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 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 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]     

Mixed-layer heat advection and entrainment during the sea breeze

A model is developed to simulate the potential temperature and the height of the mixed layer under advection conditions. It includes analytic expressions for the effects of mixed-layer conditions upwind of the interface between two different surfaces on the development of the mixed layer downwind from the interface. Model performance is evaluated against tethersonde data obtained on two summer days during sea breeze flow in Vancouver, Canada. It is found that the mixed-layer height and temperature over the ocean has a small but noticeable effect on the development of the mixed layer observed 10 km inland from the coast. For these two clear days, the subsidence velocity at the inversion base capping the mixed layer is estimated to be about 30 mm s^–1 from late morning to late afternoon. When the effects of subsidence are included in the model, the mixed-layer height is considerably underpredicted, while the prediction for the mean potential temperature in the mixed layer is considerably improved. Good predictions for both height and temperature can be obtained when values for the heat entrainment ratio,c, 0.44 and 0.68 for these two days respectively for the period from 1000 to 1300 LAT, were used. These values are estimated using an equation including the additional effects on heat entrainment due to the mechanical mixing caused by wind shear at the top of the mixed layer and surface friction. The contribution of wind shear to entrainment was equal to, or greater than, that from buoyant convection resulting from the surface heat flux. Strong wind shear occurred near the top of the mixed layer between the lower level inland flow and the return flow aloft in the sea breeze circulation.Symbols c entrainment parameter for sensible heat - c _p specific heat of air at constant pressure, 1010 J kg^–1 K^–1 - d ₁ the thickness of velocity shear at the mixed-layer top, m - Q _H surface sensible heat flux, W m^–2 - u _m mean mixed-layer wind speed, m s^–1 - u _* friction velocity at the surface, m s^–1 - w subsidence velocity, m s^–1 - W subsidence warming,^oC s^–1 - w _e entrainment velocity, m s^–1 - w _* convection velocity in the mixed layer, m s^–1 - x downwind horizontal distance from the water-land interface, m - y dummy variable forx, m - Z height above the surface, m - Z _i height of capping inversion, m - Z _m mixed-layer depth, i.e.,Z _i–Z_s, m - Z _s height of the surface layer, m - lapse rate of potential temperature aboveZ _i, K m^–1 - potential temperature step atZ _i, K - u _h velocity step change at the mixed-layer top - _m mean mixed-layer potential temperature, K     

Latitudinal variation of measured NO2 photolysis frequencies over the Atlantic Ocean between 50° N and 30° S

Using a filter radiometer, the meridional profile of the NO₂ photolysis frequency, J(NO₂), was measured between 50° N and 30° S during the cruise ANTVII/1 September/October 1988 of the research vessel Polarstern on the Atlantic Ocean. Simultaneously, global broadband irradiance and acrosol were monitored. Clean marine background air with low aerosol loads (b _sp=(1–2)×10^-5 m^-1) was encountered at the latitudes 25° N–30° N and 18° S–27° S, respectively. Under these conditions and an almost cloudless sky J(NO₂) reached 7.3×10^-3 s^-1 (2 sr) for a zenith angle of 30°. Between 30° N and 30° S, the latitudinal variation of the J(NO₂) noontime maxima was less than ± 10%, while the mean value at noon was 7.8×10^-3 s^-1. For the set of all data between 50° N and 30° S, a nearly linear correlation of J(NO₂) vs. global broadland irradiance was found. The slope of (8.24±0.03)×10^-5 s^-1/mW cm^-2 agrees within 10% with observations in Jülich (51° N, 6.2° E).     

