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.     

Interpretation of Mauna Loa atmospheric transmission relative to aerosols,using photometric precipitable water amouts

Precipitable water measurements made coincident in time and space with direct broadband solar irradiance measurements are used in conjunction with an atmospheric transmission model to derive a parameter whose major dependence is on total aerosol extinction. Irradiance measurements are used to calculate an atmospheric transmission factor (ATF) that is independent of the instrument calibration and the extraterrestrial solar constant. The dependency of the ATF on precipitable water is determined using LOWTRAN5, an atmospheric transmission model with high spectral resolution. Precipitable water measurements are then used to adjust the measured ATF to correspond to an ATF value obtained for a constant precipitable water amount. The remaining variability in the adjusted ATF is due mostly to aerosol extinction. The technique is applied to a 6-year period (1978–1983) for clear-sky mornings at Mauna Loa, Hawaii (MLO). MLO ATF aerosol residuals are compared with independently measured monochromatic aerosol optical depth. Results show that the ATF aerosol residual is nearly equal to the 500 nm aerosol optical depth prior to the eruption of E1 Chichon, at which time a nonlinear time-dependent relationship between the two quantities is evident. ATF aerosol residuals reflect the spectrally integrated aerosol influence on transmission and, therefore, could indicate better than monochromatic optical depth the radiation balance perturbations due to aerosols. The 6-year precipitable water record for MLO, determined from a dual-channel sunphotometer, has a mean value of 0.3 cm. An annual cycle in precipitable water is evident, as is a 4-month 5-standard-deviation drought from December 1982 through March 1983.     

The conductance of a maize crop and the underlying soil to ozone under various environmental conditions

Flux measurements of ozone and water vapour employing the eddy correlation technique were used to determine the surface conductance and canopy conductance to ozone. In the surface conductance to ozone, all surfaces at which ozone is destroyed and the transport process to these surfaces are included. The canopy conductance to ozone represents the ozone uptake of transpiring plant parts. The surface conductance to ozone of the maize crop and the underlying soil was generally larger than the canopy conductance to ozone. This means that beside the uptake by stomata, there was another important ozone sink. Under wet soil surface conditions, the surface conductance and the canopy conductance to ozone coincided. This indicates that the resistance of wet soil and the remaining plant parts (cuticle) to ozone was much larger than the stomatal or soil resistance. On the other hand, under dry soil conditions the conductances differ, largely caused by a variation in the transport process to the soil. The transport of ozone to soil increased with increasing friction velocity (u _*) and decreased with increasing atmospheric stability, leaf area index (LAI) or crop height (h). These effects for midday (unstable) conditions were parameterized with an in-crop aerodynamic resistance,r _inc in a very straightforward way;r _inc=13.9 LAIh/u _*+67 (cc.=0.77). If the ozone flux in air pollution models is described with a simple resistance model (Big Leaf model), the extra destruction at the soil should be modelled using an in-crop aerodynamic resistance. For these measurements the ozone flux to the soil was 0–65% of the total ozone flux measured above the crop. Under wet soil conditions, this was less than 20%; under dry soil conditions, this was 30–65%.     

General circulation model experiments with surface albedo changes

In 1975, Charney proposed a biogeophysical feedback mechanism to partly explain the droughts that occur in desert border areas. He showed that a perturbation of albedo (due to a natural or anthropogenic decrease of vegetation) can be unstable and lead to a variation of precipitation in the region where albedo is changed.Several numerical experiments have been achieved with general circulation models to study the sensitivity of climate to surface albedo. We compare the GLAS and LMD model results for the Sahel. For all models, rainfall decreases when albedo increases and net radiative heating of soil decreases. We show the variations of circulation simulated by the LMD model that we obtain when albedo is increased. These changes are compared to the weakening of Easterly Jet at 200 mb observed during dry years.     

Surface-Layer Fluxes in Stable Conditions

Micrometeorological tower data from the Microfronts experiment are analyzed. Scale-dependencies of the flux and flux sampling error are combined to automatically determine Reynolds turbulence cut-off time scales for computing fluxes from time series. The computed downward heat flux at the 3 m height averaged over nine nights with 7.3 hours each night is 20% greater than the downward heat flux computed at the 10 m height. In contrast, there is only a 1.2% difference between 3 m and 10 m heat fluxes averaged over daytime periods, and there is less than a 2% difference between 3 m and 10 m momentum fluxes whether averaged over nighttime or daytime periods.Stability functions, M(z/L) and H(z/L) are extended to z/L up to 10, where z is the observational height and L is the Obukhov length. For 0.01 < z/L < 1 the estimated functions generally agree with Businger-Dyer formulations, though the H estimates include more scatter compared to the M estimates. For 1 < z/L < 10, the flux intermittency increases, the flux Richardson number exceeds 0.2, and the number of flux samples decreases. Nonetheless the estimates of the stability function M based on 3-m fluxes are closer to the formula proposed by Beljaars and Holtslag in 1991 while the M functions based on 10-m fluxes appears to be closer to the formula proposed by Businger et al. in 1971. The stability function H levels off at z/L = 0.5.     

