Henry's law coefficients of formic and acetic acids

The Henry's law constants, K _H, of dilute aqueous formic and acetic acids were determined experimentally as a function of concentration and temperature using a new counterflow packed-column technique. K _H was found to be (8.9±1.3)×10³ and (4.1±0.4)×10³ M atm^-1 at 25°C for HCOOH and CH₃COOH, respectively. The reaction enthalpies, H, were found to be –51±2 kJ mol^-1 and –52±1 kJ mol^-1 for formic and acetic acid, respectively. These are in good agreement with calculated thermochemical values.Whereas the K _H values are in reasonably good agreement with certain other experimentally determined values, K _H (HCOOH) is two to three times higher than calculated thermochemical values while K _H (CH₃COOH) is lower than the two calculated values.The best experimental values appear to be (11±2)×10³ M atm^-1 and (7±3)×10³ M atm^-1 for HCOOH and CH₃COOH, respectively.     

Solubility of HOCl in water and aqueous H2SO4 to stratospheric temperatures

Henry's law constants K_H (mol kg^–1 atm^–1) for the reaction HOCl_(g)=HOCl_(aq) near room temperature, literature data for the associated enthalpy change, and solubilities of HOCl in aqueous H₂SO₄ (46 to 60 wt%) at temperatures relevant to the stratosphere (200 KT230 K) are shown to be thermodynamically consistent. Effective Henry's law constants [H*=mHOCl/pHOCl, in mol kg^–1 atm^–1] of HOCl in aqueous H₂SO₄ are given by: ln(H*)=6.4946–mH₂SO₄(–0.04107+54.56/T)–5862 (1/T_o–1/T) where T(K) is temperature and T_o=298.15K. The activity coefficient of HOCl in aqueous H₂SO₄ has a simple Setchenow-type dependence upon H₂SO₄ molality.     

The Henry's Law Constants of the Haloacetic Acids

Henry's law constants K_H (mol kg^-1 atm^-1) have been measured between 278.15 K and 308.15 K for the following organic acids: CH₂FCOOH (ln(K_H[298.15 K]) = 11.3 ± 0.2), CH₂ClCOOH (11.59 ± 0.14), CH₂BrCOOH (11.94 ± 0.21), CHF₂COOH (10.32 ± 0.10), CHCl₂COOH (11.69 ± 0.11), CHBr₂COOH (12.33 ± 0.29), CBr₃COOH (12.61 ± 0.21), and CClF₂COOH (10.11 ± 0.12). The variation of K_H with temperature was determined for all acids except CH₂FCOOH and CBr₃COOH, with _r H° for the dissolution reaction ranging from –85.2 ± 2.6 to –57.1 ± 2.5 kJ mol^-1, meaning that their solubility is generally more sensitive to temperature than is the case for the simple carboxylic acids. The Henry's law constants show consistent trends with halogen substitution and, together with their high solubility compared to the parent (acetic) acid (ln(K_H[298.15 K]) = 8.61), present a severe test of current predictive models based upon molecular structure. The solubility of haloacetic acids and strong dissociation at normal pH mean that they will partition almost entirely into cloud and fog in the atmosphere (0.05–1.0 g H₂O m^-3), but can reside in both phases for the liquid water contents typical of aerosols (10^-5-10^-4 g H₂O m^-3).     

The Mechanism of Reactive NO3 Uptake on Dry NaX (X=Cl, Br)

A simple kinetic mechanism of nitrate radicals uptake on dry sea-salt NaCl, NaBr surfaces is proposed. The mechanism includes adsorption/desorption equilibrium and unimolecular decomposition of the adsorbed complex: NO₃(g) + NaX(s) (NO₃-NaX)(s); (NO₃-NaX)(s) NaNO₃ + X(s) Two techniques were used: the matrix isolation ESR and mass spectrometry. The uptake coefficient () is found to be dependent on exposure time of salt to NO₃ for raw coating. The initial (t0) is higher than the observable steady-state _obs. At room temperature _obs is independent of [NO₃] at low [NO₃] = 3 × 10⁹ - 10¹¹ cm^-3, but it is inversely proportional to [NO₃] at concentrations higher than 10¹² cm^-3. At temperatures above 100 °C, _obs becomes independent of [NO₃] in a wider range of [NO₃]. An increased number of dislocations is supposed to exist in the case of raw coating. Due to a wide spread of the surface sites binding energy with the ionic lattice near dislocations, the part of surface complexes has lower binding energy and "burns" more rapidly. That burning determines the transition from (t0) down to _obs.The kinetic parameters and elementary rate coefficients are obtained. The recommended for low atmospheric NO₃ concentration are in the range of 0.002 ± 0.04 for NaCl and 0.1-0.3 for NaBr depending on a mechanism of the (t) relaxation.     