Eddy correlation measurements of CO2, latent heat,and sensible heat fluxes over a crop surface

Eddy correlation equipment was used to measure mass and energy fluxes over a soybean crop. A rapid response CO₂ sensor, a drag anemometer, a Lyman-alpha hygrometer and a fine wire thermocouple were used to sense the fluctuating quantities.Diurnal fluxes of sensible heat, latent heat and CO₂ were calculated from these data. Energy budget closure was obtained by summing the sensible and latent heat fluxes determined by eddy correlation which balanced the sum of net radiation and soil heat flux. Peak daytime CO₂ fluxes were near 1.0 mg m^–2 (ground area) s^–1.The eddy correlation technique was also employed in this study to measure nocturnal CO₂ fluxes caused by respiration from plants, soil, and roots. These CO₂ fluxes ranged from - 0.1 to - 0.25 mg m^–2s^–1.From the data collected over mature soybeans, a relationship between CO₂ flux and photosynthetically active radiation (PAR) was developed. The crop did not appear to be light-saturated at PAR flux densities < 1800 Ei m^–2 s^–1. The light compensation point was found to be about 160 Ei m^–2 s^–1.Published as Paper No. 7402, Journal Series, Nebraska Agricultural Experiment Station. The work reported here was conducted under Nebraska Agricultural Experiment Station Project 27-003 and Regional Research Project 11–33.Post-doctoral Research Associate, Professor and Professor, respectively. Center for Agricultural Meteorology and Climatology, Institute of Agriculture and Natural Resources, University of Nebraska, Lincoln, NE 68583-0728.     

Prediction of the abiotic degradability of organic compounds in the troposphere

A statistically relevant correlation between the reaction rate coefficient, k _OH, for the OH radical reaction with 161 organic compounds in the gas phase at 300 K, and the corresponding vertical ionisation energies E _i,v, reveals two classes of compounds: aromatics where –log(k _OH/cm³s^-1)3/2E _i,v(eV)–2 and aliphatics where –log(k _OH/cm³s^-1)4/5E _i,v(eV)+3. The prediction of the rate coefficient, k _OH, for the reaction of OH with organic molecules from the above equations has a probability of about 90%. Assuming a global diurnal mean of the OH radical concentration of 5×10⁵ cm³, the upper limit of the tropospheric half-life of organic compounds and their persistence can be estimated.     

Henry's law and the behavior of weak acids and bases in fog and cloud

Experimental data from two field experiments on ground based clouds were used to study the distribution of formic acid, acetic acid, ammonia and S(IV) species between liquid and gas phase. The ratio of the concentrations of these compounds between the phases during concurrent measurements was compared to ratios expected according to Henry's law (considering the pH influence). Large discrepancies of several orders of magnitude were seen. Three hypotheses have been investigated to explain the observed discrepancies: The existence of a microscale equilibrium which does not persist in a bulk sample, a thermodynamic shift of the equilibrium due to competing reactions, and nonequilibrium conditions due to mass transfer limitations. Approximate quantitative calculations show that none of these hypotheses is sufficient to explain all of the discrepancies, so a combination of different effects seems to be responsible for this observation. The same theoretical considerations also suggest that mass transfer limitation may be an important factor for highly soluble compounds. The data presented here indicates that it is not possible to simply extrapolate interstitial gas phase composition from measured bulk liquid phase concentrations of a fog or cloud.Notation [r _max] liquid phase molar uptake rate (mol l^–1 s^–1) - [A _g ] concentration ofA in gas phase (atm) - [A _l ] concentration ofA in liquid phase (mol l^–1) - [A _g , 0] concentration ofA in gas phase (atm) at time 0 - LWC liquid water content (g m^–3) - R universal gas constant (0.082 l atm mol^–1 K^–1 - D _g diffusivity (for all gases 0.1 cm² s^–1 was used) - K _H ^* effective Henry's law coefficient (mol l^–1 atm^–1) - t _f lifetime of fog droplet (s) - a droplet radius (cm) - accommodation coefficient - R factor of discrepancy - T temperature (K) - v mean molecular speed (cm s^–1) formic acid: 35 000 acetic acid: 31 000 ammonia: 58 000     

Vertical distribution of dimethylsulfide,sulfur dioxide,aerosol ions,and radon over the Northeast Pacific Ocean