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.     

Parameterizing turbulent diffusion through the joint probability density

The convective mass flux parameterization often used in meteorological modeling expresses the vertical flux of a transported scalar as proportional to the product of the difference in mean values of the scalar in updrafts and downdrafts and their characteristic velocity. The proportionality factor is a constant to be specified. We show that this proportionality factor also appears in the relaxed eddy accumulation technique of Businger and Oncley. That associates the surface-layer flux of a scalar with the product of the standard deviation of vertical velocity and the mean concentration difference between updrafts and downdrafts.We show that this constant (b) is determined uniquely by the joint probability density (jpd) of vertical velocity and the scalar. Using large-eddy simulation, we generate this jpd for a conservative scalar diffusing through a convective boundary layer. It has quite different forms in top-down and bottom-up diffusion geometries. The bottom-up jpd is fairly well represented by a jointly Gaussian form and implies b ~ 0.6, in good agreement with the surface-layer value reported by Businger and Oncley. The top-down jpd is strikingly non-Gaussian and gives b ~ 0.47. Updrafts carry the bulk of the scalar flux - 70% in the bottom-up case, 60% in the top-down case.The National Center for Atmospheric Research is sponsored by the National Science Foundation.     

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.     

Intercomparison of measurements of stratospheric hydrogen fluoride

Observations of the vertical profile of hydrogen fluoride (HF) vapor in the stratosphere and of the vertical column amounts of HF above certain altitudes were made using a variety of spectroscopic instruments in the 1982 and 1983 Balloon Intercomparison Campaigns. Both emission instruments working in the far infrared spectral region and absorption instruments using solar occultation in the 2.5m region were employed. No systematic differences were seen in results from the two spectral regions. A mean profile from 20–45 km is presented, with uncertainties ranging from 20% to 50%. Total columns measured from ground and from 12 km are consistent with the profile if the mixing ratio for HF is small in the tropophere and low stratosphere.     

Thermal comfort of man in different urban environments

Summary On July 29, 1985, a hot summer day, biometeorological measurements were performed simultaneously in three different urban structures within the city of Munich and in the trunk space of a nearby tall spruce forest. Based on the results of these experiments the following thermophysiologically relevant biometeorological indices were calculated: Predicted mean vote, skin wettedness and physiologically equivalent temperature. These three indices are derived from different models for the human energy balance. They allow the assessment of the thermal components of the microclimates at the selected sites with regard to application in urban planning. The results quantitatively show the great heat stress in the urban structure street canyon, exposed to south, whereas in the trunk space of the tall spruce forest there is nearly an optimal climate even on hot summer days. Between these extremes the results for street canyon, exposed to north show a little higher heat load than for backyard with trees.

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Zusammenfassung An einem heißen Sommertag, dem 29. Juli 1985, wurden in drei Stadtstrukturen in München und im Stammraum eines nahegelegenen Fichtenhochwaldes zeitgleich biometeorologische Messungen durchgeführt. Mit den Meßergebnissen wurden folgende thermophysiologisch relevante biometeorologische Indizes berechnet: Predicted mean vote, Hautbenetzungsgrad und physiologisch äquivalente Temperatur. Diese drei Indizes beruhen auf verschiedenen Modellen zur menschlichen Energiebilanz. Mit den drei Indizes wurden die thermischen Komponenten der Mikroklimate an den ausgewählten Meßplätzen im Hinblick auf Stadtplanungsaufgaben bewertet. Die Ergebnisse zeigen quantitativ die relativ große Hitzebelastung bei der Stadtstruktur Straßenschlucht, nach Süd exponiert, während im Stammraum des Fichtenhochwaldes selbst an heißen Sommertagen nahezu optimale Bedingungen herrschen. Zwischen diesen Extremen liegen die Ergebnisse für die anderen Meßplätze, wobei für Straßenschlucht, nach Nord exponiert die Wärmebelastung etwas höher als für Innenhof mit Bäumen ist.

