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.     

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.     

A review of flux-profile relationships

Flux-profile relationships in the constant flux layer are reviewed. The preferred relationships are found to be those of Dyer and Hicks (1970), namely, _H = _W =(1–16(z/L))^–1/2, _M =(1–16(z/L))^–1/4 for the unstable region, and _H = _W = _M = 1+5(z/L) for the stable region.The carefully determined results of Businger et al. (1971) remain a difficulty which calls for considerable clarification.     

Analytical solutions for the Ekman layer

The PBL equation that governs the transition from the constant-stress surface layer to the geostrophic wind in a neutrally stratified atmosphere for which the eddy viscosityK(z) is assumed to vary smoothly from the surface-layer value U _*z (0.4,U _*=friction velocity,z=elevation) to the geostrophic asymptoteK _GU _*d forzd is solved through an expansion in fd/U _*1 (f=Coriolis parameter). The resulting solution is separated into Ekman's constant-K solution an inner component that reduces to the classical logarithmic form forzd and isO() relative to the Ekman component forzd. The approximationKU _*d is supported by the solution of Nee and Kovasznay's phenomenological transport equation forK(z), which yieldsK–U _*d exp(–z/d), where is an empirical constant for which observation implies, 1. The parametersA andB in Kazanskii and Monin's similarity relation forG/U _* (G=geostrophic velocity) are determined as functions of . The predicted values ofG/U _* and the turning angle are in agreement with the observed values for the Leipzig wind profile. The predicted value ofB based on the assumption of asymptotically constantK is 4.5, while that based on the Nee-Kovasznay model is 5.1; these compare with the observed value of 4.7 for the Leipzig profile. A thermal wind correction, an asymptotic solution for arbitraryK(z) and 1, and an exact (unrestricted ) solution forK(z)=U _*d[1–exp(–z/d)] are developed in appendices.     

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     

On the temperature coefficient of PCO 2 in seawater

The commonly reported temperature coefficient of P. the equilibrium partial pressure of CO₂, is (P/T) _A,C ,which is about 15 ppm/°C, or 5% of the atmospheric partial pressure of CO₂. This coefficient, however, applies only to deep water, not to surface water which can exchange CO₂ with the atmosphere. The coefficient (P/T) _A,C ,, where designates constancy of the sum of atmospheric and surface-ocean CO₂, is the appropriate value for air-sea exchange. Numerical values are mass-dependent because the depth of the exchanging ocean layer must be specified. For a 100-m surface layer, the value is ca. 1.5 ppm/°C, or 0.5% of ambient CO₂. Editor's Note:In view of the interdisciplinary importance of the carbon dioxide-climate problem, this note on seawater chemistry should be of interest to specialists beyond the discipline of ocean chemistry.     

Three-dimensional modeling of synthetic cold fronts interacting with northern Alpine foehn

Summary The effect of the Alpine orography on prototype cold fronts approaching from the west is investigated by three-dimensional numerical model simulations. The numerical experiments cover a range of parameter constellations which govern the prefrontal environment of the front. Especially, the appearance and intensity of prefrontal northern Alpine foehn varies from case to case.The behaviour of a cold front north of the Alps depends much on the prefrontal condition it encounters. It is found that prefrontal foehn can either accelerate or retard the approaching front.An important feature is the pressure depression along the northern Alpine rim that results from the southerly foehn flow. In cases where this depression compensates the eastward directed pressure gradient associated with the largescale flow, the front tends to accelerate and the foehn breaks down as soon as the front passes. In contrast, the foehn prevents the front from a rapid eastward propagation if it is connected with a strong southerly wind component.No-foehn experiments are performed for comparison, where either the mountains are removed, or the static stability is set to neutral. Also shown are effects of different crossfrontal temperature contrasts.List of Symbols c _F propagation speed of a front - x, y horizontal grid spacing (cartesian system) - , horizontal grid spacing (geographic system) - t time step - z vertical grid spacing (cartesian system) - cross-frontal potential temperature difference - _i potential temperature step at an inversion - E turbulent kinetic energy - f Coriolis parameter - FGP frontogenesis parameter (see section 2.2) - g gravity acceleration (g=9.81 m s^–2) - vertical gradient of potential temperature - h terrain elevation (above MSL) - h _i height of an inversion (h _i =1000 m MSL) - H height of model lid (H=9000 m MSL) - K _M exchange coefficient of momentum - K _H exchange coefficient of heat and moisture - longitude - N Brunt-Väisäla-frequency - p pressure - Exner function (=T/) - latitude - q _v specific humidity - R _d gas constant of dry air (R _d =287.06 J kg^–1 K^–1) - density of dry air - t time - T temperature - potential temperature - TFP thermal front parameter (see section 2.2) - u, v, w cartesian wind components - u _g ,v _g geostrophic wind components - horizontal wind vector - x, y, z cartesian coordinates Abbreviations GND (above) ground level - MSL (above) mean sea level - UTC universal time coordinated With 20 Figures     

