The spectral velocity tensor for homogeneous boundary-layer turbulence

We have postulated a simple model for the spectral tensor _ij (k) of an anisotropic, but homogeneous turbulent velocity field. It is a simple generalization of the spectral tensor _inf ^{ij piso}(k) for isotropic turbulence and we show how in the limit of isotropy, _ij (k) becomes equal to _inf ^{ij piso}(k). Whereas _inf ^{ij piso}(k) is determined entirely by one scalar function of k = ¦k¦, namely the energy spectrum, we need three independent scalar functions of k to specify _ij (k). We show how it is possible by means of the three stream-wise velocity component spectra to determine the three scalar functions in _ij (k) by solving two uncoupled, ordinary linear differential equations of first and second order. The analytic form of the component spectra each has a set of three parameters: the variance and the integral length scale of the velocity component and a dimensionless parameter, which governs the curvature of the spectrum in the transition domain from the inertial subrange towards lower wave numbers. When the three sets of parameters are the same, the three spectra correspond to isotropic turbulence and they are all interrelated and related to the energy spectrum. We show how it is possible to obtain these spectral forms in the neutral surface layer and in the convective boundary layer from data reported in the literature. The spectral tensor is used to predict the lateral coherences for all three velocity components and these predictions are compared with coherences obtained in two experiments, one using three masts at a horizontally homogeneous site in Denmark and one employing two aircraft flying in formation over eastern Colorado. Comparison shows reasonable agreement although with considerable experimental scatter.The National Center for Atmospheric Research is sponsored by the National Science Foundation.     

The behaviour of aerosol optical depth during clear summer days in Athens,Greece

Summary The integral aerosol optical depths (k ) at the hour of 08:20 Local Standard Time (LST), are compared with those calculated previously at 11:20 and 14:20 LST, for clear days during summer in Athens over the period 1962–1988. The mean values at 08:20 LST were consistently lower than the values at 11:20 and 14:20 LST. The influence of the vertical wind profile on the values ofk was also investigated. A comparison was made of the wind profiles at 02:00 and 14:00 LST, for days in which the 11:20 and 14:20 LST values ofk were 0.200 andk 0.350, respectively. The corresponding bulk wind shear s was also found for the period 1980–1988. The most significant results occurred with the first category of days. The resultant wind velocities from the surface to the 900 hPa level, in each hour were higher by 2–4 m·s^–1 with respect to the corresponding values for the second category. At 02:00 LST the bulk wind shear showed a considerable difference (1.8) between the two categories of days in the surface to 700 hPa layer at 02:00 LST. Finally, the associated weather conditions that appear to initiate a period of low values ofk (k 0.200) at 11:20 and 14:20 LST were examined for the period 1980–1988. Fifteen such cases were identified and it was found that they all occurred after the passage of weak cold fronts.With 6 Figures     

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.     

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.     

Kinetics of the Reactions of IO with HO2 and O(3P)

A discharge-flow tube coupled with resonance fluorescence and chemiluminescence detection has been used to investigate the reactions IO + HO₂ products (1) and IO + O(³P) I + O₂(2), at T = 296 ± 1 K and P = 1.7 - 2 Torr. The rate constants k_-1 and k₂ have been found to be (7.1 ± 1.6) × 10^-11 cm³ molecule^-1 s^-1 and (1.35 ± 0.15) × 10^-10 cm³ molecule^-1 s^-1, respectively.     

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.     

An alternative analysis of flux-gradient relationships at the 1976 ITCE

An extensive micrometeorological data set from the 1976 International Turbulence Comparison Experiment (ITCE) is analysed to determine flux-gradient relationships in an unstable atmosphere for momentum, sensible heat and water vapour transfers. The data are first analysed for internal consistency, resulting in the rejection of some data. Following a least-square fit to the remaining data in the form /k = (1 – z/L)^-/k, rounded-off values of k, , and are selected for each form of transfer consistent with the statistical accuracy of the measurements. The equations finally adopted are _M = (1 – 28z/L)^-1/4 and _{H, W} = (1 – 14z/L)^-1/2 with k _M = k_H = k_W = 0.40.These expressions fit the averaged observations to within a few per cent in the stability range of the experiment (-4 < z/L < -0.004).     

