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.     

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

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

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

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

Regular and seasonal behaviour of atmospheric radio noise field strength (ARNFS) over low latitude station calcutta

Summary The electromagnetic radiation of cloud discharge known as atmospheric radio noise field strength (ARNFS) shows a gradual fall from a frequency of 9 kHz to 81 kHz as studied over a period of two years at Calcutta, very close to Bay of Bengal. The main characteristic features of ARNFS at Calcutta are that-(i) ARNFS shows that midday median value is smaller than midnight median value in all months, (ii) level of daily minimum is higher in February and monsoon compared to other seasons, (iii) sunrise effect and sunset effect are well correlated with local sunrise and sunset times, (iv) the magnitude of sunrise fade and sunrise fade rate are maximum in April and lowest during winter period, (v) the magnitude of sunset fade is higher in premonsoon and postmonsoon while it is lowest in monsoon, (vi) number of occurrence of both sunrise effect and sunset effect is remark-ably smaller in monsoon. The positions of the sun and of atmospheric sources are jointly the causes of seasonal and diurnal variations. The missing of sunrise effect and sunset effect are due to local cloud activity and variation of electron density during geomagnetic storms.With 7 Figures     

Observed variations of σθ and σΦ in the nocturnal drainage flow in a deep valley

The variations of and in the drainage flow in the Brush Creek valley of western Colorado are investigated using data from Doppler acoustic sodars and instrumented towers. The data were obtained on two experimental nights during the 1984 ASCOT field study. There is good agreement between the variations derived from low-level observations of the sodars and those derived from the towers located throughout the valley. The observed hourly average and in the nocturnal drainage flow are about 20 ° to 25 ° and 5 °, respectively; these values are much larger than those generally observed over flat terrain during nighttime stable conditions. After sunrise (about 0600 MST), as the valley warms and the flow direction changes to up-valley, these parameters increase sharply to their peak values at about 0800 MST and then decrease to their normal daytime values after about two hours.In the drainage flow, the hourly average varies inversely with wind speed according to the relation u 0.7ms^-1. The vertical standard deviation is much less enhanced by complex terrain than the horizontal standard deviation. The observed values are predicted fairly well by the local similarity theory.Oak Ridge Associated Universities (ORAU) Summer Research Participant at ATDD in 1987 andOak Ridge Associated Universities (ORAU) Summer Research Participant at ATDD in 1987 and     

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     

The validation of various schemes for parameterizing evaporation from bare soil for use in meteorological models: A numerical study using in situ data

Parameterization of evaporation from a non-plant-covered surface is very important in the hierarchy strategy of modelling land surface processes. One of the representations frequently used in its computation is the resistance formulation. The performance of the evaporation schemes using the , , and their combination resistance approaches to parameterize evaporation from bare soil surfaces is discussed. For that purpose, the nine schemes, based on a different dependence of and on volumetric soil moisture content and its saturated value, are used.The tests of performances of the considered schemes are based on time integrations by the land surface module (BARESOIL) using observed data. The 23 data sets at a bare surface experimental site in Rimski anevi, Yugoslavia on chernozem soil, were used for the resistance algorithm evaluation. The quality of the schemes was compared with the observed values of the latent heat flux using several statistical parameters.     

A study of the sensitivity of bare soil evaporation schemes to soil surface wetness,using the coupled soil moisture and surface temperature prediction model,BARESOIL

Summary The performance of evaporation schemes with and approach and their combination within resistance representation of evaporation from bare soil surface is discussed. For this purpose nine schemes, based on different functions of or , on the ratio of the volumetric soil moisture content and its saturated value are used.The quality of the chosen schemes has been evaluated using the results of time integration by the coupled soil moisture and surface temperature prediction model, BARESOIL, using in situ data. A sensitivity analysis was made using two sets of data derived from the volumetric soil moisture content of the top soil layer. One with values below the wilting point (0.17 m³m^–3) and the second with values above 0.20m³m^–3. Data sets were obtained at the experimental site Rimski anevi, Yugoslavia, from the bare surface of a chernozem soil.With 4 Figures     

Similarity of atmospheric Reynolds shear stress and heat flux fluctuations over a rough surface

Horizontal u and vertical w velocity fluctuations have been measured together with temperature fluctuations in the atmospheric surface layer, at a small height above a wheat crop canopy. Marginal probability density functions are presented for both individual fluctuations u, w, and for the instantaneous Reynolds stress uw, and heat fluxes w and u. Probability density functions of the velocity fluctuations deviate less significantly from the Gaussian form than the probability density of temperature. There appears to be closer similarity between statistics of the instantaneous heat fluxes than between the momentum flux and either of the heat fluxes investigated. The mean momentum flux receives equal contributions from the events referred to as ejections and sweeps in laboratory boundary layers. Sweeps provide the largest contribution to the heat fluxes.     

