Application of the Priestley-Taylor evaporation model to assess the influence of soil moisture on the evaporation from a large weighing lysimeter and class a pan

The influence of soil moisture on evaporation from a 6-m grass-covered lysimeter and from Class A pans was assessed for one summer using the -parameter of the Priestley-Taylor evaporation model appropriate for the individual surfaces computed on a daily basis. Net radiation over the pan was estimated from above-grass measurements using a correlation established between the two, using measurements made in the previous two summers. Changes in heat storage of the water were considered in the derivation of for the pan. A unique relationship for the particular conditions of the site was determined between the for the lysimeter and soil moisture, approaching 1.29 at soil moisture near field capacity, but decreasing to as low as 0.5 for dry soil. The corresponding relationship for the pan showed more scatter, but this was improved by using 5-day running means of evaporation and stratifying the data in terms of wind speed to yield a family of curves. Values for at wet soil conditions varied from 1.07 for 100 km day^–1 wind run to 1.17 for 250 km day^–1 wind run. For each curve, values of increased by about 20%; as the soil dried. The relationships may be used to reduce observed Class A pan evaporation to equivalent values for wet-soil conditions and to estimate near-surface soil moisture and actual evapotranspiration for this particular site. Extension of the technique to other areas requires derivation of similar relationships appropriate for those other locations     

A Generalized Structure-Activity Relationship for the Decomposition of (Substituted) Alkoxy Radicals

A novel and readily applicable Structure-Activity Relationship (SAR) for predicting the barrier height E_b to decomposition by C-C scission of (substituted) alkoxy radicals is presented. Alkoxy radicals are pivotal intermediates in the atmospheric oxidation of (biogenic) volatile organic compounds, and their fate is therefore of crucial importance to the understanding of atmospheric VOC degradation mechanisms. The SAR is based on available theoretical energy barriers and validated against barriers derived from experimental data. The SAR is expressed solely in terms of the number(s) N_i of alkyl-, hydroxy- and/or oxo-substituents on the - and -carbons of the breaking bond: E_b(kcal/mol) =17.5 – 2.1 × N(alk) – 3.1 ×N(alk) – 8.0 × N_,(OH) – 8.0 × N(O=) – 12 × N(O=). For barriers below 7 kcal/mol, an additional, second-order term accounts for the curvature. The SAR reproduces the available experimental and theoretical data within 0.5 to 1 kcal/mol. The SAR generally allows conclusive predictions as to the fate of alkoxy radicals; several examples concerning oxy radicals from prominent atmospheric VOC are presented. Specific limitations of the SAR are also discussed. Using the predicted barrier height E_b, the high-pressure rate coefficient for alkoxy decomposition k _diss (298 K) can be obtained from k _diss (298 K) = L ×1.8 × 10¹³ exp(–E_b/RT) s^–1, with L the reaction path degeneracy.     

Ly(α) absorption cross-section of H2O and O2

The absorption cross-sections of water vapor and oxygen were measured, using a low-pressure radio frequency discharge through traces of hydrogen in argon as a light source for Ly() radiation. The cross-sections are H₂O = 1.59 × 10^–17 cm² and O₂ = 1.13 × 10^–20 + 1.72 × 10^–23 for water and oxygen, respectively, where P is the oxygen pressure in units of Torr. Ly() lamps, such as used for this work, are important light sources for photochemical laboratory work and find applications for trace-gas detection in the atmosphere. For the latter application, accurate cross-sections of water vapor and oxygen are needed.     

Free convection frequency spectra of atmospheric turbulence over the sea

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

Inertial subrange correlation between temperature and humidity fluctuations in the unstable surface layer above vegetated terrains

Observations of the temperature-humidity cospectrum and correlation spectrum were made with a cold platinum wire and a Ly- hygrometer at 3.7 and 10 m above vegetated surfaces during unstable atmospheric conditions. It was found theoretically that a separation between the temperature and humidity sensors causes a drop-off of the correlation spectrum at wavenumbers > 0.3 ^–1. The observed drop-off follows the theoretical one reasonably well. Measurements made with the temperature sensor placed in the center of the Ly- gap reveal a % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaaccaGae8NKby% kaaa!37B5!\[f\]^–5/3 dependence of the temperature-humidity cospectrum in the inertial subrange up to frequencies of 20 Hz. The drop-off at higher frequenties is thought to be caused by limitations inherent to the Ly- humidiometer.     