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With 6 Figures     

Statistical properties of 49 years of rainfall rate events

Summary The paper presents a detailed investigation of magnitudes and properties pertaining to the large population of rainfall events recorded during 49 years at the Fabra Observatory in Barcelona. The study includes a statistical analysis of event durationT and rainfall quantityQ together with the statistical rainfall rate parameters: , ²(R) and maximum Rm within an event. The decorrelation time is also analysed. It is found thatQ, T, and can be well modelled by a lognormal distribution, but , ² and Rm are only so for a limited range of precipitation ratesR. The regression analysis between pairs of logarithms of the magnitudes investigated is generally good and a regression coefficient is often better than 0.9. Comparison with published work is also carried out. An attempt is made to discriminate between heavy and non-heavy rainfall rates, and the 50 mm/h threshold is used for the study. The twelve-monthly running average indicates that the rainfall amount has a small increasing trend over the fifty year period. However, this trend is reversed when considering heavy rains. Finally, the return period in years to exceeding a thresholdR within an event is also investigated and the distribution of the population of annual extremes is found to be Gumbel II.With 6 Figures     

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.     

Periodicity of annual precipitation in different climate regions of Croatia

Summary The periodicity of a 100-year series of annual precipitation over Croatia has been studied by means of power spectrum analysis at 3 stations representing the different climatic regions of Croatia. The annual precipitation variance spectra in the continental lowland (Osijek) and at the north East Adriatic coast (Crikvenica) can be fitted by Markov white noise continuum, but in the transitional region between the Dinaric Alps and the Pannonian lowland (Zagreb-Gri) a non-white noise continuum is necessary. Quasi-periodic oscillations appear in two spectra ranges: short (2.2 and 4.7 years) and medium (25.0 and 33.3 years). These results are compared with those of other authors for other parts of the Europe.With 2 Figures     

Air quality model performance evaluation

Summary This paper reviews methods to evaluate the performance of air quality models, which are tools that predict the fate of gases and aerosols upon their release into the atmosphere. Because of the large economic, public health, and environmental impacts often associated with the use of air quality model results, it is important that these models be properly evaluated.A comprehensive model evaluation methodology makes use of scientific assessments of the model technical algorithms, statistical evaluations using field or laboratory data, and operational assessments by users in real-world applications. The focus of the current paper is on the statistical evaluation component. It is important that a statistical model evaluation exercise should start with clear definitions of the evaluation objectives and specification of hypotheses to be tested. A review is given of a set of model evaluation methodologies, including the BOOT and the ASTM evaluation software, Taylors nomogram, the figure of merit in space, and the CDF approach. Because there is not a single best performance measure or best evaluation methodology, it is recommended that a suite of different performance measures be applied. Suggestions are given concerning the magnitudes of the performance measures expected of good models. For example, a good model should have a relative mean bias less than about 30% and a relative scatter less than about a factor of two.In order to demonstrate some of the air quality model evaluation methodologies, two simple baseline urban dispersion models are evaluated using the Salt Lake City Urban 2000 field data. The importance of assumptions concerning details such as minimum concentration and pairing of data are shown. Typical plots and tables are presented, including determinations of whether the difference in the relative mean bias between the two models is statistically significant at the 95% confidence level.     

Numerical Simulation of Strongly Stratified Flow Over a Three-Dimensional Hill

A numerical study of stably stratified flow over a three-dimensional hill is presented. Large-eddy simulation is used here to examine in detail the laboratory experimental flows described in the landmark work of Hunt and Snyder about stratified flow over a hill. The flow is linearly stratified and U/Nh is varied from 0.2 to 1.0. Here N and U are the buoyancy frequency and freestream velocity respectively, and h is the height of the hill. The Reynolds number based on the hill height is varied from 365 to 2968. The characteristic flow patterns at various values of U/Nh have been obtained and they are in good agreement with earlier theoretical and experimental results. It is shown that the flow field cannot be predicted by Drazin's theory when recirculation exists at the leeside of the hill even at UNh 1. The wake structure agrees well with a two-dimensional wake assumption when U/Nh 1 but lee waves start to influence the wake structure as U/Nh increases. The dividing-streamline heights obtained in the simulation are in accordance with experimental results and Sheppard's formula. The energy loss along the dividing streamline due to friction/turbulence approximately offsets the energy gained from pressure field. When lee waves are present, linear theory always underestimates the amplitude and overestimates the wavelength of three-dimensional lee waves. The simulated variations of drag coefficients with the parameterK (=ND/ U) are qualitatively consistent with experimental data and linear theory. Here D is the depth of the tank.     