An observational aircraft-based study of sea-breeze frontogenesis

In the summer of 1988/89 flights were carried out in the Coorong coastal area of South Australia to investigate sea-breeze fronts. The flights yielded data sets of the structure of the fronts in the cross-frontal direction with a spatial resolution of approximately 3 m. The study is focused on the budgets of sensible and latent heat in the vicinity of the front and on frontogenesis/frontolysis processes which are closely related to budget considerations.The frontogenesis relationships and the budgets were established on a 2 km length scale by low-pass filtering of the space series. As the wind components were measured with high accuracy, all processes which determine frontogenesis could be evaluated and are displayed in x,z-cross-sections: these are the confluence, shear and diabatic effects, all of which play a role in q/x-, q/z-, /x- as well as /z-frontogenesis. A detailed analysis is given for two different states of frontal development. The presented results shed much light on the governing physical processes in the frontal region with strong emphasis on the effects of confluence-generated updrafts, on shear instabilities causing bulges and clefts in the frontal surface as well as producing the elevated frontal head, and on processes related to differential heating and moistening.     

Equilibrium evaporation beneath a growing convective boundary layer

Expressions for the equilibrium surface Bowen ratio ( _s ) and equilibrium evaporation are derived for a growing convective boundary layer (CBL) in terms of the Bowen ratio at the top of the mixed layer _i and the entrainment parameter A _R . If A_R is put equal to zero, the solution for _s becomes-that previously obtained for the zero entrainment or closed box model. The Priestley-Taylor parameter is also calculated and plotted in terms ofA _R and _i . Realistic combinations of the atmospheric parameters give values of in the range 1.1 to 1.4.     

Effect of finite sampling on atmospheric spectra

The effect of a finite averaging time on variances is well known, but its effect on power spectra is less clearly understood. We present numerical solutions for the spectral distortion arising from sampling over a finite time interval T and show that the commonly used filter function (1 – sinc²f T), valid for variances, is a reasonable approximation for power spectra only when T 10 _m , where f is the cyclic frequency, and _m is the dominant time scale of the process. Our results exhibit an increasingly steeper low-frequency roll-off as T decreases relative to _m , indicating that the measured spectrum is subject to a greater suppression of the lower frequencies (f > 1/T) than predicted by (1 – sinc²f T). This suppression is, in a sense, compensated by an overestimation of spectral estimates in the frequency range f 1/T.     

Boundary-layer parameterizations for applied dispersion modeling over urban areas

Many applied dispersion models require the knowledge of boundary-layer parameters such as sensible heat flux,Q _H , friction velocity,u _*, and turbulent energy components, _w and _v . Formulas are suggested for calculating these parameters over a wide variety of types of ground surfaces, based on simple observations of wind speed near the ground and fractional cloud cover, and specification of constants such as roughness length, albedo, and soil moisture availability. Observations ofu _*,Q _H , _w , and _v during field experiments in St. Louis and Indianapolis are used to test the formulas for urban sites. Relative errors of about ±20% in the predictions are seen to occur whenu _*,Q _H , _w , and _v are large. However, when these quantities are small (e.g.,u _* < 0.2 m/s), the errors in the predictions are as large as the mean value of the quantity itself.In addition, it is concluded from studies of available field data and theories that the magnitude of _w is not well-known at elevations above about 100m during the late afternoon and night. Some simple parameterizations for _w . are suggested that are consistent with the observed steady decrease in ground-level concentration in the afternoon and the sudden increase in concentration that can occur a few hours after sunset due to wind shears associated with a low-level jet, for continuous plumes emitted from moderate to tall stacks.     