Experimental determination of HONO mass accommodation coefficients using two different techniques

The mass accommodation coefficient _HONO of gaseous nitrous acid on water surfaces has been determined in a cooperation between the Universities of Strasbourg and Bonn. The droplet train technique (Strasbourg) yielded 0.04<_HONO<0.09 for an estimated surface temperature of 245 K, while the liquid jet technique (Bonn) yielded 0.03<_HONO<0.15 for a surface temperature of 297 K. The uncertainty ranges allow for experimental scatter and estimated uncertainties in diffusion coefficients. The same HONO source and analytical equipment were used for both experiments, which were run in parallel. The results indicate that the exchange rate of HONO between atmospheric water droplets and interstitial air is not inhibited by interfacial resistance.     

Microwave vegetation optical depth and inverse modelling of soil emissivity using Nimbus/SMMR satellite observations

Summary A radiative transfer model has been used to determine the large scale effective 6.6 GHz and 37 GHz optical depths of the vegetation cover. Knowledge of the vegetation optical depth is important for satellite-based large scale soil moisture monitoring using microwave radiometry. The study is based on actual observed large scale surface soil moisture data and observed dual polarization 6.6 and 37 GHz Nimbus/SMMR brightness temperatures over a 3-year period. The derived optical depths have been compared with microwave polarization differences and polarization ratios in both frequencies and with Normalized Difference Vegetation Index (NDVI) values from NOAA/AVHRR. A synergistic approach to derive surface soil emissivity from satellite observed brightness temperatures by inverse modelling is described. This approach improves the relationship between satellite derived surface emissivity and large scale top soil moisture fromR ²=0.45 (no correction for vegetation) toR ²=0.72 (after correction for vegetation). This study also confirms the relationship between the microwave-based MPDI and NDVI earlier described and explained in the literature.List of Symbols f frequency [Hz] - f _i(p) fractional absorption at polarizationp - h surface roughness - h h cos² - H horizontal polarization - n _i complex index of refraction - p polarization (H orV) - R _s microwave surface reflectivity - T _B(p) brightness temperature at polarizationp - T ^* normalized brightness temperature - T polarization difference (T _v-T _H) - T _s temperature of soil surface - T _c temperature of canopy - T _max daily maximum air temperature - T _min daily minimum air temperature - V vertical polarization - soil moisture distribution factor; also used for the constant to partition the influence of bound and free water components to the dielectric constant of the mixture - empirical complex constant related to soil texture - microwave transmissivity of vegetation (=e ^–) - ^* effective transmissivity of vegetation (assuming =0) - microwave emissivity - _s emissivity of smooth soil surface - _rs emissivity of rough soil surface - _vs emissivity of vegetated surface - soil moisture content (% vol.) - K dielectric constant [F·m^–1] - K _fw dielectric constant of free water [F·m^–1] - K _ss dielectric constant of soil solids [F·m^–1] - K _m dielectric constant of mixture [F·m^–1] - K _o permittivity of free space [8.854·10^–12 F·m^–1] - high frequency limit ofK _wf [F·m^–1] - wavelength [m] - incidence angle [degrees from nadir] - polarization ratio (T _H/T _V) - b soil bulk density [gr·cm^–3] - s soil particle density [gr·cm^–3] - R surface reflectivity in red portion of spectrum - NIR surface reflectivity in near infrared portion of spectrum - _eff effective conductivity of soil extract [mS·cm^–1] - vegetation optical depth - _6.6 vegetation optical depth at 6.6 GHz - ₃₇ vegetation optical depth at 37 GHz - ^* effective vegetation optical depth (assuming =0) - single scattering albedo of vegetation With 12 Figures     

The effects of orography on precipitation

In this paper, a model simulating the effects of topography and altitude on precipitation is presented. Topography has its maximum effect on precipitation when the angle which the wind makes with the slope direction approaches zero and the inclination of the slope is near 45°. The smaller the angle , the greater the influence of slope on precipitation. When <45°, the larger the inclination, the greater the influence of slope on precipitation and the less the difference in precipitation between the windward and the leeward slopes. When <45°, the reverse holds. But for in the range of 0°–45° and in the range 30°–60°, differences in precipitation on both the windward and leeward slopes are not so well marked and can be neglected in general. In condition of uniform slope inclination, precipitation on the windward slope increases with altitude at first and then decreases after attaining a height (H _m ) of maximum precipitation; alsoH _m is greater, the drier the air mass. When the terrain on the windward side is stepped in shape, it is possible that more than one height of maximum precipitation will occur.     