Dimethylsulfide (DMS), sulfur dioxide (SO₂), methanesulfonate (MSA), nonsea-salt sulfate (nss-SO₄ ^2–), sodium (Na⁺), ammonium (NH₄ ⁺), and nitrate (NO₃ ^–) were determined in samples collected by aircraft over the open ocean in postfrontal maritime air masses off the northwest coast of the United States (3–12 May 1985). Measurements of radon daughter concentrations and isentropic trajectory calculations suggested that these air masses had been over the Pacific for 4–8 days since leaving the Asian continent. The DMS and MSA profiles showed very similar structures, with typical concentrations of 0.3–1.2 and 0.25–0.31 nmol m^–3 (STP) respectively in the mixed layer, decreasing to 0.01–0.12 and 0.03–0.13 nmol m^–3 (STP) at 3.6 km. These low atmospheric DMS concentrations are consistent with low levels of DMS measured in the surface waters of the northeastern Pacific during the study period.The atmospheric SO₂ concentrations always increased with altitude from <0.16–0.25 to 0.44–1.31 nmol m^–3 (STP). The nonsea-salt sulfate (ns-SO₄ ^2–) concentrations decreased with altitude in the boundary layer and increased again in the free troposphere. These data suggest that, at least under the conditions prevailing during our flights, the production of SO₂ and nss-SO₄ ^2– from DMS oxidation was significant only within the boundary layer and that transport from Asia dominated the sulfur cycle in the free troposphere. The existence of a sea-salt inversion layer was reflected in the profiles of those aerosol components, e.g., Na⁺ and NO₃ ^–, which were predominantly present as coarse particles. Our results show that long-range transport at mid-tropospheric levels plays an important role in determining the chemical composition of the atmosphere even in apparently remote northern hemispheric regions.     

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.     

Influence of Transport over a Mountain Ridge on the Chemical Composition of Marine Aerosols during the ACE-2 Hillcloud Experiment

Aerosol chemical composition and trace gas measurements were made at twolocations on the northeastern peninsula of Tenerife during the ACE-2HILLCLOUD experiment, between 28 June and 23 July 1997. Measurementswere made of coarse (#gt;2.5 m aerodynamic diameter) and fine (#lt; 2.5m) aerosol Cl^–, NO₃ ^–,SO₄ ^2–, non-sea saltSO₄ ^2– (NSSS),CH₃SO₃ ^– (MSA) andNH₄ ⁺, and gas phase dimethylsulphide (DMS), HCl,HNO₃, SO₂, CH₃COOH, HCOOH andNH₃. Size distributions were measured using a cascadeimpactor. Results show that in marine air masses NSSS and MSA wereformed via DMS oxidation, with additional NSSS present in air massescontaining a continental component. Using a Eulerian box model approachfor aerosols transported between upwind and downwind sites, a mean NSSSproduction rate of 4.36 × 10^–4 gm^–3 s^–1 was calculated for daytimeclear sky periods (highest insolation), with values for cloudy periodsduring daytime and nighttime of 3.55 × 10^–4 and2.40 × 10^–4 g m^–3s^–1, respectively. The corresponding rates for MSA were6.23 × 10^–6, 8.49 × 10^–6and 6.95 × 10^–6 g m^–3s^–1, respectively. Molar concentration ratios forMSA/NSSS were 8.7% (1.8–18.2%) and 1.9%(1.3–3.5%) in clean and polluted air masses, respectively.Reactions occurring within clouds appeared to have a greater influenceon rates of MSA production, than of NSSS, while conversely daytime gasphase reactions were more important for NSSS. For MSA, nighttimein-cloud oxidation rates exceeded rates of daytime gas phase productionvia OH oxidation of DMS. NSSS, MSA and ammonium had trimodal sizedistributions, with modes at 0.3, 4.0 and >10.0 m (NSSS andNH₄ ⁺), and 0.3, 1.5 and 4.0 m (MSA). Nosignificant production of other aerosol species was observed, with theexception of ammonium, which was formed at variable rates dependent onneutralisation of the aerosol with ammonia released from spatiallynon-uniform surface sources. Seasalt components were mainly present incoarse particles, although sub-micrometre chloride was also measured.Losses by deposition exceeded calculated expectations for all species,and were highest for the seasalt fraction and nitrate.     

