Further studies of the temperature dependence of the rate coefficients for the reactions of OH with a series of ethers under simulated atmospheric conditions

The following temperature-dependent rate coefficients (k/cm³ molecule^–1 s^–1) of the reactions of hydroxyl radicals with aliphatic ethers have been determined over the temperature range 247–373 K by a competitive flow technique: diethyl ether,k _OH=5.2×10^–12 exp[(262±150)/T]; methyln-butyl ether,k _OH=5.4×10^–12 exp[(309±150)/T]; ethyln-butyl ether,k _OH=7.3×10^–12 exp[(335±150)/T]; di-n-butyl ether,k _OH=5.5×10^–12 exp[(502±150)/T] and di-n-pentyl ether,k _OH=8.5×10^–12 exp[(417±150)/T]. The data have been measured relative to the rate coefficientk(OH + 2,3-dimethylbutane)=6.2×10^–12 cm³ molecule^–1 s^–1 independent of temperature.Previous discrepancies in the room-temperature rate coefficients for the OH reactions with ethyln-butyl ether and di-n-butyl ether, obtained in the flow and static experiments of Bennett and Kerr (J. Atmos. Chem. 8, 87–94, 1989;10, 29–38, 1990) compared with those of Wallingtonet al. (Int. J. Chem. Kinet. 20, 541–547, 1988;21, 993–1001, 1989) and of Nelsonet al. (Int. J. Chem. Kinet. 22, 1111–1126, 1990) have been resolved. The results are considered in relation to the available literature data and evaluated rate expressions are deduced where possible. The data are also discussed in terms of structure-activity relationships.     

Estimates of diabatic wind speed profiles from near-surface weather observations

In this paper we analyse diabatic wind profiles observed at the 213 m meteorological tower at Cabauw, the Netherlands. It is shown that the wind speed profiles agree with the well-known similarity functions of the atmospheric surface layer, when we substitute an effective roughness length. For very unstable conditions, the agreement is good up to at least 200 m or z/L–7(z is height, L is Obukhov length scale). For stable conditions, the agreement is good up to z/L1. For stronger stability, a semi-empirical extension is given of the log-linear profile, which gives acceptable estimates up to ~ 100 m. A scheme is used for the derivation of the Obukhov length scale from single wind speed, total cloud cover and air temperature. With the latter scheme and the similarity functions, wind speed profiles can be estimated from near-surface weather data only. The results for wind speed depend on height and stability. Up to 80 m, the rms difference with observations is on average 1.1 m s^–1. At 200 m, 0.8 m s^–1 for very unstable conditions increasing to 2.1 m s^–1 for very stable conditions. The proposed methods simulate the diurnal variation of the 80 m wind speed very well. Also the simulated frequency distribution of the 80 m wind speed agrees well with the observed one. It is concluded that the proposed methods are applicable up to at least 100 m in generally level terrain.     

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.     

Kinetics of the reactions of hydroxyl radicals with alkyl nitrates and with some oxygen-containing organic compounds studied under simulated atmospheric conditions

Rate constants have been measured for the reactions of hydroxyl radicals with alkyl nitrates and with some oxygen-containing organic compounds by a competitive technique. Mixtures of synthetic air containing a few ppm of nitrous acid, ethylene and the organic substrate were photolysed in a Teflon bag smog chamber. Based on the value k _HO+C2H₄}=8.1×10^-12 cm³ molecule^-1 s^-1 the following rate constants were obtained for the hydroxyl radical reactions at 750 Torr and at 303 K in units of 10^-12 cm³ molecule^-1: CH₃ONO₂, 0.37±0.09; C₂H₅ONO₂, 0.48±0.20; n-C₃H₇ONO₂, 0.70±0.22; C₂H₅OH, 3.6±0.4; CH₃COCH₃, 0.26±0.08; CH₃CO₂ i-C₃H₇, 3.0±0.8; CH₃CO₂ n-C₃H₇, 2.4±0.2. The results are discussed in relation to the available literature data and the implications of the results are considered in terms of the smog reactivity of these molecules.     

