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.     

An improved calibration for tethered balloon wind measurements

A previously published technique for using tethered spherical balloons as anemometers for measuring light low-level winds has been further developed. Earlier data on the relationship between the aerodynamic drag coefficient and the Reynolds number of spherical rubber balloons were combined with a large number of new data and re-analysed; and the errors in the relationship were estimated. The results allowed a more accurate calculation of wind speed from the deflection of a tethered balloon from the vertical. When combined with a new technique for calculating the effects of the tether, this enabled light to moderate low-level winds at fixed heights up to 600 m or more to be measured with simple, cheap, and readily mobile equipment; and a slight modification of the technique allowed measurement of winds in and above fog. Wind speeds measured by the ballon technique showed reasonably good agreement with measurements by an anemometer carried beneath the balloon.Glossary of Symbols a, b, c Coefficients in the relationship between lnC _d and lnR - A Quantity under square root in solution for lnV whena0 - C _d Wind drag coefficient for balloon - C _dc Value ofC _d given by calibration curve of Table I - D Dynamic wind pressure force on balloon - F Buoyant free lift of balloon with load - Re Reynold's number of balloon (sphere) - R = Re/10⁵ - r Radius of sphere - T Tension in tether - V Wind speed - ₈₃() =(lnC _dc -lnC _d ) when 83° , or 0 for other - Error in lnC _d - Elevation of tether where attached to balloon - Elevation of balloon from ground tether point - Molecular viscosity of air - Ratio of circumference to diameter of circle - Density of air     

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).     

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.     

Turbulence Reynolds number and the turbulent kinetic energy balance in the atmospheric surface layer

The relation between the turbulence Reynolds numberR and a Reynolds numberz* based on the friction velocity and height from the ground is established using direct measurements of the r.m.s. longitudinal velocity and turbulent energy dissipation in the atmospheric surface layer. Measurements of the relative magnitude of components of the turbulent kinetic energy budget in the stability range 0 >z/L 0.4 indicate that local balance between production and dissipation is maintained. Approximate expressions, in terms of readily measured micrometeorological quantities, are proposed for the Taylor microscale and the Kolmogorov length scale .     

An observational study of the vertical profile of the high frequency fluctuations of the wind in the atmospheric boundary layer

This paper summarizes some measurements of high-frequency turbulence made at Cardington during the years 1968, 1969 and 1970 at heights up to 900 m. It discusses the statistical distribution of the data which appears to be closely log-normal. Also it is shown how the mean profiles of the derived dissipation of turbulent kinetic energy () can be rationalized to some extent in terms of atmospheric stability and low-level wind speed. A close correlation between and the mean wind and temperature profiles up to 900 m is illustrated and some discussion of the turbulent energy budget throughout the boundary layer is presented. The use and limitations of the constant flux layer relations in calculatingz ₀ andL from the estimates of, at the lower heights, is brought out.     

On the mean monthly equivalent potential temperature and rainfall in West Africa

Summary Rainfall in West Africa is examined in relation to monthly mean equivalent potential temperature ( _e )at the earth's surface. The study revealed that monthly mean equivalent potential temperature ( _e ) and monthly rainfall (R) generally decreased northwards from the equator.A good relationship existed betweenR and _e in the northern zone of West Africa (i.e., north of 7.5° N). No definite relationship existed in the southern zone. In the northern zone, the departure of _e from its annual mean ( ) first became positive about a month before the onset of the rains. Positive departures from ) generally resulted in more than normal (or average) rainfall in this zone. In general, little or no rainfall occurred in West Africa whenever _e was less than 320 K.

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Zusammenfassung Der Niederschlag (MonatssummeR) in Westafrika wird in Zusammenhang mit der mittleren monatlichen Äquivalent-temperatur ( _e ) an der Erdoberfläche untersucht. Es zeigte sich, daß die Monatswerte beider Elemente im allgemeinen vom Äquator nach Norden abnehmen.ZwischenR und _e ergab sich für das nördliche Westafrika (nördlich von 7.5° N) eine gute, für die südliche Zone jedoch keine beweisbare Übereinstimmung. In der nördlichen Zone übertraf _e das Jahresmittel erstmals etwa einen Monat vor Beginn der Regenzeit. Positive Abweichungen vom mittleren _e hatten immer übernormalen Niederschlag in dieser Zone zur Folge. Dagegen gab es wenig oder keinen Niederschlag in Westafrika, wenn _e unter 320 K lag.