A study of the seasonal migration of ITCZ and the quasi-periodic oscillations in a simple monsoon system using an energy balance model

Summary A zonally averaged global energy balance model with feedback mechanisms was constructed to simulate (i) the poleward limits of ITCZ over the continent and over the ocean and (ii) a simple monsoon system as a result of differential heating between the continent and the ocean. Three numerical experiments were performed with lower boundary as (1) global continent, (2) global ocean and (3) continent-ocean, with freezing latitudes near the poles. Over the continent, midlatitude deserts were found and the ITCZ migrates 25° north and south with seasons. Over a global swamp ocean results do not show migration of ITCZ with time but once the ocean currents are introduced the ITCZ migrates 5° north and south with seasons. It was found that the seasonal migration of ITCZ strongly depends on the meridional distribution of the surface temperature. It was also found that continent influences the location of the oceanic ITCZ. In the tropics northward progression of quasi-periodic oscillations called events are found during the pre- and post-monsoon periods with a period of 8 to 15 days. This result is consistent with the observed quasi-periodic oscillations in the tropical region. Northward propagation of the surface temperature perturbation appears to cause changes in the sensible heat flux which in turn causes perturbations in vertical velocity and latent heat flux fields.List of Symbols vertical average - ₀ zonal average - vertical mean of the zonal average - _0s zonal average at the surface - _0a zonal average at 500 mb level - latitude We now define the various symbols used in the model rate of atmospheric heating due to convective cloud formation (K/sec) - dp/dt (N/m²/sec) - density - potential temperature (K) - rate of rotation of the earth (rad/sec) - empirical constant - humidity mixing ratio - ^* saturated humidity mixing ratio - opacity of the atmosphere - ₁,₂ factors for downward and upward effective black body long wave radiation from the atmosphere - Stefan-Boltzmann constant - emissivity of the surface - _D subsurface temperature (K) - a specific volume - _0xs ,_0ys eastward and northward components of surface frictional stress - ^* vertical velocity at the top of the boundary layer (N/m²/sec) - P Thickness of the boundary layer (mb) - nondimensional function of pressure - P pressure - P _a pressure of the model atmosphere (N/m²) - P _s pressure at the surface (N/m²) - t time (sec) - U eastward wind speed (m/sec) - V northward wind speed (m/sec) - surface water availability - T absolute temperature (K) - heat addition due to water phase changes - g acceleration due to gravity (m²/sec) - a radius of the earth (m) - R gas constant for dry air (J/Kg/K) - C _p specific heat of air at constant pressure (J/Kg/K) - k R/C _p - L latent heat of condensation (J/Kg) - f coriolis parameter (rad/sec) - H _s H _0s ⁽¹⁾ +H _0s ⁽²⁾ +H _0s ⁽³⁾ +H _0s ⁽⁴⁾ +H _0s ⁽⁵⁾ (J/m²/Sec)=sum of the rates of vertical heat fluxes per unit surface area, directed toward the surface - H _a H _0a ⁽¹⁾ +H _0a ⁽²⁾ +H _0a ⁽³⁾ +H _0a ⁽⁴⁾ (J/m²/Sec)=sum of the rates of heat additions to the atmospheric column per unit horizontal area by all processes - H _0s ⁽¹⁾ ,H _0a ⁽¹⁾ heat flux due to short wave radiation - H _0s ⁽²⁾ ,H _0a ⁽²⁾ heat flux due to long wave radiation - H _0s ⁽³⁾ ,H _0a ⁽³⁾ heat flux due to small scale convection - H _0s ⁽⁴⁾ heat flux due to evaporation - H _0a ⁽⁴⁾ heat flux due to condensation - H _0s ⁽⁵⁾ heat flux due to subsurface conduction and convection - e ^* saturation vapor pressure - R solar constant (W/m²) - r _a albedo of the atmosphere - r _s albedo of the surface - b ₂ empirical constant (J/m²/sec) - c ₂ empirical constant (J/m²/sec) - e ₂ nondimensional empirical constant - f ₂ empirical constant (J/m₂/sec) - factor proportional to the conductive capacity of the surface medium - a _s constant used in Sellers model - b _s positive constant of proportionality used in the Sellers model (kg m²/J/sec²) - K _HT coefficient for eddy diffusivity of heat (m²/sec) - K _HE exchange coefficient for water vapor (m²/sec) - h depth of the water column (m) - z height (m) - V _0ws meridional component of surface current (m/sec) - n cloud amount - G _0,n long wave radiation form the atmosphere for cloud amount n (W/m²) - B ₀ long wave radiation from the surface (W/m²) - S _0,n short wave radiation from the atmosphere for cloud amount n (W/m²) - A _n albedo factor for a cloud amount n - R _f1 large scale rainfall (mm/day) - R _f2 small scale rainfall (mm/day) With 22 Figures     