A smog chamber for studies of the reactions of terpenes and alkanes with ozone and OH

The design and performance of a smog chamber for the study of photochemical reactions under simulated environmental conditions is described. The chamber is thermostated for aerosol experiments, and it comprises a gas chromatographic sample enrichment system suitable for monitoring hydrocarbons at the ppbv level. By irradiating NO _x /alkane-mixtures rate constants for the reaction of OH radicals with n-alkanes are determined from n-pentane to n-hexadecane to be (k±2)/10^–12 cm³ s^–1=4.29±0.16, 6.2±0.6, 7.52 (reference value), 8.8±0.3, 10.2±0.3, 11.7±0.4, 13.7±0.3, 15.1±0.5, 17.5±0.6, 19.3±0.7, 22.3±1.0, and 25.0±1.3, respectively at 312 K. Rate constants, (k±2)/10^–17 cm³ s^–1, for the reaction of ozone with trans-2-butene (21.2±1.0), cis-3-methylpentene-(2) (47.2±1.7), cyclopentene (62.4±3.5), cyclohexene (7.8±0.5), cycloheptene (28.3±1.5), -pinene (8.6±1.3), and -pinene (1.4±0.2) are determined in the dark at 297 K using cis-2-butene (13.0) as reference standard.     

A comparison of airborne eddy correlation and bulk aerodynamic methods for ocean-air turbulent fluxes during cold-air outbreaks

Four bulk schemes (LKB, FG, D and DB), with the flux-profile relationships of Liuet al. (1979), Francey and Garratt (1981), Dyer (1974), and Dyer and Bradley (1982), are derived from the viscous interfacial-sublayer model of Liuet al. These schemes, with stability-dependent transfer coefficients, are then tested against the eddy-correlation fluxes measured at the 50 m flight level above the western Atlantic Ocean during cold-air outbreaks. The bulk fluxes of momentum (), sensible heat (H), and latent heat (E) are found to increase with various von Kármán constants (k _M for k _H forH, andk _E forE). Except that the LKB scheme overestimates by 28% (46Wm^–2), on the average, the fluxes estimated by the four bulk schemes appear to be in fairly good agreement with those of the eddy correlation method (magnitudes of biases within 10% for , 17% forH, and 13% forE). The results suggest that the overall fluxes and surface-layer scaling parameters are best estimated by FG and thatk _H <k _E . On the average, the FG scheme underestimates by 10% (0.032N m^–2) andE by 4% (12Wm^–2), and overestimatesH by 0.3% (0.5W m^–2). The equivalent neutral transfer coefficients at 10 m height of the FG scheme compare well with some schemes of those tested by Blanc (1985).The relative importance of various von Kármán constants, dimensionless gradients and roughness lengths to the oceanic transfer coefficients is assessed. The dependence of transfer coefficients on wind speeds and roughness lengths is discussed. The transfer coefficients for andE agree excellently between LKB and FG. However, the ratio of the coefficient forH of LKB to that of FG, increasing with decreasing stability, is very sensitive to stability at low winds, but approaches the neutral value of 1.25 at high winds.     

Measurements of fluctuations of vertical wind velocity,temperature and radio-refractive index above the sea

Mean spectra of vertical wind velocity, temperature, and humidity and co-spectra of vertical turbulent heat and moisture fluxes are reported, normalized in terms of the similarity theory of Monin-Obukhov. The measurements were made in April 1967 at light-house Alte Weser at a height of 30 m above the German Bight. Ten spectra measured under conditions of moderate instability (z/L –0.08) have been used for the evaluation of a mean spectral curve. The humidity fluctuations have been determined from simultaneous turbulence measurements of temperature and radiorefractive-index, which were obtained by a microwave refractometer.Similar to the BOMEX measurements discussed by Phelps and Pond (1971) our results also show a dissimilarity between the fluctuations of temperature and humidity. Accordingly, in the range of lower and higher natural frequencies, significant differences were present between the co-spectra of the vertical heat and moisture fluxes, although the mean peak frequencies of both the fluxes nearly correspond to that of the mean vertical wind-velocity spectrum (f _m 0.35).     

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 discharge flow mass-spectrometric study of the reaction between the NO3 radical and isoprene

The kinetics and mechanism of the reactionNO₃+CH₂=C(CH₃)–CH=CH₂productswere studied in two laboratories at 298 K in the pressure range 0.7–3 torr using the discharge-flow mass-spectrometric method. The rate constant obtained under pseudo-first-order conditions with excess of either NO₃ or isoprene was: k ₁=(7.8±0.6)×10^–13 cm³ molecule^–1 s^–1. The product analysis indicated that the primary addition of NO₃ occurred on both -bonds of the isprene molecule.     