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With 7 Figures     

A comparison of bowen ratio and eddy correlation sensible and latent heat flux measurements above deciduous forest

Sensible and latent heat flux densities (H and E) were measured above a mature, 18 m deciduous forest during July and August, 1988, using the Bowen ratio-energy balance (BREB) and eddy correlation (EC) methods. EC estimates ofH and E underestimated day-time surface available energy by 11%. EC also partitioned available energy differently than BREB. for/L<0.0, EC favouredH and BREB favoured E. Practical and theoretical limitations of the BREB and EC methods above forests are discussed. The most plausible causes for the failure of EC to close the surface energy balance are a low frequency loss of flux and the failure of a single point measurement to account for the spatial dispersive flux. The most plausible causes of the EC-BREB energy partitioning anomaly are the invalidity of the BREB similarity assumption and the violation of flux-gradient diffusion assumptions in the near-field diffusion region.     

Mass transfer to bean leaves

A vapour of radio-lead (²¹²Pb) has been used to measure the Sherwood number, Sh, of model leaves at various angles of incidence,, to the airstream in a wind tunnel. The results for=0 are compared with Pohlhausen's formula and the results for 0, with Powell's experiments. The local values of Sh on the upwind and downwind sides of discs have been obtained. For leaves in the canopy, Sh was found to be about 25% greater than would be predicted by applying Pohlhausen's equation without correction for orientation.     

Transport-Dissipation Analytical Solutions to the E-∈Turbulence Model and their Role in Predictions of the Neutral ABL

E- turbulence model predictions of the neutralatmospheric boundary layer (NABL) are reinvestigated to determine thecause for turbulence overpredictions found in previous applications. Analytical solutions to the coupled E and equations for the case of steady balance between transport and dissipation terms, the dominant balance just below the NABL top, are derived. It is found that analytical turbulence profiles laminarizeat a finite height only for values of closure parameter ratio c ₂ /_e equal toor slightly greater than one, with laminarization as z for greater . The point = 2 is additionally foundthat where analytical turbulent length scale (l) profilesmade a transition from ones ofdecreasing ( < 2) to increasing ( > 2)values with height. Numerically predicted profiles near the NABL topare consistent with analytical findings. The height-increasingvalues of l predicted throughout the NABL with standard values ofclosure parameters thus appear a consequence of 2.5(> 2), implied by these values (c ₂ = 1.92, _{= 1.3}, _{e = 1}). Comparison of numericalpredictions with DNS data shows that turbulence overpredictions obtained with standard-valued parameters are rectifiedby resetting and _e to 1.1 and 1.6, respectively, giving, with c ₂ = 1.92, 1.3, and laminarization of the NABL's cappingtransport-dissipation region at a finite height.     

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.     

Turbulence Closures In Neutral Boundary Layer Over Complex Terrain

In this work, three turbulence closure models, Mellor andYamada level 2.5, E - l and E - implemented in a circulation model, are compared in neutral condition over complex terrain. They are firstly applied to a one-dimensional case on flat terrain and then to a schematic two-dimensional valley. The simulation results, in terms of wind field and turbulent kinetic energy, are tested against measurements from a wind-tunnel experiment. The empirical constants defining the characteristic length scales of the closures are modified based on turbulence parameters estimated in the experiment. The formulation of the diffusion coefficients is analysed to explain the differences among the various closures in the simulation results. Regarding the mean flow, both on flat and complex terrain, all the closures yield satisfactory results. Concerning the turbulent kinetic energy, the best results are obtained by E - l and E - closures.     

The use of σ T as a temperature scale in the atmospheric surface layer

The standard deviation of temperature _T is proposed as a temperature scale and as a velocity scale to describe the behaviour of turbulent flows in the Atmospheric Surface Layer (ASL), instead of _* andu _* of the Monin—Obukhov similarity theory, and ofT _f andU _f used for free convection stability conditions. On the basis of experimental evidence reported in the literature, it is shown that _T T _f andv _* U _f in the free convection region, and _{T *} andv _* U _* in nearneutral and stable conditions. This implies that the proposed scales can be applied for all stabilities. Furthermore, a new length scale is proposed and its relation with Obukhov length is given. Also, a simple semi-empirical expression is presented with which _T andv _* can be evaluated in a rather simple way. Some examples of practical applications are given, e.g., a stability classification for unstable conditions.     