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     

Arctic hazes in summer over Greenland and the North American Arctic. III: A contribution from the natural burning of carbonaceous materials and pyrites

Airborne measurements of the emissions from natural fires, fueled by pyrites and organic materials, at the Smoking Hills in the Northwest Territories, show that they are a regionally significant source of SO₂ (0.3 kg s^–1 or 10⁴ T yr^–1) and particles (0.3 kg s^–1). It appears likely that the Smoking Hills are a source for some of the dense, lower-level, haze layers that occur in the North American Arctic.     

Airborne measurements of dimethylsulfide,sulfur dioxide,and aerosol ions over the Southern Ocean South of Australia

Vertical distributions of dimethylsulfide (DMS), sulfur dioxide (SO₂), aerosol methane-sulfonate (MSA), non-sea-salt sulfate (nss-SO₄ ^2-), and other aerosol ions were measured in maritime air west of Tasmania (Australia) during December 1986. A few cloudwater and rainwater samples were also collected and analyzed for major anions and cations. DMS concentrations in the mixed layer (ML) were typically between 15–60 ppt (parts per trillion, 10^–12; 24 ppt=1 nmol m^–3 (20°C, 1013 hPa)) and decreased in the free troposphere (FT) to about <1–2.4 ppt at 3 km. One profile study showed elevated DMS concentrations at cloud level consistent with turbulent transport (cloud pumping) of air below convective cloud cells. In another case, a diel variation of DMS was observed in the ML. Our data suggest that meteorological rather than photochemical processes were responsible for this behavior. Based on model calculations we estimate a DMS lifetime in the ML of 0.9 days and a DMS sea-to-air flux of 2–3 mol m^–2 d^–1. These estimates pertain to early austral summer conditions and southern mid-ocean latitudes. Typical MSA concentrations were 11 ppt in the ML and 4.7–6.8 ppt in the FT. Sulfur-dioxide values were almost constant in the ML and the lower FT within a range of 4–22 ppt between individual flight days. A strong increase of the SO₂ concentration in the middle FT (5.3 km) was observed. We estimate the residence time of SO₂ in the ML to be about 1 day. Aqueous-phase oxidation in clouds is probably the major removal process for SO₂. The corresponding removal rate is estimated to be a factor of 3 larger than the rate of homogeneous oxidation of SO₂ by OH. Model calculations suggest that roughly two-thirds of DMS in the ML are converted to SO₂ and one-third to MSA. On the other hand, MSA/nss-SO₄ ^2- mole ratios were significantly higher compared to values previously reported for other ocean areas suggesting a relatively higher production of MSA from DMS oxidation over the Southern Ocean. Nss-SO₄ ^2- profiles were mostly parallel to those of MSA, except when air was advected partially from continental areas (Africa, Australia). In contrast to SO₂, nss-SO₄ ^2- values decreased significantly in the middle FT. NH₄ ⁺/nss-SO₄ ^2- mole ratios indicate that most non-sea-salt sulfate particles in the ML were neutralized by ammonium.     