Henry's law constant and hydrolysis of peroxyacetyl nitrate (PAN)

The effect of temperature on the solubility of PAN and on its hydrolysis rate in near-neutral and slightly acidic water were studied in a bubble column apparatus. The results obtained are a Henry's law coefficient H=10^–9.04±0.6 exp[(6513±376)/T] M atm^–1, and a first-order hydrolysis rate constant k=10^6.60±1.0 exp[(–6612±662)/T] s^-1, which was independent of pH in the range 3.2pH6.7. The products formed are nitrite and nitrate in approximately equal proportions under near-neutral conditions. At a pH<4, nitrite is oxidized in a secondary reaction, and nitrate becomes the only product at low pH. Previously measured deposition velocities of PAN on stagnant water surfaces are shown to be hydrolysis rate limited.     

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]     

Solubilities of pyruvic acid and the lower (C1-C6) carboxylic acids. Experimental determination of equilibrium vapour pressures above pure aqueous and salt solutions

Henry's law constantsK _H (mol kg^–1 atm^–1) have been determined at 298.15 K for the following organic acids: formic acid (5.53±0.27×10³); acetic acid (5.50±0.29×10³); propionic acid (5.71±0.34×10³);n-butyric acid (4.73±0.18×10³); isobutyric acid (1.13±0.12×10³); isovaleric acid (1.20±0.11×10³) and neovaleric acid (0.353±0.04×10³). They have also been determined fromT=278.15 K toT=308.15 K forn-valeric acid (ln(K _H)=–14.3371+6582.96/T);n-caproic acid (ln(K _H)=–13.9424+6303.73/T) and pyruvic acid (ln(K _H)=–4.41706+5087.92/T). The influence of 9 salts on the solubility of pyruvic acid at 298.15 K has been measured. Pyruvic acid is soluble enough to partition strongly into aqueous atmospheric aerosols. Other acids require around 1 g of liquid water m^–3 (typical of clouds) to partition significantly into the aqueous phase. The degree of partitioning is sensitive to temperature. Considering solubility and dissociation (to formate) alone, the ratio of formic acid to acetic acid in liquid water in the atmosphere (at equilibrium with the gas phase acids) is expected to increase with rising pH, but show little variation with temperature.     

Intercomparison of instruments for tropospheric measurements using differential optical absorption spectroscopy

The results of an intercomparison campaign of eight different long path UV-visible DOAS instruments measuring NO₂, O₃ and SO₂ concentrations in a moderately polluted urban site are presented. For effective optical path lengths of 230 and 780 m the overall spread of these measurements (±1) are 5×10¹⁰, 6×10¹⁰ and 1×10¹⁰ molec·cm^-3 (2.0, 2.4, and 0.4 ppb) for these molecules respectively when all instruments used a common set of absorption cross sections. The remaining differences are not completely random and the systematic differences are attributed to the different retrieval methods used for each instrument.     

Characterization of Organic Acids in Dew Collected on Surrogate Surfaces

Levels of formate and acetate in dew were measured at Dayalbagh, India, usingsurrogate surfaces. The dew formed per night ranged between 0.06 lm^–2 and 1.38 l m^–2, with an average of 0.59l m^–2. pH ranged between 6.7 and 7.4. Mean concentrations offormate and acetate in dew were 10.2 ± 10.2 eql^–1 and 7.5 ± 4.5 eq l^–1,respectively. The correlation coefficient between the two ions was 0.80 (p =0.001), which suggested that concentrations of these species in dew are linkedtogether. They have either common or different sources with fairly constantstrengths or products of same reaction. Good correlation of formate andacetate with Ca (r = 0.82 and r = 0.70, respectively) and Mg (r = 0.74 and r= 0.71, respectively) suggested that these ions may be associated with Ca andMg after the neutralization process. Deposition rates for formate and acetatein dew per night were 10.2 ± 7.22 mol m^–2 pernight and 4.6 ± 2.2 mol m^–2 per night,respectively. The theoretical Henry's law constant (K^* _H)and the field-observed Henry's law coefficient (K^* _H) ascalculated from concurrent measurements of gas phase and dew for both acidsshowed large discrepancies of three orders of magnitude.     