Three-dimensional modeling of synthetic cold fronts approaching the Alps

Summary A numerical model was used to study the behaviour of prototype cold fronts as they approach the Alps. Two fronts with different orientations relative to the Alpine range have been considered. One front approaches from west, a second one from northwest. The first front is connected with southwesterly large-scale air-flow producing pre-frontal foehn, whereas the second front is associated with westerly largescale flow leading to weak blocking north of the Alps.Model simulations with fully represented orography and parameterized water phase conversions have been compared with control runs where either the orography was cut off or the phase conversions were omitted. The results show a strong orographic influence in case of pre-frontal foehn which warms the pre-frontal air and increases the cross-frontal temperature contrast leading to an acceleration of the front along the northern Alpine rim. The latent heat effect was found to depend much on the position of precipitation relative to the surface front line. In case of pre-frontal foehn precipitation only falls behind the surface front line into the intruding cold air where it partly evaporates. In contrary, precipitation already appears ahead of the front in the case of blocking. Thus, the cooling effect of evaporating rain increases the cross-frontal temperature difference only in the first case causing an additional acceleration of the front.List of symbols C _pd specific heat capacity of dry air at constant pressure (C _pd =1004.71 J kg^–1 K^–1) - C _pv specific heat capacity of water vapour at constant pressure (C _pv =1845.96 J kg^–1 K^–1) - C _f propagation speed of a front - x, y horizontal grid spacing (cartesian system) - , horizontal grid spacing (geographic system) - t time step - E turbulent kinetic energy - f Coriolis parameter - g gravity acceleration (g=9.81 ms^–1) - h terrain elevation - H height of model lid (H=9000 m) - k Karman constant (k=0.4) - K _Mh horizontal exchange coefficient of momentum - K _Hh horizontal exchange coefficient of heat and moisture - K _Mz vertical exchange coefficient of momentum - K _Hz vertical exchange coefficient of heat and moisture - l mixing length - l _c specific condensation heat (l _c =2500.61 kJ kg^–1) - l _f specific freezing heat (l _f =333.56 kJ kg^–1) - l _s specific sublimation heat (l _s =2834.17 kJ kg^–1) - longitude - m ₁,m ₂,m ₃ metric coefficients - p pressure - Exner function - Pr Prandtl number - latitude - _M profile function - q _v specific humidity - q _c specific content of cloud droplets - q _i specific content of cloud ice particles - q _R specific content of rain drops - q _S specific content of snow - R _d gas constant of dry air (R _d =287.06 J kg^–1 K^–1) - R _v gas constant of water vapour (R _v =461.51 J kg^–1 K^–1) - r _E radius of earth (r _E =6371 km) - Ri _F flux Richardson number - density of dry air - t time - T temperature - _dia period of diastrophy - potential temperature - _v virtual potential temperature - _e equivalent potential temperature - U relative humidity - u, v, w cartesian wind components - u _F ,v _F front-normal and front-parallel wind components - x, y, z cartesian coordinates - w ^* transformed vertical wind component - W _R speed of falling rain - W _S speed of falling snow - z ^* transformed vertical coordinate Abbreviations GND (above) ground level - MSL (above) mean sea level With 12 Figures     

The Reactivity of Biogenic Monoterpenes towards OH· and SO4-· Radicals in De-Oxygenated Acidic Solution

The reactivity of some selected biogenic monoterpenecompounds towards important aqueous phase free-radicaloxidants, namely OH· and SO₄ ^-·, have beeninvestigated using the complementary experimentaltechniques of pulse radiolysis and laser flashphotolysis ( = 248 nm). Rate constants forthe reactions of the OH· radical with cis-verbenol andmethacrolein have been determined to be (6.8 ± 0.5) ×10⁹ dm³ mol^-1 s^-1 and (8.0± 0.7) × 10⁹ dm³ mol^-1s^-1,respectively (T = 20 °C, pH 4.0, Ionic strength 0 mol dm^-3). Rate constants and activationenergies for the reactions of the SO₄ ^-·radical have been measured for the following compounds(T = 20 °C, pH 4.0, Ionic strength = 0.03 moldm^-3): -pinene (k = (3.1 ± 0.1) ×10⁹ dm³ mol^-1 s^-1;E _act. =(8.9 ± 1.3) kJ mol^-1), -terpineol(k = (4.1 ± 0.1) × 10⁹ dm³mol^-1s^-1; E _act. = (13.4 ± 0.6) kJmol^-1), cis-verbenol (k = (3.2 ± 0.2) ×10⁹ dm³ mol^-1 s^-1;E _act. =(10.0 ± 0.7) kJ mol^-1), verbenone (k = (1.6± 0.1) × 10⁹ dm³ mol^-1s^-1;E _act. = (6.1 ± 0.7) kJ mol^-1), myrtenal(k = (1.85 ± 0.1) × 10⁹ dm³mol^-1s^-1; E _act. = (7.5 ± 0.7) kJmol^-1)and methacrolein (k = (1.18 ± 0.1) × 10⁹dm³ mol^-1 s^-1). In most instances theabsorption spectra of the intermediate products formedby these reactions have been measured which, inconjunction with strategic conductiometric studies,have been used to suggest plausible mechanisms for theoxidation in acidic de-oxygenated solution.     