Occurrence of roll circulations in a shallow boundary layer

Meteorological measurements taken at the Näsudden wind turbine site during slightly unstable conditions have been analyzed. The height of the convective boundary layer (CBL) was rather low, varying between 60 and 300 m. Turbulence statistics near the ground followed Monin-Obukhov similarity, whereas the remaining part of the boundary layer can be regarded as a near neutral upper layer. In 55% of the runs, horizontal roll vortices were found. Those were the most unstable runs, with -z _i/L > 5. Spectra and co-spectra are used to identify the structures. Three roll indicators were identified: (i) a low frequency peak in the spectrum of the lateral component at low level; (ii) a corresponding increase in the vertical component at mid-CBL; (iii) a positive covariance {ovvw} together with positive wind shear in the lateral direction (V/z) in the CBL. By applying these indicators, it is possible to show that horizontal roll circulations are likely to be a common phenomenon over the Baltic during late summer and early winter.     

Free convection frequency spectra of atmospheric turbulence over the sea

Frequency spectra of atmospheric turbulenceS (f) in the inertial subrange are considered in the free convection regime over the sea surface in a case of motionless instrument measurements (Eulerian frequency spectra). The frequency spectra formulaef _* S (f)/ ² =c (f _*/f)^5/3 for wind velocity (=1–3), temperature (=t) and humidity (=e) fluctuations are derived on the basis of similarity theory and the –5/3 law. These relations also can be derived from a consideration of convective large-scale advection of small eddies. The frequency scalef _* = (N ^{1 2}/)^1/2 (H/z ²)^1/3 is the lower bound of the inertial subrange and it is of order 10^–2 Hz.The spectra formulae are compared with direct measurements of atmospheric turbulence from the fixed research tower in the coastal zone of the Black Sea in calm weather. It is shown that these formulae are realized at least over two to three decades of the frequency range (approximately from 10^–2 to 10 Hz) and values of the numerical coefficients are found. The derived formulae can be used for calculations of sensible and latent heat fluxes by measuring the high-frequency range of spectra at a fixed point at low wind speeds when the conventional inertial dissipation method is not applicable.     

Markov-chain simulation of particle dispersion in inhomogeneous flows: The mean drift velocity induced by a gradient in Eulerian velocity variance

The Langevin equation is used to derive the Markov equation for the vertical velocity of a fluid particle moving in turbulent flow. It is shown that if the Eulerian velocity variance _wE is not constant with height, there is an associated vertical pressure gradient which appears as a force-like term in the Markov equation. The correct form of the Markov equation is: w(t + t) = aw(t) + b _wE + (1 – a)T _L ( _wE ²)/z, where w(t) is the vertical velocity at time t, a random number from a Gaussian distribution with zero mean and unit variance, T _L the Lagrangian integral time scale for vertical velocity, a = exp(–t/T _L), and b = (1 – a ²)^1/2. This equation can be used for inhomogeneous turbulence in which the mean wind speed, _wE and T _L vary with height. A two-dimensional numerical simulation shows that when this equation is used, an initially uniform distribution of tracer remains uniform.     

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.     

Numerical modeling of the nocturnal urban boundary layer

A numerical case study with a second-order turbulence closure model is proposed to study the role of urban canopy layer (UCL) for the formation of the nocturnal urban boundary layer (UBL). The turbulent diffusion coefficient was determined from an algebraic stress model. The concept of urban building surface area density is proposed to represent the UCL. Calculated results were also compared with field observation data. The height of the elevated inversion above an urban center was simulated and found to be approximately twice the average building height. The turbulent kinetic energy k, energy dissipation rate , and turbulence intensities u ² and w ² increase rapidly at the upwind edge of the urban area. The Reynolds stress uw displayed a nearly uniform profile inside the UBL, and the vertical sensible heat flux w had a negative value at the inversion base height. This indicates that the downward transport of sensible heat from the inversion base may play an important role in the formation of the nocturnal UBL.     

Diurnal variation of horizontal wind direction fluctuations in complex terrain at Geysers,Cal.