Energy efficiency and greenhouse abatement costs (comment on Lovins and Lovins)

Comment on Amory B. and L. Hunter Lovins:Profitably Stabilizing Global Climate - An Editorial, this issue, Clim. Change.     

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

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

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.     

Shear convection

The paper discusses convection in the presence of wind shear, a condition analysed previously by Zilitinkevich (1971). This region (between the forced and fully developed convective layers) was also considered by Betchov and Yaglom (1971). In the present paper the author endeavors to develop a consistent analysis from the basic hypothesis of a very weak interaction between the vertical convective motions and mechanical turbulence, employing a new similarity model of the turbulent regime. Additional experimental data are introduced. Unlike the notation used in the references quoted above, this regime is termed shear convection rather than free convection. The latter is traditionally regarded as synonymous with the terms pure or fully developed convection.     

On Trajectory Curvature as a Selection Criterion for Valid Lagrangian Stochastic Dispersion Models

Recently Wilson and Flesch (Boundary-Layer Meteorology, 84, 411-426, 1997) suggested that the average increment d z to the orientation = arctan(w/u) of the Lagrangian velocity-fluctuation vector can be used to distinguish the better Lagrangian stochastic models within the well-mixed class. Here it is demonstrated that the specification of d z constitutes neither a sufficient or universally applicable criterion to distinguish the better Lagrangian stochastic models within the well-mixed class. The hypothesis made by Wilson and Flesch that Lagrangian stochastic models with /P_E irrotational are zero-spin models, having d z=0, is proven     

A study of a fair weather boundary layer in TOGA-COARE: Parameterization of surface fluxes in large scale and regional models for light wind conditions

The study focuses on a way to parameterize the effect of subgrid scale convective motions on surface fluxes in large scale and regional models for the case of light surface winds. As previously proposed, these subgrid effects are assumed to scale with the convection intensity through the relationship: where is the mean velocity of the wind, U₀ the velocity of the mean wind, w_* the free convection velocity, and an empirical coefficient to be determined. Both observations and numerical simulation are presently used to determine the free convection coefficient .Large eddy simulation of a fair weather convective boundary layer case observed during TOGA-COARE is performed. Comparisons between observations and the simulation of surface properties and vertical profiles in the planetary boundary layer are presented. The simulated vertical turbulent fluxes of heat, moisture and buoyancy range well within estimates from aircraft measurements.The most important result is that the true free convection coefficient , directly estimated from simulation, leads to a value of 0.65, smaller than the ones estimated from temporal and spatial variances. Using observations and simulation, estimates of from temporal and spatial variances are obtained with similar values 0.8. From both theoretical derivations and numerical computations, it is shown that estimates of the true from variances are possible but only after applying a correction factor equal to 0.8. If this correction is not used, is overestimated by about 25%. The time and space sampling problem is also addressed in using numerical simulations.     

An observational study of heat fluxes and their relationships with net radiation

Experimental evidence indicates that the diurnal behaviour of the fluxes of heat into the ground and into the atmosphere versus the net flux of radiation can be modelled by closed curves, the hourly values folowing one another in either a clockwise or counter clockfashion. A general formulation to express the different heat fluxes as a function of net radiation is proposed. This relationship between the different heat fluxes and can be expressed as a sum of three terms: the first indicates a direct proportionality to , the second gives the deviation from linearity and depends on /t, and the third gives the value of the flux when = 0. The formulae are then expressed as a function of time and the ratios between the heat fluxes and are evaluated. A comparison with the approximations generally used shows that the latter may be considered as particular cases of the more general equations proposed here.     

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.     

Analytical investigations of horizontal meso-scale momentum equations with Newtonian nudging

Summary This study presents an analytical investigation of the local behaviour of the solution to a mesoscale model with Newtonian nudging when observed winds are time varying. The analysis examines each Fourier component of the time series of observed winds. Unlike the case with a constant observed wind, the nudged wind vector does not asymptotically approach the observed wind. In response to sinusoidal oscillation of the observed wind, the nudged wind vector is always on a half circle connecting the vector ends of the observed and un-nudged modelled winds. When nudging parameter 0, the nudged wind vector approaches the un-nudged wind; when , the nudged wind vector approaches the observed wind. For commonly used values of nudging parameter , the modelled wind field always carries errors.A target nudging scheme is devised in this study in order to ensure the model result is identical to observed winds with sinusoidal oscillation. Investigation shows that such a target wind exists for a finite value of , and the magnitude of the target-nudging term is about the same as that of a normal nudging term if f, wheref is the Coriolis parameter and is the frequency of the wind oscillation.With 7 Figures