Gas-Phase Ozone Oxidation of Monoterpenes: Gaseous and Particulate Products

Atmospheric oxidation of monoterpenes contributes to formation of tropospheric ozone and secondary organic aerosol, but their products are poorly characterized. In this work, we report a series of outdoor smog chamber experiments to investigate both gaseous and particulate products in the ozone oxidation of four monoterpenes: -pinene, -pinene, ³-carene, and sabinene. More than ten oxygenated products are detected and identified in each monoterpene/O₃ reaction by coupling derivatization techniques and GC/MS detection. A denuder/filter pack sampling system is used to separate and simultaneously collect gas and aerosol samples. The identified products, consisting of compounds containing carbonyl, hydroxyl, and carboxyl functional groups, are estimated to account for about 34–50%, 57%, 29–67%, and 24% of the reacted carbon mass for -pinene, sabinene, -pinene, and ³-carene, respectively. The identified individual products account for >83%, 100%, >90%, and 61% of the aerosol mass produced in the ozone reaction of -pinene, sabinene, -pinene, and ³-carene. The uncertainty in the yield data is estimated to be ±50%. Many of the products partition between gas and aerosol phases, and their gas-aerosol partitioning coefficients are determined and reported here. Reaction schemes are suggested to account for the products observed.     

The prediction of dust erosion by wind: An interactive model

We have devised a partial differential equation for the prediction of dust concentration in a thin layer near the ground. In this equation, erosion (detachment), transport, deposition and source are parameterised in terms of known quantities. The interaction between a wind prediction model in the boundary layer and this equation affects the evolution of the dust concentration at the top of the surface layer. Numerical integrations are carried out for various values of source strength, ambient wind and particle size. Comparison with available data shows that the results appear very reasonable and that the model should be subjected to further development and testing.Notation (x, y, z, t) space co-ordinates and time (cm,t) - u, v components of horizontal wind speed (cm s^–1) - u _g, v_g components of the geostrophic wind (cm s^–1) - V=(u²+v²)^1/2 (cm s^–1) - (û v)= 1/(h – k) _k ^h(u, v)dz(cm s^–1) - V _* friction velocity (cm s^–1) - z ₀ roughness length (cm) - k ₁ von Karman constant =0.4 - V _d deposition velocity (cm s^–1) - V _g gravitational settling velocity (cm s^–1) - h height of inversion (cm) - k height of surface layer (cm) - potential temperature (°K) - _gr potential temperature at ground (°K) - _K potential temperature at top of surface layer (°K) - P pressure (mb) - P ₀ sfc pressure (mb) - C _p/C_v - (t)= /z lapse rate of potential temperature (°K cm^–1) - A(z) variation of wind with height in transition layer - B(z) variation of wind with height in transition layer - Cd drag coefficient - C _HO transfer coefficient for sensible heat - C dust concentration (g m^–3) - C _K dust concentration at top of surface layer (g m^–3) - D(z) variation with height of dust concentration - u, v, w turbulent fluctuations of the three velocity components (cm s^–1) - A ₁ constant coefficient of proportionality for heat flux =0.2 - Ri Richardson number - g gravitational acceleration =980 cm s^–2 - Re Reynolds number = - D _s thickness of laminar sub-layer (cm) - v molecular kinematic viscosity of air - coefficient of proportionality in source term - dummy variable - t time step (sec) - n time index in numerical equations On sabbatical leave at University of Aberdeen, Department of Engineering, September 1989–February 1990.     

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     

Gas and Particulate Products Distribution from the Photooxidation of α-Humulene in the Presence of NOx, Natural Atmospheric Air and Sunlight

The photooxidation of -humulene in the presence of NO_x, natural sunlight, and rural background air was investigated using a combination of gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC). Identification and quantification of gas and particulate reaction products were reported over the course of the reaction. The daytime photooxidation was carried out in a large outdoor smog chamber (190 m³). A wide range of ring retaining and ring opening products in the gas and particle phase are reported. On average, measured gas and particle phase products accounted for 44% of the reacted -humulene carbon. Measurements show that a number of reaction products with low vapor pressures (e.g. 3-seco--humulone aldehyde, 7-seco--humulone aldehyde, -humulal aldehyde, -humulene 3-oxide or -humulene 7-oxide, -humulaic/alic acid isomers, and 3-seco--14-hydroxyhumulone aldehyde) were found in the early stage of the reaction and may play an important role in the early formation of secondary organic aerosol. A detailed mechanism is proposed to account for most products observed in this investigation.     

