposition of the adsorbed complex: NO₃(g) + NaX(s) (NO₃-NaX)(s); (NO₃-NaX)(s) NaNO₃ + X(s) Two techniques were used: the matrix isolation ESR and mass spectrometry. The uptake coefficient () is found to be dependent on exposure time of salt to NO₃ for raw coating. The initial (t0) is higher than the observable steady-state _obs. At room temperature _obs is independent of [NO₃] at low [NO₃] = 3 × 10⁹ - 10¹¹ cm^-3, but it is inversely proportional to [NO₃] at concentrations higher than 10¹² cm^-3. At temperatures above 100 °C, _obs becomes independent of [NO₃] in a wider range of [NO₃]. An increased number of dislocations is supposed to exist in the case of raw coating. Due to a wide spread of the surface sites binding energy with the ionic lattice near dislocations, the part of surface complexes has lower binding energy and "burns" more rapidly. That burning determines the transition from (t0) down to _obs.The kinetic parameters and elementary rate coefficients are obtained. The recommended for low atmospheric NO₃ concentration are in the range of 0.002 ± 0.04 for NaCl and 0.1-0.3 for NaBr depending on a mechanism of the (t) relaxation.     

A determination of the CH4, NO x and CO2 emissions from the Prudhoe Bay,Alaska oil development

In this paper we quantify the CH₄, CO₂ and NO _x emissions during routine operations at a major oil and gas production facility, Prudhoe Bay, Alaska, using the concentrations of combustion by products measured at the NOAA-CMDL observatory at Barrow, Alaska and fuel consumption data from Prudhoe Bay. During the 1989 and 1990 measurement campaigns, 10 periods (called events) were unambiguously identified where surface winds carry the Prudhoe Bay emissions to Barrow (approximately 300 km). The events ranged in duration from 8–48 h and bring ambient air masses containing substantially elevated concentrations of CH₄, CO₂ and NO _y to Barrow. Using the slope of the observed CH₄ vs CO₂ concentrations during the events and the CO₂ emissions based on reported fuel consumption data, we calculate annual CH₄ emissions of (24+/–8)×10³ metric tons from the facility. In a similar manner, the annual NO _x emissions are calculated to be (12+/–4)×10³ metric tons, which is in agreement with an independently determined value. The calculated CH₄ emissions represent the amount released during routine operations including leakage. However this quantity would not include CH₄ released during non-routine operations, such as from venting or gas flaring.     

Estimation of the Monin-Obukhov similarity functions from a spectral model

From measured one-dimensional spectra of velocity and temperature variance, the universal functions of the Monin-Obukhov similarity theory are calculated for the range –2 z/L + 2. The calculations show good agreement with observations with the exception of a range –1 z/L 0 in which the function _m , i.e., the nondimensional mean shear, is overestimated. This overestimation is shown to be caused by neglecting the spectral divergence of a vertical transport of turbulent kinetic energy. The integral of the spectral divergence over the entire wave number space is suggested to be negligibly small in comparison with production and dissipation of turbulent kinetic energy.Notation a,b,c contants (see Equations (–4)) - C_i constants i=u, v, w, (see Equation (5) - k_me,k_mT peak wave numbers of 3-d moel spectra of turbulent kinetic energy and of temperature variance, respectively - k_mi peak wave numbers of 1-d spectra of velocity components i=u, v, w and of temperature fluctuations i= - k_sb, k_c characteristics wave numbers of energy-feeding by mechanical effects being modified by mean buoyancy, and of convective energy feeding, respectively - L Monin-Obukhov length - % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiiYdd9qrFfea0dXdf9vqai-hEir8Ve% ea0de9qq-hbrpepeea0db9q8as0-LqLs-Jirpepeea0-as0Fb9pgea% 0lrP0xe9Fve9Fve9qapdbaqaaeGacaGaaiaabeqaamaabaabcaGcba% Gabeivayaaraaaaa!3C5B!\[{\rm{\bar T}}\] difference of mean temperature and mean potential temperature - T* Monin-Obukhov temperature scale - velocity of mean flow in positive x-direction - u* friction velocity - u, v, w components of velocity fluctuations - z height above ground - von Kármanán constant - temperature fluctuation - _m nondimensional mean shear - _H nondimensional mean temperature gradient - nondimensional rate of lolecular dissipation of turbulent kinetic energy - _D nondimensional divergence of vertical transports of turbulent linetic energy     

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.     

Analysis and trends of atmospheric turbidity parameters over Cairo

Summary This work deals with the Linke turbidity factor, based on total spectrum observations of the direct solar beam and aerosol turbidity parametersa _a , , and based on observations in broad spectral bands. Diurnal and seasonal variations of these turbidity parameters were analyzed for the period 1975 to 1991.Annual variations of these parameters show low values in winter and high values in both spring and summer. The extinction coefficients decrease with increase of both wavelength and optical airmass. Trend analysis shows an increase in aerosol extinction coefficient below 0.63 m, and a slight decrease for longer wave-lengths.Linear regression relations are also constructed to estimate botha _a and whenT _L is available. The relations show thata _a can be estimated with errors below 20%. The relation with the parameter, may give better results when it is estimated by assigning a fixed value of .Nomenclature AV Monthly and total average of the measured parameter - a Atmospheric optical thicknes - a _a Aerosol optical thickness - a _r Mean value of optical thickness of. Rayleigh atmosphere over all wavelengths - a _o Ozone optical thickness - a _o Ozone absorption coefficient - a _w Water vapor optical thickness - COR Correlation coefficient of the linear relation in percentage - Ex₁, Ex₂, Ex₃ Aerosol extinction coefficients in the bands .2–.53, .53–.63, .63–.695, respectively - I _(o) Normal incident direct solar radiation, under clear sky condition - I _o Extraterrestrial insolation at normal incidence - m _r Relative (optical) air mass - NO Number of the observations used in either making the relation or the verification - RMSE Root mean square error of the linear relation - RMSE% Percentage value of the root mean square error relative to the average measured value AV - T _L Linke turbidity factor - T Dry bulb temperature in °C - u _o Ozone layer thickness, cm - Z Zenith angle - Ångström wavelength exponent - Ångström turbidity coefficient - Wavelength - Y The year number after 1975 With 5 Figures     

Modelling of the vertical fluxes of nitric acid,ammonia, and ammonium nitrate

Results from numerical investigations regarding the exchange of HNO₃, NH₃, and NH₄NO₃ between the atmosphere and the biosphere are presented. The investigations were performed with a modified inferential method which 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 nitrogen compounds. This modified inferential method calculates the micrometeorological quantities (such as the friction velocity and the fluxes of sensible and latent heat), the height-invariant fluxes of the composed chemically conservative trace species with group concentrationsc ₁=[HNO₃]+[NH₄NO₃] (total nitrate),c ₂=[NH₃]+[NH₄NO₃] (total ammonia), andc ₃=[HNO₃]-[NH₃] as well as the fluxes of the individual nitrogen compounds. The parameterization of the fluxes is based on the flux-gradient relationships in the turbulent region of the atmospheric surface layer. The modified inferential method requires only the data of wind velocity, temperature, humidity and concentrations (HNO₃, NH₃, and NH₄NO₃) measured at a reference height by stations of a monitoring network.