Atmospheric Dry Deposition to Marble and Red Stone

This paper presents dry deposition flux and deposition velocity of atmospheric particles on white marble and red stone at Dayalbagh, a suburban site of semi arid region, which is 10 km away from the industrial sector of the Agra city where due to agricultural practices vegetation predominates. The wind speed at Agra is mostly in the range of 1–2 m s^–1. The atmospheric calm conditions at Agra in summer, monsoon, and winter seasons are 47%, 35%, and 76%, respectively. Industrial areas of the city are away from Dayalbagh and are located in the NE, E, SE, and SW sectors. The main industrial activities, which are in operation in Agra city and its outskirts, are foundry and forging industry. The other industrial activities in Agra are rubber processing, lime oxidation and pulverization, chemicals, engineering and brick refractory kilns. Dry deposition samples were collected on dry days on white marble and red stone (0.224 m × 0.224 m × 0.02 m) using surface washing method. Both slabs were fixed to an iron stand (1.5 m height) at an angle of about 80 from the horizontal and exposed for 24 h on the roof of the faculty building. The order of deposition flux on white marble is NH₄⁺ > Mg²⁺ > Ca²⁺ > Na⁺ > Cl^– > K⁺ > NO₃^– > SO₄^2– > F^– and that on red stone is NH₄⁺ > Mg²⁺ > Ca²⁺ > SO₄^2– > Na⁺ > NO₃^– > K⁺ > F^– > Cl^–. Average dry deposition flux of major ions varies from 3.4 to 128.5 M m^–2 d^–1. The sum of major cations on white marble and red stone are 516.4 and 450.4 eq m^–2 d^–1, respectively while sum of major anions are 425.3 and 400.4 eq m^–2 d^–1 on white marble and red stone, respectively. Higher deposition of all ions was observed when wind blows from NE as most of the Agra Iron foundries and Ferozabad glass industries lie in this direction. The mean values of dry deposition velocity of ions vary between 0.22 cm s^–1 to 1.49 cm s^–1. Deposition velocity for all ions is higher on white marble than red stone inspite of rougher surface of red stone as compared to white marble. This could be due to the chemical nature of white marble, which is made of dolomite and hence adds significant amount of ions by dissolution during washing. Seasonally the deposition velocity was highest in winter.     

Seasonal variations of atmospheric sulfur dioxide and dimethylsulfide concentrations at Amsterdam Island in the southern Indian Ocean

Daily measurements of atmospheric sulfur dioxide (SO₂) concentrations were performed from March 1989 to January 1991 at Amsterdam Island (37°50 S–77°30 E), a remote site located in the southern Indian Ocean. Long-range transport of continental air masses was studied using Radon (²²²Rn) as continental tracer. Average monthly SO₂ concentrations range from less than 0.2 to 3.9 nmol m^-3 (annual average = 0.7 nmol m^-3) and present a seasonal cycle with a minimum in winter and a maximum in summer, similar to that described for atmospheric DMS concentrations measured during the same period. Clear diel correlation between atmospheric DMS and SO₂ concentrations is also observed during summer. A photochemical box model using measured atmospheric DMS concentrations as input data reproduces the seasonal variations in the measured atmospheric SO₂ concentrations within ±30%. Comparing between computed and measured SO₂ concentrations allowed us to estimate a yield of SO₂ from DMS oxidation of about 70%.     

Meteorological results of MONSOON-88 expedition (pre-monsoon period)

Mean atmospheric circulation, moisture budget and net heat exchange were studied during a pre-monsoon period (18th March to 3rd May, 1988), making use of the data collected on board Akademik Korolev in the central equatorial and southern Arabian Sea region. The net heat exchange (R _n ) is found to be about 20 W m^–2 for a small area (0–4° N; 55–60° E), 50% less than the dimatological value. The mean value of net radiation (140 W m^–2) is less than the climatological value, which was due to higher cloud amount. The higher SST enhanced both the latent and sensible heat fluxes.The mean atmospheric circulation obtained from the upper air data is quite convincing. The mean exchange coefficient (C _e ) estimated from the moisture budget is about 1.0 × 10^–3 for a wind speed of 4 m s^–1. This value is slightly lower than that obtained by the usual methods.National Institute of Oceanography, RC, 52-Kirlampudi layout, Visakhapatnam — 530 023.India Meteorological Department, Gauhati.     

Influences on surface energy fluxes in simulated present and doubled CO2 climates