A numerical model study of the structure and similarity scaling of the nocturnal boundary layer (NBL)

A one-dimensional numerical model based on the equations of mean motion and turbulent kinetic energy (TKE), with Delage's (1974) mixing-length parameterization has been used to simulate the mean and turbulent structure of the evolving stably stratified nocturnal boundary layer (NBL). The model also includes a predictive equation for the surface temperature and longwave radiational cooling effects.In the absence of advective and gravity wave effects, it is found that the model-simulated structure, after a few hours of evolution, could be ordered fairly well by a similarity scaling (u _*0, _*0, L ₀, and h) based on surface fluxes and the NBL height. Simple expressions are suggested to describe the normalized profiles of momentum and heat fluxes, TKE, eddy-viscosity and energy dissipation. A good ordering of the same variables is also achieved by a local scaling (u _*0, _* and L) based on the height-dependent local fluxes. The normalized TKE, eddy viscosity and energy dissipation are unique functions of z/L and approach constant values as z/L , where L is the local Monin-Obukhov length. These constants are close to the values predicted for the surface layer as z/L , thus suggesting that the Monin-Obukhov similarity theory can be extended to the whole NBL, by using the local (height-dependent) scales in place of surface-layer scales. The observed NBL structure has been shown to follow local similarity (Nieuwstadt, 1984).     

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     

Temperature distribution and current system in a convectively mixed lake

During spring and autumn, many lakes in temperate latitudes experience intensive convective mixing in the vertical, which leads to almost isothermal conditions with depth. Thus the regime of turbulence appears to be similar with that characteristic of convective boundary layers in the atmosphere. In the present paper a simple analytical approach, based on boundary-layer theory, is applied to convective conditions in lakes. The aims of the paper are firstly to analyze in detail the temperature distribution during these periods, and secondly to investigate the current system, created by the horizontal temperature gradient and wind action. For these purposes, simple analytical solutions for the current velocities are derived under the assumption of depth-constant temperatures. The density-induced current velocities are shown to be small, in the order of a few mm/sec. The analytical model of wind-driven currents is compared with field data. The solution is in good qualitative agreement with observed current velocities under the condition that the wind field is steady for a relatively long time and that residual effects from former wind events are negligible.The effect of the current system on an approximately depth-constant temperature distribution is then checked by using the obtained current velocity fields in the heat transfer equation and deriving an analytical solution for the corrected temperature field. These temperature corrections are shown to be small, which indicates that it is reasonable to describe the temperature distribution with vertical isotherms.Notation T temperature - t time - x, y, z cartesian coordinates - molecular viscosity - _h , _v horizontal and vertical turbulent viscosity - K _h ,K _v horizontal and vertical turbulent conductivity - Q heat flux through the water surface - D depth - u, v, w average current velocity components inx, y andz directions - f Coriolis parameter - p pressure - density - g gravity acceleration - a constant in the freshwater state equation - h _s deviation from the average water surface elevation - L _*,H _* length and depth scale - U _*,W _* horizontal and vertical velocity scale - T temperature difference scale - bottom slope - u _* friction velocity at the water surface - von Karman constant - L Monin-Obukhov length scale - buoyancy parameter - l turbulence length scale - C ₁,C ₂,C ₃ dimensionless constants in the expressions for the vertical turbulent viscosity - , dimensionless vertical coordinate and dimensionless local depth - angle between surface stress direction andx-axis - T _bx ,T _by bottom stress components - c bottom drag coefficient     

Similarity theory of diffusion and the observed vertical spread in the diabatic surface layer

The extension of Lagrangian similarity theory of diffusion to stratified flow is examined, to improve its prediction of the vertical spread of a passive substance. In the basic equation, where is the average height of a cluster of particles,u _* is the friction velocity andL is Monin-Obukhov length. It is shown theoretically, under the assumption of an equivalence between the diffusivities of heat and matter, that the unspecified function is the reciprocal of a more familiar meteorological parameter _n , the dimensionless temperature gradient. The universal constantb is found to be approximately equal to von Karman's constant for various stability conditions. The predicted effect of stability on vertical spread shows excellent agreement with that of the published data from the O'Neill experiments.     

