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.     

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.     

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.     

Effects of water vapour on the structure parameter of the refractive index for near-infrared radiation

The refractive index of air (n) mainly depends on temperature andwater vapour content. For near-infrared radiation, temperature isthe main determining factor. To determinethe structure parameter of temperature ( ) fromthe structure parameter of the refractive index( ), the influence ofwater vapour content on n needs to be taken into account as acorrection. Three levels of approximation are presented. The firstinvolves the standard deviations of T and q (_T and_q) as well as the correlation coefficient betweenT and q (R_Tq). The second approximation involvesR_Tq and the Bowen ratio (), and the last uses only the Bowen ratio.The latter is the classical Bowen ratio correction.Evaluation of the validity of the assumptions used in the derivationreveals that a large error may be introduced (for situations withR_Tq < 0.8) by replacing _T/_qwith the Bowen ratio.Consequently, estimating from using the Bowen ratiocan contain errors of 5–40% for || < 1. Adding R_Tqas extra information reduces the errors only marginally. For || > 1,the correction is small, and all three approximations give errors of lessthan 1% in . When is used to compute the sensible heat flux,the influence of the quality of the correction forwater vapour fluctuations on the measured energy balance is small: forsmall ||, the correction is large, but the absolute value ofthe heat flux is small, whereas for large ||, the correctionis insignificant.     

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.     

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.     

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.     

An improved calibration for tethered balloon wind measurements

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

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     

The carbon isotopic ratio of atmospheric carbon dioxide at Tsukuba,Japan

To find out the secular and seasonal trends of the ¹³C value and CO₂ concentration in the surface air and the determination of the ¹³C in the atmospheric CO₂ collected at Tsukuba Science City was carried out during the period from July 1981 to October 1983. The monthly average of the ¹³C value of CO₂ in the surface air collected at 1400 LMT ranged from -7.52 to \s-8.45 with an average of -7.96±0.25 and the CO₂ concentration in the air varied from 334.5 l 1^-1 to 359 l 1^-1 with an average of 347.2±6.3 l 1^-1. The ¹³C value is high in summer and low in winter and is negatively correlated with the CO₂ concentration. In general, the relationship between the ¹³C and the CO₂ concentration is explainable by a simple mixing model of two different constant carbon isotopic species but the relationship does not always follow the model. The correlation between the ¹³C value and the CO₂ concentration is low during the plant growth season and high at other times. The observed negative deviation of the ¹³C value from the simple mixing model in the plant growth season is partly due to the isotopic fractionation process which takes place in the land biota.     

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.     

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.     

On the inner-layer scale height of boundary-layer flow over low hills

Jackson and Hunt's (1975) equation for the depth of the inner layer of flows over low hills does not depend on any closure assumption as contrarily supposed in literature. This equation contains a constant which can arbitrarily be specified. It is suggested that this inner-layer constant should be determined from experimental data. A preliminary check with some data from the Askervein experiment suggests that Jackson and Hunt's equation fits these data almost as well as Jensen's equation provided that fitted inner-layer constants are used.     

Carbon dioxide emissions in a methane economy

Increasing reliance on natural gas (methane) to meet global energy demands holds implications for atmospheric CO₂ concentrations. Analysis of these implications is presented, based on a logistic substitution model viewing energy technologies like biological species invading an econiche and substituting in case of superiority for existing species. This model suggests gas will become the dominant energy source and remain so for 50 years, peaking near 70 percent of world supply. Two scenarios of energy demand are explored, one holding per capita consumption at current levels, the second raising the global average in the year 2100 to the current U.S. level. In the first (efficiency) scenario concentrations peak about 450 ppm, while in the second (long wave) they near 600 ppm. Although projected CO₂ concentrations in a methane economy are low in relation to other scenarios, the projections confirm that global climate warming is likely to be a major planetary concern throughout the twenty-first century. A second finding is that data on past growth of world per capita energy consumption group neatly into two pulses consistent with longwave theories in economics.     

Estimating product yields of carbon-containing products from the atmospheric photooxidation of ambient air alkenes

The yields of products have been calculated for the reactions of hydroxyl radicals and ozone with 19 of the two-through-six carbon anthropogenic alkenes. Based on their rate of reaction, mechanisms of reactions and the ambient air distribution for these alkenes their seasonal ambient air yields have been estimated.Aldehydes predominate as products irrespective of season, with smaller yields of several ketones. Other minor products include carboxylic acids, carbon monoxide, carbon dioxide, and alkenes. About a two-fold increase is estimated in the yields of hot biradicals and their products from summer to winter.One sensitivity analysis was made by recomputing yields at a different OH radical to O₃ concentration than assumed most likely in the calculations discussed above. In addition, the sensitivity of product yields to an estimated range of seasonally averaged sunset-to-sunrise NO₃ radical concentrations was calculated. The effects of free radical reactions are discussed, but these are believed to make a relatively minor contribution within the NO _x -rich atmospheres that contain anthropogenic alkenes.The uncertainties in product yields associated with the range of NO₃ radical concentrations assumed present is relatively small for aldehydes, as is the decrease in yield of the one carbon hot biradical. Larger uncertainties occur for ketones. Significant decreases in yields occur for larger hot biradicals, especially the branched-chain hot radicals in the presence of NO₃ radicals.     

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     

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     

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.     

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 .     

A Comparative Analysis of Transpiration and Bare Soil Evaporation

Transpiration E^v and bare soil evaporation E^b processes are comparatively analysed assuming homogeneous and inhomogeneous areal distributions of volumetric soil moisture content . For a homogeneous areal distribution of we use a deterministic model, while for inhomogeneous distributions a statistical-deterministic diagnostic surface energy balance model is applied. The areal variations of are simulated by Monte-Carlo runs assuming normal distributions of .The numerical experiments are performed for loam. In the experiments we used different parameterizations for vegetation and bare soil surface resistances and strong atmospheric forcing. According to the results theE^v()-^Eb() differences are great, especially in dry conditions. In spite of this, the available energy flux curves of vegetation A^v() and bare soil A^b() surfaces differ much less than the E^v() and ^Eb() curves. The results suggest that E^v is much more non-linearly related to environmental conditions than ^Eb. Both E^v and ^Eb depend on the distribution of , the wetness regime and the parameterization used. With the parameterizations, ^Eb showed greater variations than E^v. These results are valid when there are no advective effects or mesoscale circulation patterns and the stratification is unstable.