The surface energy fluxes simulated by the CSIRO9 Mark 1 GCM for present and doubled CO₂ conditions are analyzed. On the global scale the climatological flux fields are similar to those from four GCMs studied previously. A diagnostic calculation is used to provide estimates of the radiative forcing by the GCM atmosphere. For 1 × CO₂, in the global and annual mean, cloud produces a net cooling at the surface of 31 W m^–2. The clear-sky longwave surface greenhouse effect is 311 W m^–2, while the corresponding shortwave term is –79 W m^–2. As for the other GCM results, the CSIRO9 CO₂ surface warming (global mean 4.8°C) is closely related to the increased downward longwave radiation (LW ). Global mean net cloud forcing changes little. The contrast in warming between land and ocean, largely due to the increase in evaporative cooling (E) over ocean, is highlighted. In order to further the understanding of influences on the fluxes, simple physically based linear models are developed using multiple regression. Applied to both 1 × CO₂ and CO₂ December–February mean tropical fields from CSIRO9, the linear models quite accurately (3–5 W m^–2 for 1 × CO₂ and 2–3 W m^–2 for CO₂) relate LW and net shortwave radiation to temperature, surface albedo, the water vapor column, and cloud. The linear models provide alternative estimates of radiative forcing terms to those from the diagnostic calculation. Tropical mean cloud forcings are compared. Over land, E is well correlated with soil moisture, and sensible heat with air-surface temperature difference. However an attempt to relate the spatial variation of LWt within the tropics to that of the nonflux fields had little success. Regional changes in surface temperature are not linearly related to, for instance, changes in cloud or soil moisture.     

Degradation of Isoprene in the Presence of Sulphoxy Radical Anions

Autoxidation of S(IV) initiated by manganese sulphate or potassium peroxydisulphate in alkaline aqueous solutions was significantly slowed down by dissolved isoprene, which decayed in the process. The laboratory experiments were carried out in a batch, perfectly mixed reactor, which had no gas space. The concentration–time profiles of oxygen were measured with a Clark-type electrode. The profiles of sulphite species and of isoprene were evaluated from the UV spectra of solutions. The kinetic analysis indicated that isoprene reacted directly with sulphate radical anions produced during the S(IV) autoxidation. A relative second-order rate constant of (2.12 ± 0.37) × 10⁹ M^–1 s^–1 was determined for this reaction at 25 °C, pH (8.0–8.5) and ionic strength of (1.7–4.9) × 10^–3 M (the reference rate constant of the reaction of sulphate radical anions with sulphite ions equalled 3.4 × 10⁸ M^–1 s^–1). A tentative mechanism of isoprene oxidation during S(IV) autoxidation, which included formation of isoprene – SO^– ₄ adduct, was based on the analogy to the gas-phase reactions of isoprene and to the liquid-phase reactions of sulphate radical anions with other compounds. Atmospheric significance of the aqueous-phase reaction of isoprene with sulphate radicals was discussed. Approximate analysis showed the reaction is a potential sink for isoprene in the aqueous phase and in the gas–liquid systems of high liquid water content (LWC > 10^–5 m³ m^–3). The aqueous-phase oxidation of isoprene can produce secondary pollutants, and influence transformation and the long-range transport of SO₂ in the atmosphere.     

Surface-layer scintillation measurements of daytime sensible heat and momentum fluxes

Line-averaged measurements of the structure parameter of refractive index (C _n ² ) were made using a semiconductor laser diode scintillometer above two markedly different surfaces during hours of positive net radiation. The underlying vegetation comprised in the first instance a horizontally homogeneous, pasture sward well-supplied with water, and in the second experiment, a sparse thyme canopy in a semi-arid environment. Atmospheric stability ranged between near neutral and strongly unstable (–20). The temperature structure parameterC _T ² computed from the optical measurements over four decades from 0.001 to 2 K² m^–2/3 agreed to within 5% of those determined from temperature spectra in the inertial sub-range of frequencies. Spectra were obtained from a single fine thermocouple sensor positioned near the midway position of the 100m optical path and at the beam propagation height (1.5m).With the inclusion of cup anemometer measurements, rule-of-thumb assumptions about surface roughness, and Monin-Obukhov similarity theory, path-averaged optical scintillations allow calculation of surface fluxes of sensible heat and momentum via a simple iterative procedure. Excellent agreement was obtained between these fluxes and those measured directly by eddy correlation. For sensible heat, agreement was on average close to perfect over a measured range of 0 to 500 W m^–2 with a residual standard deviation of 30 W m^–2. Friction velocities agreed within 2% over the range 0–0.9 m s^–1 (residual standard deviation of 0.06 m s^–1). The results markedly increase the range of validation obtained in previous field experiments. The potential of this scintillation technique and its theoretical foundation are briefly discussed.