Carbon dioxide,water vapor and sensible heat exchanges of a grain sorghum canopy

With the aid of eddy correlation instrumentation, the components of the energy budget and CO₂ flux were measured over grain sorghum grown at Mead, Nebraska. Diurnal patterns of sensible heat, latent heat, CO₂ and momentum flux are examined for typical days. On a mostly clear day when the crop leaf area index was 3.7, net radiation reached a mid-day peak of 560 W m^-2, while sensible and latent heat fluxes peaked at 50 and 460 W m^-2, respectively. The peak CO₂ flux occurring just prior to solar noon was 1.5 mg m^-2(ground area) s^-1. CO₂ flux (respiration from plants, soil and roots) in the early evening was about -0.28 mg m^-2 (ground area) s^-1.A relationship between CO₂ flux and photosynthetically active radiation (PAR) was developed. Except during the late stage of growth (growth stage 8.5, toward the initiation of senescence), the crop showed no evidence of saturation up to PAR 1800 Ei m^-2s^-1. The light compensation point was found to be about 211 Ei m^-2s^-1. Examination of CO₂ flux-PAR relationships for selected days through the season indicated an aging effect in terms of a decrease in photosynthetic activity of the sorghum canopy. Measurements made on two consecutive days demonstrate the effects of weather conditions on CO₂ flux and carbon-water flux ratio (a measure of water use efficiency of the crop). The occurrence of regional sensible heat advection with concommitant high vapor pressure deficit and air temperature-limited CO₂ exchange reduced the carbon-water flux ratio.Published as Paper No. 7717, Journal Series, Nebraska Agricultural Research Division. The work was conducted under Regional Research Project 11-33 and Nebraska Agricultural Research Division Project 27-003.Formerly Post Doctoral Research Associate (now at the University of Connecticut Department of Renewable Natural Resources Storrs CT)     

A model of turbulence spectra in the atmospheric surface layer

The spectral equations of turbulent kinetic energy and temperature variance have been solved by using Onsager's energy cascade model and by extending Onsager's model to closure of terms that embody the interaction of turbulent and mean flow.The spectral model yields the following results: In a stably stratified shear flow, the peak wave numbers of the spectra of energy and temperature variance shift toward larger wave numbers as stability increases. In an unstably stratified flow, the peak wave numbers of energy spectra move toward smaller wave numbers as instability increases, whereas the opposite trend is observed for the peak wave numbers of temperature variance spectra. Hence, the peak wave numbers of temperature spectra show a discontinuity at the transition from stable to unstable stratification. At near neutral stratification, both spectra reveal a bimodal structure.The universal functions of the Monin-Obukhov similarity theory are predicted to behave as _m ~ _H ~ (- Z/L)^-1/3 in an extremely unstable stratification and as _m ~ _H ~ z/L in an extremely stable stratification. For a stably stratified flow, a constant turbulent Prandtl number is expected.     

Free convection scaling over the ocean derived from buoy measurements during gate

The structure of atmospheric turbulence in the surface layer over the open ocean is examined under conditions of local free convection. The raw data consist of profile and fluctuation measurements of wind and temperature as obtained from a meteorological buoy. For near neutral conditions and for waves running approximately along the wind direction, wave-induced wind fluctuations can be described by a simplified linear theory based on Miles (1957). In this case, the spectrum of wind velocity is given as the sum of two parts; for the turbulent part, the parameterization as obtained by Kaimal et al. (1972) applies, while the wave-induced part is parameterized using a simplification of Miles' linear theory. For cases of local free convection, the measurements of the vertical component of the wind velocity are well described by similarity theory; as expected, _w /(-uw)^1/2 is proportional to (- z/L)^1/3. In order to scale the longitudinal wind velocity component, it seems to be reasonable to extend the list of relevant parameters by the height of the mixed layer z _i. We obtain _u /(- uw)^1/2 (z/z _i)^1/3(- z/L)^1/3 with only a poor correlation coefficient of r = 0.6. Overall, the results of local free convection scaling obtained from direct measurements show good agreement with those obtained from profile measurements. A comparison between direct and indirect determination of turbulent fluxes of momentum shows an unexplained difference of about 20%. This discrepancy is mainly due to a gap in the uw-cospectrum at the swell frequency.