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.     

Trace gas exchange at the air/water interface: Measurements of mass accommodation coefficients

A liquid jet of 90 m diameter and variable length has been utilized to determine absorption rates and, hence, mass accommodation coefficients , of atmospheric trace gases. The compounds investigated are HCl (0.01), HNO₃ (0.01), N₂O₅ (0.005), peroxyacetyl nitrate (>0.001), and HONO (0.005). It is concluded that the absorption of these trace gases by liquid atmospheric water is not significantly retarded by interfacial mass transport. The strengths and limitations of the liquid jet technique for measuring mass accommodation coefficients are explored.     

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     

A new theory of the energy spectrum

In a recent paper, the author introduced a new viscous boundary layer, called the mesolayer, in turbulent shear flow. Its importance stems from its location between the inner and outer regions which are controlled by the law of the wall and Reynolds number similarity, respectively. This intrusion prevents the classical overlap assumption which appears to be fundamental in the derivation of the classical logarithmic behavior. The mesolayer has a thickness proportional to Taylor's microscale . This, and the analogy between the energy equation for the spectrum function of isotropic turbulence and the momentum equation for shear flow, suggest the existence of a similar region in wavenumber space with wavenumber k ~ ^-1. This mesoregion separates the inner region k ~ k _s(where k _s^-1 and is the Kolmogorov length) and the outer region k k _e(where k _e ^-1 and l is the energy-containing eddy size) and again invalidates the overlap assumption which appears to be fundamental in the derivation of the classical k ^-5/3-behavior of the inertial subrange.Incorporation of the mesoregion into the argument leads to a new theory with k ^-5/3-behavior in two regions (^-1 k k _s) and (k _e k ^-1) although with two different coefficients of proportionality (Kolmogorov constants). This leads to a wandering of the spectrum curve about the classical k ^-5/3 line similar to a wandering in turbulent shear flow about the logarithmic curve. This is clearly indicated by the data for the variation of the Kolmogorov constant.Other data support the new theory. In particular, the location of the point k _mwhere the curve of the nonlinear energy-transfer function goes through zero shows agreement with the theory, i.e., k _m^-1.     

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     

On the similarity in atmospheric fluctuations of carbon dioxide,water vapor and temperature over vegetated fields

This paper describes the similarity between atmospheric fluctuations of carbon dioxide, water vapor and temperature using data which cover a wide range of instability (0.02 < < 10). The is the Monin-Obukhov stability parameter including the humidity effect.The spectral analysis shows that the coherency between fluctuations of carbon dioxide and water vapor or temperature is very close to unity, and the phase difference is basically out of phase for whole frequency ranges analyzed. The stability dependence of the normalized standard deviation of carbon dioxide is very similar to those of water vapor and temperature. The normalized standard deviation is about 2.5 under near neutral conditions, and it decreases with increasing instability following the -1/3; power law as (-)^-1/3. The skewness factors of carbon dioxide, water vapor and temperature show a systematic departure with increasing instabilities for 0.02 < s- < 1, and level off at high instabilities for 1 < -\s < 10. The stability dependence of the flatness factors is not so clear as that noted in the standrard deviation and skewness factors. Dissipation rates of carbon dioxide, water vapor and temperature variance are well related to the spectral peak wavelength. This seems to be real since the local production and local dissipation rates are the main terms, almost balancing one another in the variance budget equations for scalar entities.     

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.     

