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.     

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     

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.     

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     

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.     

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.     

A non-linear climate oscillator controlled by biogeochemical cycling in the ocean: an alternative model of Quaternary ice age cycles

A new, biogeochemical model of ice age cycles is developed and applied which explains major features of climate variations in the late Quaternary —rapid ice age terminations, large glacial-interglacial amplitudes and 100-kyr cycles — in a way consistent with the paleorecord. Existing models which invoke non-linear, ice-sheet-earth-crust dynamics to explain ice age cycles are not consistent with simultaneous terminations in both hemispheres and other phase relationships implied by the paleorecord. The present model relates climate change to oscillations of oceanic primary (new) production controlled by the availability of inorganic nitrogen. Large oscillations follow shelf erosion events triggered by small sea-level drops. These drops are due to glacial buildup associated with a minimum in Northern Hemisphere insolation. Rapid global warming at terminations is initiated by open ocean denitrification events leading to new production crashes and rapid modification of atmospheric trace gas concentrations (CO₂, DMS, N₂O). Other feedbacks of the land-ice-atmosphere-ocean system control the rest of the climate cycle. 100-kyr cycles derive from orbital pacemaking of the strong, low-frequency model response. Results suggest that the climate regime transition near 800 kyr B.P. may be related to changes in the continental shelf slope, that existing chronologies based on orbital tuning may need to be revised and that temporary increases in atmospheric N₂O concentrations at terminations, due to the denitrification events, may have caused significant greenhouse warming. A spike of elevated N₂O concentration at terminations may be recorded in polar ice.     

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.     

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%.     

Kritische Bemerkung zur Frage der Temperatur-abhängigkeit der Ozonverteilung

Zusammenfassung A. undE. Vassy haben in der Frage der Temperatur-abhängigkeit des Ozongehalts der Atmosphäre aus der Gleichung loge _n –logJ _n logK(T _n ) geschlossen, daß auch die Gleichung loge _n logJ _n +logK(T _n ) gültig sei. Es wird hier nun gezeigt, daß die bei der ersten Gleichung erlaubten Vernachlässigungen bei der zweiten zu großen Fehlern führen können und daß daher von A. undE. Vassy kein Beweis für die Richtigkeit der Beziehunge=J.K(T) erbracht ist.

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Summary In the question of temperature dependence of ozone content of the atmosphere A. andE. Vassy have concluded from the equation loge _n –logJ _n logK(T _n ) that also the formula loge _n logJ _n +logK(T _n ) must be valid. In this paper it is proved that the neglections which may be admitted for the first equation, can conduct to great errors. Therefore A. andE. Vassy have not produced a proof for the correctness of the equatione=J.K(T).

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Résumé A. etE. Vassy en étuidant le problème de la teneur de l'ozone atmosphérique en relation avec la température ont admis que l'équation loge _n –logJ _n logK(T _n ) entraînait aussi la relation loge _n logJ _n +logK(T _n ). On montre ici que les simplifications admises pour la première équation conduisent pour l'application de la seconde à de fortes erreurs, et que par conséquent ces auteurs n'ont pas fourni de preuve de la justesse de la relatione=J.K(T).

     

Model-based estimates of water loss from “patches” of the understory mosaic of the Hartheim Scots pine plantation

Summary During the Hartheim Experiment (HartX) 1992 conducted in the Upper Rhine Valley, Germany, we estimated water vapor flux from the understory and the forest floor by several methods. At the vegetation patch level, direct estimates were made with small weighing lysimeters, and water loss was scaled-up to the stand level based on vegetation patchtype distribution. At the leaf level, transpiration flux was determined with a CO₂/H₂O porometer for the dominant understory plant species,Brachypodium pinnatum, Carex alba, andCarex flacca. Measured leaf transpiration was scaled-up to patch level with a canopy light interception and leaf gas exchange model, and then to stand level as in the case of lysimeter data, but with further consideration of patchtype leaf area index (LAI). On two days, total understory latent heat flux was estimated by eddy correlation methods below the tree canopy.The understory vegetation was subdivided into five major patch-types which covered 62% of the ground area and resulted in a cumulative LAI of approx. 1.54 when averaged over total stand ground area and compared to the average tree canopy LAI of 2.8. The remaining 38% of ground area was unvegetated bare soil and/or covered by moss (mainly byScleropodium purum) or litter. The evapotranspiration from the understory and unvegetated areas equaled approx. 20% of total forest stand transpiration during the HartX period. The understory vegetation transpired about 0.4 mm d^–1 (13%) estimated over the period of May 13 to 21, whereas evaporation from moss and soil patches amounted 0.23 mm d^–1 (7.0%). On dry, sunny days, total water vapor flux below the tree canopy exceeded 0.66 mm d^–1. Using the transpiration rates derived from the GAS-FLUX model together with estimates of evaporation from moss and soil areas and a modified application of the Penman-Monteith equation, the average daily maximum conductance of the understory and the forest floor was 1.7 mm s^–1 as compared to 5.5 mm s^–1 for the tree canopy.With 6 Figures     