The behaviour of a mixed-layer model of the convective boundary layer coupled to a big leaf model of surface energy partitioning

Daily mean values of the Priestley-Taylor coefficient, ¯, are derived from a simple model of the daily growth of a convective boundary layer. For a particular control set of driving environmental variables, ¯ is related to the prescribed bulk surface resistance, r_S by 1/¯ = 1/₀ + mr_S for parameters ₀ and m. The dependence of the parameters ₀ and m on weather is explored and a potential use of this linear relation to provide information about regional values of r_S is indicated.     

Absolute Rate Coefficients for the Gas-Phase Reactions of NO3 Radical with a Series of Monoterpenes at T = 298 to 433 K

The aim of this work is to study the reactivity of some naturally emitted terpenes, 2-carene, sabinene, myrcene, -phellandrene, d-limonene, terpinolene and -terpinene, towards NO3 radical to evaluate the importance of these reactions in the atmosphere and their atmospheric impact. The experiments with these monoterpenes have been carried out under second-order kinetic conditions over the range of temperature 298–433 K, using a discharge flow system and monitoring the NO3 radical by Laser Induced Fluorescence (LIF). This work is the first temperature dependence study for the reactions of the nitrate radical with the above-mentioned monoterpenes. The measured rate constants at 298 K for the reaction of NO3 with such terpenes are as follows: 2-carene, 16.6 ± 1.8, sabinene 10.7 ± 1.6, myrcene 12.8 ± 1.1, -phellandrene 42 ± 10, d-limonene 9.4 ± 0.9, terpinolene 52 ± 9 and -terpinene 24 ± 7, in units of 10-12 cm3 molecule-1 s-1. The proposed Arrhenius expressions, for the reactions of NO3 with 2-carene, sabinene, myrcene and -phellandrene are, respectively k1 = (1.4 ± 0.7) × 10-12 exp[(741 ± 190/T)] (cm3 molecule-1 s-1), k2=(2.3 ± 1.3) × 10-10 exp[–(940 ± 200/T)] (cm3 molecule-1 s-1), k3 = (2.2 ± 0.2) × 10-12 exp[(523 ± 35/T)] (cm3 molecule1 s-1) and k4 = (1.9 ± 1.3) × 10-9 exp[–(1158 ± 270/T)] (cm3 molecule-1 s-1). A decrease in the rate constants when raising the temperature has also been found for the reaction of d-limonene with NO3 while an increase in the rate constant with temperature has been observed for the reactions of terpinolene and -terpinene with NO3. Tropospheric half-lives for these terpenes have been calculated at night and during the day for typical NO3 and OH concentrations showing that both radicals provide an effective tropospheric sink for these compounds and that the night-time reaction with NO3 radical can be an important, if not dominant, loss process for these naturally emitted organics and for NO3 radicals.     

Emissions of Volatile Organic Compounds from Sunflower and Beech: Dependence on Temperature and Light Intensity

Emissions of volatile organic compounds (VOCs) from sunflower (Helianthus annuus L. cv. giganteus) were measured in a continuously stirred tank reactor. The compounds predominantly emitted from sunflower were: isoprene, the monoterpenes -pinene, -pinene, sabinene, 3-carene and limonene, an oxygenated terpene, not positively identified so far and the sesquiterpene -caryophyllene. Emission rates ranged from 0.8 x 10^–16 to 4.3 x 10 ^–15 mol cm^–2 s^–1 at a temperature of 25°C and at a light intensity of 820 µEm^–2 s^–1. A dependence of the emission rates on temperature as well as on light intensity was observed. The emission rates of -pinene, sabinene and thujene from beech (Fagus sylvatica L.) were also affected by temperature as well as by light intensity. Our results suggest that an emission algorithm for all compounds emitted from sunflower and beech has to consider temperature and light intensity simultaneously. The observations strongly indicate that the emissions of VOCs from sunflower and beech are in part closely coupled to the rate of biosynthesis and in part originate from diffusion out of pools. The emission rates can be described by an algorithm that combines the model given by Tingey and coworkers with the algorithm given by Guenther and coworkers after slight modification.     