The carbon isotopic ratio of atmospheric carbon dioxide at Tsukuba,Japan

To find out the secular and seasonal trends of the ¹³C value and CO₂ concentration in the surface air and the determination of the ¹³C in the atmospheric CO₂ collected at Tsukuba Science City was carried out during the period from July 1981 to October 1983. The monthly average of the ¹³C value of CO₂ in the surface air collected at 1400 LMT ranged from -7.52 to \s-8.45 with an average of -7.96±0.25 and the CO₂ concentration in the air varied from 334.5 l 1^-1 to 359 l 1^-1 with an average of 347.2±6.3 l 1^-1. The ¹³C value is high in summer and low in winter and is negatively correlated with the CO₂ concentration. In general, the relationship between the ¹³C and the CO₂ concentration is explainable by a simple mixing model of two different constant carbon isotopic species but the relationship does not always follow the model. The correlation between the ¹³C value and the CO₂ concentration is low during the plant growth season and high at other times. The observed negative deviation of the ¹³C value from the simple mixing model in the plant growth season is partly due to the isotopic fractionation process which takes place in the land biota.     

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.     

Photochemical aspects of tropospheric iodine behaviour

The I-atom sensitised decomposition of ozone in air at 1 atm pressure and ambient temperature has been investigated. Iodine atoms were produced by photolysis of I₂ using visible light or of CH₃I using ultraviolet light. In both cases, the quantum yield for O₃ decomposition was 1.25 (±0.11) per I atom. An important role is proposed for the self-reaction of IO radicals leading to higher oxides of iodine, IO+IO(+M)I₂O₂(+M)higher oxides, which predominated over the bimolecular reaction leading to regeneration of I atoms, IO+IO2I+O₂, with k _2a/k _2b4. Simple computer modelling calculations indicate that reaction (2a) may be important in determining the fate of photolabile iodine species in the atmosphere. The consequences for the behaviour of radioiodine releases are also discussed.     

Numerical studies of heat island circulations

A two dimensional model has been set up to investigate the circulation induced by an urban heat island in the absence of synoptic winds. The boundary conditions need to be formulated carefully and due to difficulties arising here, we restrict our attention to cases of initially stable thermal stratification. Heat island circulations are allowed to develop from rest and prior to the appearance of the final symmetric double cell pattern, a transitional multi-cell pattern is observed in some cases. The influence on the steady state circulation of various parameters is studied, among which are eddy transfer coefficients, the heat island intensity, the initial temperature stratification and the heat island size. Some results are presented for a case in which differential surface cooling beneath an initially stable atmosphere produces a circulation and an unstable layer capped by an elevated inversion over the city. It is hoped that this case is vaguely representative of the night-time heat island with no geostrophic wind.Notation c_p Specific heat at constant pressure - g Acceleration due to gravity - H Top of integration region - K_z Vertical eddy transfer coefficient - K_x, K_xH, K_xm Horizontal eddy transfer coefficients for heat and momentum - l ixing length - p Pressure - p₀ Reference surface pressure (1000 mb) - P_H (x, t) Pressure at z = H - R Specific gas constant for dry air - t Time - u, w Horizontal and vertical velocities - x, z Horizontal and vertical coordinates - x₁, x₂ Positions of discontinuities in surface temperature field (see Figure 2) - x_a Heat island half-width - x_b Boundary of integration region - Parameter in formula for eddy coefficients (variable-K case) = 18.0 - _s Intensity of heat island - Potential temperature field - Reference absolute temperature (variable-K case) - _r Reference temperature (° C) - _s Surface temperature - Q Air density     

A discharge flow mass-spectrometric study of the reaction between the NO3 radical and isoprene

The kinetics and mechanism of the reactionNO₃+CH₂=C(CH₃)–CH=CH₂productswere studied in two laboratories at 298 K in the pressure range 0.7–3 torr using the discharge-flow mass-spectrometric method. The rate constant obtained under pseudo-first-order conditions with excess of either NO₃ or isoprene was: k ₁=(7.8±0.6)×10^–13 cm³ molecule^–1 s^–1. The product analysis indicated that the primary addition of NO₃ occurred on both -bonds of the isprene molecule.