The Influence of NaBr/NaCl Ratio on the Br--Catalysed Production of Halogenated Radicals

The activation of Br^- and Cl^- to atomic Br and Cl in sea-spray aerosol was investigated in smog-chamber experiments. In the presence of O₃, hydrocarbons and NaCl aerosol alone no activation was observed. By adding Br^- to the aerosol, the chain reaction: Br + O₃ BrO, BrO + HO₂ HOBr, HOBr HOBr(aq), HOBr(aq) + H⁺ + Br^- Br₂ (6), HOBr(aq) + H⁺ + Cl^- BrCl (7) was verified. The step from reaction (6) to (7) is accompanied by a decrease of the Br^-/Cl^- ratio from 1/600 to less than 1/2000. In the absence of sulphate, the chain is initiated by the reaction of OH(aq) with Br^-. The pH value decreases to less than 2 during the first minutes of the experiment and later on to almost 1 (in the absence of NO_x or SO₂). This is caused by the formation of oxalic acid from alkanes and toluene. In stopped flow experiments, the reduction of Br₂ by oxalic acid was observed to occur through a two-step mechanism: HC₂O₄ ^- + Br₂ Br^- + BrC₂O₄H (k₂₂, k_-22), BrC₂O₄H Br^- + H⁺ + 2 CO₂ (23) with the following rate constants and ratios of rate constants, k ± 2: k₂₂k_-23 / k_-22 = (2.9 ± 0.3) · 10^-4 s^-1, k_-22 / k_-23 = 7000 ± ₃₀₀₀ ¹³⁰⁰⁰ M^-1, k₂₂ = 2 ±_-1 ⁴ M^-1 s^-1, and k_-23 > 0.1 s^-1, k_-22 > 600 M^-1 s^-1. Oxalic acid may be responsible for the inhibition of the chain reaction observed at the end of the experiments.     

Size-Resolved Characterisation of Soluble Ions in the Particles in the Tropospheric Plume of Masaya Volcano, Nicaragua: Origins and Plume Processing

We present the first application of a multi-stage impactor to study volcanic particle emissions to the troposphere from Masaya volcano, Nicaragua. Concentrations of soluble SO₄ ^2–,Cl^–, F^–, NO₃ ^–, K⁺, Na⁺,NH₄ ⁺, Ca²⁺ and Mg²⁺ were determined in 11 size bins from 0.07 m to >25.5 m. The near-source size distributions showed major modes at 0.5m (SO₄ ^2–, H⁺,NH₄ ⁺); 0.2 m and 5.0 m (Cl^–) and 2.0–5.0 m(F^–). K⁺ and Na⁺ mirrored the SO₄ ^2– size-resolvedconcentrations closely, suggesting that these were transported primarily asK₂SO₄ and Na₂SO₄ in acidic solution, while Mg²⁺ andCa²⁺ presented modes in both <1 m and >1 m particles. Changes in relative humidity were studied by comparing daytime (transparent plume) and night-time (condensed plume) results. Enhanced particle growth rates were observed in the night-time plume as well as preferential scavenging of soluble gases, such as HCl, by condensed water. Neutralisation of the acidic aerosol by background ammonia was observed at the crater rim and to a greater extent approximately 15 km downwind of the active crater. We report measurements of re-suspended near-source volcanic dust, which may form a component of the plume downwind. Elevated levels ofSO₄ ^2–, Cl^–, F^–,H⁺, Na⁺, K⁺ and Mg²⁺ were observed around the 10 m particle diameter in this dust. The volcanic SO₄ ^2– flux leaving the craterwas 0.07 kg s^–1.     