Modelling evaporation from wetland tundra

Evapotranspiration is a major component of both the energy and water balances of wetland tundra environments during the thaw season. Reliable estimates of evapotranspiration are required in the analysis of climatological and hydrological processes occurring within a wetland and in interfacing the surface climate with atmospheric processes. Where direct measurements are unavailable, models designed to accurately predict evapotranspiration for a particular wetland are used.This paper evaluates the performance, sensitivity and limitations of three physically-based, one-dimensional models in the simulation of evaporation from a wetland sedge tundra in the Hudson Bay Lowland near Churchill, Manitoba. The surface of the study site consists of near-saturated peat soil with a sparse sedge canopy and a constantly varying coverage of standing water. Measured evaporation used the Bowen ratio energy balance approach, to which the model results were compared. The comparisons were conducted with hourly and daily simulations.The three models are the Penman-Monteith model, the Shuttleworth-Wallace sparse canopy model and a modified Penman-Monteith model which is weighted for surface area of the evaporation sources.Results from the study suggest that the weighted Penman-Monteith model has the highest potential for use as a predictive tool. In all three cases, the importance of accurately measuring the surface area of each evaporation source is recognized. The difficulty in determining a representative surface resistance for each source and the associated problems in modelling without it are discussed.

List of Symbols

Models BREB Bowen ratio energy balance - P-M Penman-Monteith combination - S-W Shuttleworth-Wallace combination - W-P-M Weighted Penman-Monteith combination Other AE Available energy-all surfaces - AE _c Available energy-canopy (S-W, W-P-M) - AE _s Available energy-bare soil (S-W, W-P-M) - AE _w Available energy-open water (W-P-M) - C _p Specific heat of air - D Vapor pressure deficit - DAI Dead area index - FAI Foliage area index - LAI Leaf area index - Q ^* Net radiation - Q _e Latent heat flux-total - Q _ec Latent heat flux-canopy (S-W, W-P-M) - Q _es Latent heat flux-bare soil (S-W, W-P-M) - Q _ew Latent heat flux-open water (W-P-M) - Q _g ground heat flux - Q _h Sensible heat flux - S Proportion of area in bare soil - W Proportion of surface in open water - r _a Aerodynamic resistance (P-M, W-P-M) - r _c Canopy resistance - r _s Generalized optimized surface resistance - r _st Stomatal resistance - r _c ^a Bulk boundary layer resistance (S-W) - r _s ^a Aerodynamic resistance below mean canopy level (S-W) - r _s ^s Soil surface resistance (S-W, W-P-M) Greek Bowen ratio - Psychrometer constant - Air density - Slope of saturation vapour pressure vs temperature curve     

In-situ measurements of the aerosol size distributions,physicochemistry and light absorption properties of Arctic haze

Thermal and optical techniques were used at Barrow, Alaska during AGASP II (3/20/86–4/7/86) to measure in-situ variability of major aerosol components present in Arctic Haze. The experiment provided continuous data on the concentration, size distribution and relative proportions of sulfate species and refractory aerosol for particle diameters of 0.15 to 5 m. Filter samples were also taken for determination of aerosol optical absorption due to soot (EC-elemental carbon). Although pronounced haze events were absence during this period the haze aerosol present varied in concentration between 2 and 6 g/m³ but showed little change in relative constituents. Apart from local influences, the optical data indicated a persistent fine-mode sulfate aerosol with a NH₄ ⁺/SO₄ ^– molar ratio of about 0.4 and a refractory component of somewhat less than 10% by mass. A preliminary comparison of soot estimates determined from the light absorption data with the size distributions of refractory aerosol observed independently by the optical particle counter showed good agreement during the sample period. In the absence of local pollution, values of single scatter albedo derived from light scattering and light absorption showed similar variation about the average value of 0.86 found by us during flights north of Barrow three years earlier during AGASP I.     

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     

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.     

Effect of land management on ecosystem carbon fluxes at a subalpine grassland site in the Swiss Alps

Summary The influence of agricultural management on the CO₂ budget of a typical subalpine grassland was investigated at the Swiss CARBOMONT site at Rigi-Seebodenalp (1025m a.s.l.) in Central Switzerland. Eddy covariance flux measurements obtained during the first growing season from the mid of spring until the first snow fall (17 Mai to 25 September 2002) are reported. With respect to the 10-year average 1992–2001, we found that this growing season had started 10 days earlier than normal, but was close to average temperature with above-normal precipitation (100–255% depending on month). Using a footprint model we found that a simple approach using wind direction sectors was adequate to classify our CO₂ fluxes as being controlled by either meadow or pasture. Two significantly different light response curves could be determined: one for periods with external interventions (grass cutting, cattle grazing) and the other for periods without external interventions. Other than this, meadow and pasture were similar, with a net carbon gain of –128±17g Cm^–2 on the undisturbed meadow, and a net carbon loss of 79±17g Cm^–2 on the managed meadow, and 270±24g Cm^–2 on the pasture during 131 days of the growing season, respectively. The grass cut in June reduced the gross CO₂ uptake of the meadow by 50±2% until regrowth of the vegetation. Cattle grazing reduced gross uptake over the whole vegetation period (37±2%), but left respiration at a similar level as observed in the meadow.     

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 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.     

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.     

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.