An alternative analysis of flux-gradient relationships at the 1976 ITCE

An extensive micrometeorological data set from the 1976 International Turbulence Comparison Experiment (ITCE) is analysed to determine flux-gradient relationships in an unstable atmosphere for momentum, sensible heat and water vapour transfers. The data are first analysed for internal consistency, resulting in the rejection of some data. Following a least-square fit to the remaining data in the form /k = (1 – z/L)^-/k, rounded-off values of k, , and are selected for each form of transfer consistent with the statistical accuracy of the measurements. The equations finally adopted are _M = (1 – 28z/L)^-1/4 and _{H, W} = (1 – 14z/L)^-1/2 with k _M = k_H = k_W = 0.40.These expressions fit the averaged observations to within a few per cent in the stability range of the experiment (-4 < z/L < -0.004).     

Formation of Organic Aerosols from the Oxidation of Biogenic Hydrocarbons

Measurements of aerosol formation during thephotooxidation of -pinene, -pinene,d-3-carene, d-limonene, ocimene, linalool, terpinene-4-ol, andtrans-caryophyllene were conducted in anoutdoor smog chamber. Daylight experiments in thepresence of and dark experiments withelevated ozone concentrations were performed. Theevolution of the aerosol was simulated by theapplication of a gas/particle absorption model inconnection with a chemical reaction mechanism. Thefractional aerosol yield is shown to be a function ofthe organic aerosol mass concentration andtemperature. Ozone and, for selected hydrocarbons, theNO₃ reaction of the compounds were found torepresent efficient routes to the formation ofcondensable products. For initial hydrocarbon mixingratios of about 100 ppb, the fractional aerosol yieldsfrom daylight runs have been estimated to be 5%for open-chain hydrocarbons, such as ocimene andlinalool, 5–25% for monounsaturated cyclicmonoterpenes, such as -pinene, d-3-carene, orterpinene-4-ol, and 40% for a cyclic monoterpenewith two double bonds like d-limonene. For the onlysesquiterpene investigated, trans-caryophyllene, afractional aerosol yield of close to 100% wasobserved. The majority of the compounds studied showedan even higher aerosol yield during dark experimentsin the presence of ozone.     

A generalization of the Kolmogorov-von Kármán relationship and some further implications on the values of the constants

A general relation between the Kolmogorov (₁) and von Kármán (k) constants appropriate to flows in the surface boundary layer is obtained by including stability and divergence dependent terms in the development. The result is used to show that the author's earlier inference of the valuek = 0.36 drawn from the observed value ,k ^4/3=0.141 cannot have been underestimated due to the neglect of stability or divergence effects. It is concluded that if k is to be 0.4, then ₁ must be 0.5.Work performed under the auspices of the U.S. Energy Research and Development Administration.     

The behaviour of aerosol optical depth during clear summer days in Athens,Greece

Summary The integral aerosol optical depths (k ) at the hour of 08:20 Local Standard Time (LST), are compared with those calculated previously at 11:20 and 14:20 LST, for clear days during summer in Athens over the period 1962–1988. The mean values at 08:20 LST were consistently lower than the values at 11:20 and 14:20 LST. The influence of the vertical wind profile on the values ofk was also investigated. A comparison was made of the wind profiles at 02:00 and 14:00 LST, for days in which the 11:20 and 14:20 LST values ofk were 0.200 andk 0.350, respectively. The corresponding bulk wind shear s was also found for the period 1980–1988. The most significant results occurred with the first category of days. The resultant wind velocities from the surface to the 900 hPa level, in each hour were higher by 2–4 m·s^–1 with respect to the corresponding values for the second category. At 02:00 LST the bulk wind shear showed a considerable difference (1.8) between the two categories of days in the surface to 700 hPa layer at 02:00 LST. Finally, the associated weather conditions that appear to initiate a period of low values ofk (k 0.200) at 11:20 and 14:20 LST were examined for the period 1980–1988. Fifteen such cases were identified and it was found that they all occurred after the passage of weak cold fronts.With 6 Figures     

A laboratory study of the mechanism of the oxygen airglow

Further laboratory studies of emission by O(¹ S) and by O₂ A ³ _u ⁺ ,A³ _u andc ¹ _u ^– in the oxygen afterglow lead to the conclusion that Barth's mechanism for the excitation of the auroral green line O ₂ ^* +O(³P=O₂+O(¹S)–(1) is correct and that levelsv=6 and 7 of O₂ A ³ _u ⁺ are Barth precursors. The value ofk ₁=7×10^–11 cm³ s^–1 deduced for these levels is shown to be in fair agreement with atmospheric measurements.