Basis for integration of conventional observations of cloud into global nephanalyses

Water vapour is the largest and, radiatively, the most important trace gas in the Earth's atmosphere. Cloud amount and cloud optical depth feedbacks are, as yet, poorly understood and improvements in model parameterization schemes await an adequate observational data base. Satellite retrievals do not, and will not for some time, provide more than snapshot (a few months to a few years) records. Conventional surface-based observations of cloudiness could complement the global coverage offered by satellite retrievals if a sound relationship between the two observational measurements could be found. Observations underline the importance of the vertical dimension of clouds which affects the observational geometries from satellites and the surface. A new basis for the relationship between the (vertical) earthview of cloud amount and the (whole dome) skycover of cloud amount has been sought. Over four and a half thousand all-sky camera photographs, representing a considerable range of seasonal and climatological conditions, have been analyzed to give rise to a database from which predictive relationships for earthview, E, and skycover, S, have been established.Cubic functions are the most soundly based both physically and empirically. We find: S=0.647+2.192E–0.461E ²+0.037E ³ and E=-0.001+0.082S+0.269S ²–0.019S ³ for the prediction of skycover from earthview and earthview from skycover, respectively. If earthview is required from skycover observations then ES could be used with little additional error. Hence, conventional surface observations of skycover could be compared directly with satellite-derived earthview values. More importantly, these results do not support the widespread assumption that conventional (surface) observations of cloud amount always exceed the earthview could retrieval. Furthermore, climate model predictions of total cloud amount may also be interpreted via these relationships. GCM-predicted layer cloud amounts can be synthesized into modelled E values using the random overlap formula and hence it is possible to construct modelled S values which are directly comparable with conventionally observed cloud climatologies. The baseline observation of skycover by clouds therefore provides a valuable validation tool for both satellite programmes and climate models.     

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).     

FT-IR Study of the Kinetics and Products of the Reactions of Dimethylsulphide, Dimethylsulphoxide and Dimethylsulphone with Br and BrO

Kinetics and products of the gas-phase reactions of dimethylsulphide (DMS), dimethylsulphoxide (DMSO) and dimethylsulphone (DMSO₂) with Br atoms and BrO radicals in air have beeninvestigated using on-line Fourier Transform Infrared Spectroscopy (FT-IR) as analytical technique at 740 ± 5 Torr total pressure and at 296 ± 3 K in a480 L reaction chamber. Using a relative rate method for determining the rate constants; the following values (expressed in cm³molecule^–1 s^–1) were found: k_DMS+Br = (4.9 ±1.0) ×10^–14, k_DMSO + Br < 6 × 10^–14,k_{DMSO 2} + Br 1 × 10^–15,k_DMSO + BrO = (1.0 ± 0.3) × 10^–14 andk_{DMSO 2} + BrO 3 × 10^–15 (allvalues are given with one on the experimental data). DMSO, SO₂, COS, CH₃SBr andCH₃SO₂Br were identified as the main sulphur containing products of the oxidation of DMS by Br atoms. From the reaction between DMSO and Br atoms, DMSO₂and CH₃SO₂Br were the only sulphur containing products thatwere identified. DMSO, DMSO₂ and SO₂ were identified as themain sulphur containing products of the reaction between DMS and BrO.DMSO₂ was found to be the only product of the reaction between DMSO and BrO. For the reactions of DMSO₂ with Br and BrO no products were identified because the reactions were too slow.The implications of these results for atmospheric chemistry are discussed.     