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     

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     

Kinetics of the reaction of nitrogen dioxide with ozone

The kinetics of the reaction of NO₂ with O₃ have been investigated at 296 K, using UV absorption spectroscopy to monitor decay of NO₂ or O₃ and infrared laser absorption spectroscopy to monitor formation of the reaction product N₂O₅. The results both for the rate coefficient at 296 K (k ₁=3.5×10^-17 cm³ molecule^-1 s^-1) and the reaction stoichiometry (NO₂/O₃=1.85±0.09) are in good agreement with previous studies, confirming that the two step mechanism involving formation of symmetrical NO₃ as an intermediate is predominant.% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaeOtaiaab+% eadaWgaaWcbaGaaeOmaaqabaGccqGHRaWkcaqGpbWaaSbaaSqaaiaa% bodaaeqaaOWaa4ajaSqaaaqabOGaayPKHaGaaeOtaiaab+eadaWgaa% WcbaGaae4maaqabaGccqGHRaWkcaqGpbWaaSbaaSqaaiaabkdaaeqa% aaaa!41D7!\[{\text{NO}}_{\text{2}} + {\text{O}}_{\text{3}} \xrightarrow{{}}{\text{NO}}_{\text{3}} + {\text{O}}_{\text{2}} \]% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaeOtaiaab+% eadaWgaaWcbaGaae4maaqabaGccqGHRaWkcaqGobGaae4tamaaBaaa% leaacaqGYaaabeaakiabgUcaRiaab2eadaGdKaWcbaaabeGccaGLsg% cacaqGobWaaSbaaSqaaiaabkdaaeqaaOGaae4tamaaBaaaleaacaqG% 1aaabeaakiabgUcaRiaab2eaaaa!4464!\[{\text{NO}}_{\text{3}} + {\text{NO}}_{\text{2}} + {\text{M}}\xrightarrow{{}}{\text{N}}_{\text{2}} {\text{O}}_{\text{5}} + {\text{M}}\]A possible minor role for the unsymmetrical ONOO species is suggested to account for the lower-than-expected stoichiometry factor. The importance of this reaction in the oxidation of atmospheric NO₂ is discussed.     

A study of the seasonal migration of ITCZ and the quasi-periodic oscillations in a simple monsoon system using an energy balance model

Summary A zonally averaged global energy balance model with feedback mechanisms was constructed to simulate (i) the poleward limits of ITCZ over the continent and over the ocean and (ii) a simple monsoon system as a result of differential heating between the continent and the ocean. Three numerical experiments were performed with lower boundary as (1) global continent, (2) global ocean and (3) continent-ocean, with freezing latitudes near the poles. Over the continent, midlatitude deserts were found and the ITCZ migrates 25° north and south with seasons. Over a global swamp ocean results do not show migration of ITCZ with time but once the ocean currents are introduced the ITCZ migrates 5° north and south with seasons. It was found that the seasonal migration of ITCZ strongly depends on the meridional distribution of the surface temperature. It was also found that continent influences the location of the oceanic ITCZ. In the tropics northward progression of quasi-periodic oscillations called events are found during the pre- and post-monsoon periods with a period of 8 to 15 days. This result is consistent with the observed quasi-periodic oscillations in the tropical region. Northward propagation of the surface temperature perturbation appears to cause changes in the sensible heat flux which in turn causes perturbations in vertical velocity and latent heat flux fields.List of Symbols vertical average - ₀ zonal average - vertical mean of the zonal average - _0s zonal average at the surface - _0a zonal average at 500 mb level - latitude We now define the various symbols used in the model rate of atmospheric heating due to convective cloud formation (K/sec) - dp/dt (N/m²/sec) - density - potential temperature (K) - rate of rotation of the earth (rad/sec) - empirical constant - humidity mixing ratio - ^* saturated humidity mixing ratio - opacity of the atmosphere - ₁,₂ factors for downward and upward effective black body long wave radiation from the atmosphere - Stefan-Boltzmann constant - emissivity of the surface - _D subsurface temperature (K) - a specific volume - _0xs ,_0ys eastward and northward components of surface frictional stress - ^* vertical velocity at the top of the boundary layer (N/m²/sec) - P Thickness of the boundary layer (mb) - nondimensional function of pressure - P pressure - P _a pressure of the model atmosphere (N/m²) - P _s pressure at the surface (N/m²) - t time (sec) - U eastward wind speed (m/sec) - V northward wind speed (m/sec) - surface water availability - T absolute temperature (K) - heat addition due to water phase changes - g acceleration due to gravity (m²/sec) - a radius of the earth (m) - R gas constant for dry air (J/Kg/K) - C _p specific heat of air at constant pressure (J/Kg/K) - k R/C _p - L latent heat of condensation (J/Kg) - f coriolis parameter (rad/sec) - H _s H _0s ⁽¹⁾ +H _0s ⁽²⁾ +H _0s ⁽³⁾ +H _0s ⁽⁴⁾ +H _0s ⁽⁵⁾ (J/m²/Sec)=sum of the rates of vertical heat fluxes per unit surface area, directed toward the surface - H _a H _0a ⁽¹⁾ +H _0a ⁽²⁾ +H _0a ⁽³⁾ +H _0a ⁽⁴⁾ (J/m²/Sec)=sum of the rates of heat additions to the atmospheric column per unit horizontal area by all processes - H _0s ⁽¹⁾ ,H _0a ⁽¹⁾ heat flux due to short wave radiation - H _0s ⁽²⁾ ,H _0a ⁽²⁾ heat flux due to long wave radiation - H _0s ⁽³⁾ ,H _0a ⁽³⁾ heat flux due to small scale convection - H _0s ⁽⁴⁾ heat flux due to evaporation - H _0a ⁽⁴⁾ heat flux due to condensation - H _0s ⁽⁵⁾ heat flux due to subsurface conduction and convection - e ^* saturation vapor pressure - R solar constant (W/m²) - r _a albedo of the atmosphere - r _s albedo of the surface - b ₂ empirical constant (J/m²/sec) - c ₂ empirical constant (J/m²/sec) - e ₂ nondimensional empirical constant - f ₂ empirical constant (J/m₂/sec) - factor proportional to the conductive capacity of the surface medium - a _s constant used in Sellers model - b _s positive constant of proportionality used in the Sellers model (kg m²/J/sec²) - K _HT coefficient for eddy diffusivity of heat (m²/sec) - K _HE exchange coefficient for water vapor (m²/sec) - h depth of the water column (m) - z height (m) - V _0ws meridional component of surface current (m/sec) - n cloud amount - G _0,n long wave radiation form the atmosphere for cloud amount n (W/m²) - B ₀ long wave radiation from the surface (W/m²) - S _0,n short wave radiation from the atmosphere for cloud amount n (W/m²) - A _n albedo factor for a cloud amount n - R _f1 large scale rainfall (mm/day) - R _f2 small scale rainfall (mm/day) With 22 Figures     