Horizontal diffusion in the surface layer is dependent on the standard deviation of wind direction fluctuations . Diurnal variation of this parameter in complex terrain was studied for the July 1979 Geysers, Cal., experiment using data from a network of 11 short meteorological towers in the 25 km² Anderson Creek watershed Valley side slopes are roughly 20 ° and maximum terrain difference is about 1 km.Values of for wind directions sampled for one hour at a height of 10 m are about 35 ° during the daytime. They slowly decrease to about 20 ° by 8 to 10 p.m. as stability increases but wind speeds are still relatively high. After 10 p.m. the drainage flow sets in at most stations, with speeds of 1 to 2 m s^-1, and average increases to about 30° during the period 11 p.m. to 6 a.m. In general, highest values of at night are associated with lowest values of wind speed and greatest static stability. This enhancement of by the terrain suggests that horizontal diffusion at night always conforms to that expected during nearly neutral stabilities. That is, Pasquill class D diffusion applies to the horizontal component all night in complex terrain.     

Second-order closure study of the covariance between chemically reactive species in the surface layer

A second-order modelling technique is used to investigate the influence of turbulence on chemical reactions. The covariance and variance equations for the NO-O₃-NO₂ system are developed as a function of the ratio of the timescale of turbulence ( _t ) and the timescale of chemistry (_Ch): the first Damköhler number ( _t /_Ch). Special attention is given to the calculation of the covariance between NO and O₃ normalized by the product of their means, the so-called intensity of segregation (I _S ). This parameter quantifies the state of mixing of two chemical species.The intensity of segregation is calculated as a function of the flux of NO and the first Damköhler number. The model results presented illustrate the importance of taking the effect of turbulence on chemical reactions into account for higher values of the NO flux, for values of the ratio O₃/NO larger than 12.5 and for values of the ratio _t /_CH larger than 0.1. For such cases, the effective reaction rates are slower than if the chemical species are assumed to be uniformly mixed.     

Nearly steady convection and the boundary-layer budgets of water vapor and sensible heat

The budgets of water vapor and sensible heat in the convective atmospheric boundary (mixed) layer are analyzed by means of a simple slab approach adapted to steady large-scale advective conditions with radiation and cloud activity. The entrainment flux for sensible heat is assumed to be a linear function of the surface flux. The flux of water vapor at the top of the mixed layer is parameterized by extending the first-order Betts-Deardorff approach, i.e., by adopting linear changes for both the specific humidity and the flux across the mixed layer and across the inversion layer of finite thickness. In this way the dissimilarity of sensible heat and water vapor transport in the mixed layer can be taken into account. The experimental data were obtained from the Air Mass Transformation Experiment (AMTEX). The entrainment constant for sensible heat at the top of the mixed layer was found to have values similar to those observed in other weakly convective situations, i.e., around 0.4 to 0.6. This appears to indicate that the effect of mechanical turbulence was not negligible; however, the inclusion of this effect in the formulation did not improve the correlation. In contrast to the first-order approach, the zero-order approach, i. e., the jump equation commonly used for the flux of a scalar at the inversion, (ovwc ) _h = w_e c (where w _e is the entrainment velocity and c the concentration jump across the inversion), was found to be invalid and incapable of describing the data.     

Numerical integration errors in calculated tropospheric photodissociation rate coefficients

Tropospheric photodissociation rate coefficients (J values) were calculated for NO₂, O₃, HNO₂, CH₂O, and CH₃CHO using high spectral resolution (0.1 mm wavelength increments), and compared to the J values obtained with numerically degraded resolution (=1, 2, 4, 6, 8, and 10 nm, and several commonly used nonuniform grids). Depending on the molecule, substantial errors can be introduced by the larger increments. Thus for =10 nm, errors are less than 1% for NO₂, less than 2% for HNO₂, +6.5% to -16% for CH₂O, -6.9% to +24% for CH₃CHO, and -24% to +110% for O₃. The errors for CH₂O arise from the fine structure of its absorption spectrum, and are prevalently negative (underestimate of J). The errors for O₃, and to a lesser extent for CH₃CHO, arise mainly from under-resolving the overlap of the molecular action spectrum and the tropospheric actinic flux in the wavelength region of stratospheric ozone attenuation. The sign of those errors depends on whether the actinic flux is averaged onto the grid before or after the radiative transfer calculation. In all cases studied, grids with 2 nm produced errors no larger than 5%.