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.     

Three million years of monsoon variability over the northern Sahara

We present a 3 million year record of aeolian dust supply into the eastern Mediterranean Sea, based on hematite contents derived from magnetic properties of sediments from Ocean Drilling Program Site 967. Our record has an average temporal resolution of 400 years. Geochemical data validate this record of hematite content as a proxy for the supply of aeolian dust from the Sahara. We deduce that the aeolian hematite in eastern Mediterranean sediments derives from the eastern Algerian, Libyan, and western Egyptian lowlands located north of the central Saharan watershed (21°N). In corroboration of earlier work, we relate dust flux minima to penetration of the African summer monsoon front to the north of the central Saharan watershed. This would have enhanced soil humidity and vegetation cover in the source regions, in agreement with results from green Sahara climate models. Our results indicate that this northward monsoon penetration recurred during insolation maxima throughout the last 3 million years. As would be expected, this orbital precession-scale mechanism is modulated on both short (100-kyr) and long (400-kyr) eccentricity time scales. We also observe a strong expression of the 41-kyr (obliquity) cycle, which we discuss in terms of high- and low-latitude mechanisms that involve Southern Hemisphere meridional temperature contrasts and shifts in the latitudes of the tropics, respectively. We also observe a marked increase in sub-Milankovitch variability around the mid-Pleistocene transition (0.95 Ma), which suggests a link between millennial-scale climate variability, including monsoon dynamics, and the size of northern hemisphere ice sheets.     

Flux-profile Relationships for Wind Speed and Temperature in the Stable Atmospheric Boundary Layer

Wind and temperature profiles in the stable boundary layer were analyzed in the context of MoninObukhov similarity. The measurements were made on a 60-m tower in Kansas during October 1999 (CASES-99). Fluxprofile relationships, obtained from these measurements in their integral forms, were established for wind speed and temperature. Use of the integral forms eliminates the uncertainty and accuracy issues resulting from gradient computations. The corresponding stability functions, which were nearly the same for momentum and virtual sensible heat, were found to exhibit different features under weakly stable conditions compared to those under strongly stable conditions. The gradient stability functions were found to be linear, namely _m = 1+ 5.8 and _h = 1 + 5.4 up to a limit of the MoninObukhov stability parameter = 0.8; this is consistent with earlier findings. However, for stronger stabilities beyond a transition range, both functions were observed gradually to approach a constant, with a value of approximately 7. To link these two distinct regimes, a general but pliable functional form with only two parameters is proposed for the stability functions, covering the entire stability range from neutral to very stable conditions.     

A comparative study of the performance of various vertical discretization schemes

Summary Most finite-difference numerical weather prediction models employ vertical discretizations that are staggered, and are low-order (usually second-order) approximations for the important terms such as the derivation of the geopotential from the hydrostatic equation, and the calculation of the vertically integrated divergence. In a sigma-coordinate model the latter is used for computing both the surface pressure change and the vertical velocity. All of the above-mentioned variables can diminish the accuracy of the forecast if they are not calculated accurately, and can have an impact on related quantities such as precipitation.In this study various discretization schemes in the vertical are compared both in theory and in practice. Four different vertical grids are tested: one unstaggered and three staggered (including the widely-used Lorenz grid). The comparison is carried out by assessing the accuracy of the grids using vertical numerics that range from second-order up to sixth-order.The theoretical part of the study examines how faithfully each vertical grid reproduces the vertical modes of the governing equations linearized with a basic state atmosphere. The performance of the grids is evaluated for 2nd, 4th and 6th-order numerical schemes based on Lagrange polynomials, and for a 6th-ordercompact scheme.Our interpretation of the results of the theoretical study is as follows. The most important result is that the order of accuracy employed in the numerics seems to be more significant than the choice of vertical grid. There are differences between the grids at second-order, but these differences effectively vanish as the order of accuracy increases. The sixth-order schemes all produce very accurate results with the grids performing equally well, and with the compact scheme significantly outperforming the Lagrange scheme. A second major result is that for the number of levels typically used in current operational forecast models, second-order schemes (which are used almost universally) all appear to be relatively poor, for other than the lowest modes.The theoretical claims were confirmed in practice using a large number (100) of forecasts with the Australian Bureau of Meteorology Research Centre's operational model. By comparing test model forecasts using the four grids and the different orders of numerics with very high resolution control model forecasts, the results of the theoretical study seem to be corroborated.With 8 Figures     

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 .