Nitrous oxide emissions from fertilized and unfertilized soils in a subtropical region (Andalusia,Spain)

Field measurements of N₂O emission rates were carried out from August until October 1982 in a subtropical region in Europe, i.e. in Andalusia, Spain. The measurements were performed by using an automatic sampling and analysis technique allowing the semi-continuous determination of N₂O emission rates. The N₂O emission rates were positively correlated to the soil surface temperature and exhibited a diurnal rhythm with maximum rates in the afternoon and minimum rates in the early morning with average values of 1 g N₂O–N/m²/h for the grass lawn and 15 g N₂O–N/m²/h for cultivated land. Application of urea and ammonium nitrate resulted in elevated N₂O emission rates when compared to the unfertilized control. The loss of fertilizer-nitrogen as N₂O was 0.18% for urea and 0.04% for NH₄NO₃ which compares very well with data obtained in a temperate climate (Germany). The total source strength of fertilizer-derived N₂O is estimated to be 0.01–2.2 Tg N₂O–N per year. The N₂O flux from unfertilized natural soils may be as high as 4.5 Tg N₂O–N, indicating that the N₂O emission from soils contributes significantly to the global N₂O budget.     

Uptake of the NO <Subscript>3</Subscript> Radical on Aqueous Surfaces

Using a single drop experiment, the uptake of NO₃ radicals on aqueous solutions of the dye Alizarin Red S and NaCl was measured at 293 K. Uptake coefficients in the range (1.7–3.1) ⋅ 10^{− 3} were measured on Alizarin Red S solutions. The uptake coefficients measured on NaCl solutions were in the range of (1.1–2.0) ⋅ 10⁻³ depending on the salt concentration. Both experiments lead to a consistent result for the mass accommodation coefficient of α_NO3 = (4.2_{− 1.7}^+2.2)⋅ 10⁻³. The product H(D_l k_Cl−^II)^0.5 for the NO₃ radical was determined to be (1.9 ± 0.2) M atm^{− 1} cm s^−0.5 M^−0.5 s^−0.5 by fitting the uptake data for the NaCl solutions to the so-called resistance model. The yield of the chemical NO₃ radical source was characterized using UV-VIS and FT-IR spectroscopy. The amount of gas-phase NO₃ radicals measured at elevated humidities was less than expected. Instead, a rise of the gas-phase HNO₃ concentration was found indicating a conversion of gas-phase NO₃ radicals to gas-phase HNO₃ on the moist reactor walls.     

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.     

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.