The budget of carbon dioxide variance in the surface layer over vegetated fields

The budget equation for carbon dioxide variance can be represented by production, dissipation and flux divergence terms. Each term is measured under near neutral to moderately unstable conditions over vegetated fields. The flux divergence term is about an order of magnitude smaller than production and dissipation terms, though it shows a loss for 0.006 < _v < 1 and a gain for 1 < - _v < 10. Here, _v is the Monin-Obukhov stability parameter including humidity effect. As expected from a closure of the budget, the nondimensional production and dissipation terms are basically identical and represented by the same functional form: (1–16 _v )^–1/2.     

A numerical modeling study of the marine boundary layer over the Gulf Stream during cold air advection

A two-dimensional mesoscale model has been developed to simulate the air flow over the Gulf Stream area where typically large gradients in surface temperature exist in the winter. Numerical simulations show that the magnitude and the maximum height of the mesoscale circulation that develops downwind of the Gulf Stream depends on both the initial geostrophic wind and the large-scale moisture. As expected, a highly convective Planetary Boundary Layer (PBL) develops over this area and it was found that the Gulf Stream plays an important role in generating the strong upward heat fluxes causing a farther seaward penetration as cold air advection takes place. Numerical results agree well with the observed surface fluxes of momentum and heat and the mesoscale variation of vertical velocities obtained using Doppler Radars for a typical cold air outbreak. Precipitation pattern predicted by the numerical model is also in agreement with the observations during the Genesis of Atlantic Lows Experiment (GALE).List of Symbols u east-west velocity [m s^–1] - v north-south velocity [m s^–1] - vertical velocity in coordinate [m s^–1] - w vertical velocity inz coordinate [m s^–1] - gq potential temperature [K] - q moisture [kg kg^–1] - scaled pressure [J kg^–1 K^–1] - U _g the east-south component of geostrophic wind [m s^–1] - V _g the north-south component of geostrophic wind [m s^–1] - vertical coordinate following terrain - x east-west spatial coordinate [m] - y north-south spatial coordinate [m] - z vertical spatial coordinate [m] - t time coordinate [s] - g gravity [m² s^–1] - E terrain height [m] - H total height considered in the model [m] - q _s saturated moisture [kg kg^–1] - p pressure [mb] - p ₀₀ reference pressure [mb] - P precipitation [kg m^–2] - vertical lapse rate for potential temperature [K km^–1] - L latent heat of condensation [J kg^–1] - C _p specific heat at constant pressure [J kg^–1 K^–1] - R gas constant for dry air [J kg^–1 K^–1] - R _v gas constant for water vapor [J kg^–1 K^–1] - f Coriolis parameter (2 sin ) [s^–1] - angular velocity of the earth [s^–1] - latitude [^o] - K _H horizontal eddy exchange coefficient [m² s^–1] - t integration time interval [s] - x grid interval distance inx coordinate [m] - y grid interval distance iny coordinate [m] - adjustable coefficient inK _H - subgrid momentum flux [m² s^–2] - subgrid potential temperature flux [m K s^–1] - subgrid moisture flux [m kg kg^–1 s^–1] - u _* friction velocity [m s^–1] - _* subgrid flux temperature [K] - q _* subgrid flux moisture [kg kg^–1] - w _* subgrid convective velocity [m s^–1] - z ₀ surface roughness [m] - L Monin stability length [m] - _s surface potential temperature [K] - k von Karman's constant (0.4) - v air kinematic viscosity coefficient [m² s^–1] - K _M subgrid vertical eddy exchange coefficient for momentum [m² s^–1] - K subgrid vertical eddy exchange coefficient for heat [m² s^–1] - K _q subgrid vertical eddy exchange coefficient for moisture [m² s^–1] - z _i the height of PBL [m] - h _s the height of surface layer [m]     

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.     

On the Exchange of NO3 Radicals with Aqueous Solutions: Solubility and Sticking Coefficient

The exchange of NO₃ radicals with the aqueous-phase was investigated at room temperature (293 K) in a series of wetted denuders. From these experiments, the uptake coefficient of NO₃ was determined on 0.1 M NaCl solutions and was found to be (NO₃) 2 × 10^-3 in good agreement with recent studies. The Henry coefficient of NO₃ was estimated to be K_H(NO₃) = 1.8 M · atm^-1, with a (2) uncertainty of ±3 M · atm^-1. From the upper limit for the Henry coefficient (K_H = 5 M · atm^-1) and available thermodynamic data, the redox potential of dissolved NO₃/NO ₃ ^– is estimated to be in the range of 2.3 to 2.5 V. This range is at the lower boundary of earlier estimates. The results are discussed in the light of a recent publication. Based on our data and a model of the transport and chemistry in the liquid film, an upper limit is derived for the product of the Henry coefficient K_H and the rate coefficient k ₁₀ of the potential reaction NO₃ + H₂O HNO₃ + OH. For K_H = 0.6 M · atm^-1, we find k ₁₀ < 0.05 s^-1 · atm^-1, i.e., about 100 times smaller than what was suggested by Rudich and co-workers. Because of its small solubility, heterogeneous removal of NO₃ is only important under conditions where the dissolved NO₃ is removed quickly from equilibrium, for example by reactions with Cl^– or HSO ₃ ^– ions in the liquid-phase. Otherwise, heterogenous removal should mainly proceed via N₂O₅.     

Kinetic investigation of the OH + CH3Br reaction between 248 and 390 K

The rate parameters for the reaction of the OH radical with CH₃Br have been measured using the discharge flow-electron paramagnetic resonance method. The result isk ₁=(1.86±0.48)×10^–12 exp[–(1230±150)/T] cm³ molecule^–1 s^–1. This value is compared to earlier data and is found to be in excellent agreement with the most recent results, which greatly increases the accuracy of the ozone depletion potential of CH₃Br which can be derived from these kinetic data.     

Sulfur dioxide plume dispersion and subsequent absorption by coniferous forests: Field measurements and model calculations

A Forest SO₂ Absorption Model (ForSAM) was developed to simulate (1) SO₂ plume dispersion from an emission source, (2) subsequent SO₂ absorption by coniferous forests growing downwind from the source. There are three modules: (1) a buoyancy module, (2) a dispersion module, and (3) a foliar absorption module. These modules were used to calculate hourly abovecanopy SO₂ concentrations and in-canopy deposition velocities, as well as daily amounts of SO₂ absorbed by the forest canopy for downwind distances to 42 km. Model performance testing was done with meteorological data (including ambient SO₂ concentrations) collected at various locations downwind from a coal-burning power generator at Grand Lake in central New Brunswick, Canada. Annual SO₂ emissions from this facility amounted to about 30,000 tonnes. Calculated SO₂ concentrations were similar to those obtained in the field. Calculated SO₂ deposition velocities generally agreed with published values.Notation c air parcel cooling parameter (non-dimensional) - E foliar absorption quotient (non-dimensional) - f areal fraction of foliage free from water (non-dimensional) - f _w SO₂ content of air parcel - h height of the surface layer (m) - H height of the convective mixing layer (m) - H _stack stack height (m) - k time level - k _drag coefficient of drag on the air parcel (non-dimensional) - K _z eddy viscosity coefficient for SO₂ (m²·s^–1) - L Monin-Obukhov length scale (m) - L _A single-sided leaf area index (LAI) - n degree-of-sky cloudiness (non-dimensional) - N number of parcels released with every puff (non-dimensional) - PAR photosynthetically active radiation (W m^–2) - Q emission rate (kg s^–2) - r _b diffusive boundary-layer resistance (s m^–1) - r _c canopy resistance (s m^–1) - r _cuticle cuticular resistance (s m^–1) - r _m mesophyllic resistance (s m^–1) - r _s stomatal resistance (s m^–1) - r _exit smokestack exit radius (m) - R normally distributed random variable with mean of zero and variance of t (s) - u _* frictional velocity scale, (m s^–1) - v lateral wind vector (m s^–1) - v _d SO₂ dry deposition velocity (m s^–1) - VCD water vapour deficit (mb) - z _can mean tree height (m) - Z zenith position of the sun (deg) - environmental lapse rate (°C m^–1) - dry adiabatic lapse rate (0.00986°C m^–1) - von Kármán's constant (0.04) - _B vertical velocities initiated by buoyancy (m s^–1) - canopy extinction coefficient (non-dimensional) - ()a denotes ambient conditions - ()can denotes conditions at the top of the forest canopy - ()h denotes conditions at the top of the surface layer - ()H denotes conditions at the top of the mixed layer - ()s denotes conditions at the canopy surface - ()p denotes conditions of the air parcels