Field measurements of NO and NO2 emissions from fertilized and unfertilized soils

Field measurements of NO and NO₂ emissions from soils have been performed in Finthen near Mainz (F.R.G.) and in Utrera near Seville (Spain). The applied method employed a flow box coupled with a chemiluminescent NO _x detector allowing the determination of minimum flux rates of 2 g N m^-2 h^-1 for NO and 3 g m^-2 h^-1 for NO₂.The NO and NO₂ flux rates were found to be strongly dependent on soil surface temperatures and showed strong daily variations with maximum values during the early afternoon and minimum values during the early morning. Between the daily variation patterns of NO and NO₂, there was a time lag of about 2 h which seem to be due to the different physico-chemical properties of NO and NO₂. The apparent activation energy of NO emission calculated from the Arrhenius equation ranged between 44 and 103 kJ per mole. The NO and NO₂ emission rates were positively correlated with soil moisture in the upper soil layer.The measurements carried out in August in Finthen clearly indicate the establishment of NO and NO₂ equilibrium mixing ratios which appeared to be on the order of 20 ppbv for NO and 10 ppbv for NO₂. The soil acted as a net sink for ambient air NO and NO₂ mixing ratios higher than the equilibrium values and a net source for NO and NO₂ mixing ratios lower than the equilibrium values. This behaviour as well as the observation of equilibrium mixing ratios clearly indicate that NO and NO₂ are formed and destroyed concurrently in the soil.Average flux rates measured on bare unfertilized soils were about 10 g N m^-2 h^-1 for NO₂ and 8 g N m^-2 h^-1 for NO. The NO and NO₂ flux rates were significantly reduced on plant covered soil plots. In some cases, the flux rates of both gases became negative indicating that the vegetation may act as a sink for atmospheric NO and NO₂.Application of mineral fertilizers increased the NO and NO₂ emission rates. Highest emission rates were observed for urea followed by NH₄Cl, NH₄NO₃ and NaNO₃. The fertilizer loss rates ranged from 0.1% for NaNO₃ to 5.4% for urea. Vegetation cover substantially reduced the fertilizer loss rate.The total NO _x emission from soil is estimated to be 11 Tg N yr^-1. This figure is an upper limit and includes the emission of 7 Tg N yr^-1 from natural unfertilized soils, 2 Tg N yr^-1 from fertilized soils as well as 2 Tg N yr^-1 from animal excreta. Despite its speculative character, this estimation indicates that NO _x emission by soil is important for tropospheric chemistry especially in remote areas where the NO _x production by other sources is comparatively small.     

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.     

Flux–Profile Relationships Over a Fetch Limited Beech Forest

The influence of an internal boundary layer and a roughness sublayer on flux–profile relationships for momentum and sensible heat have been investigated for a closed beech forest canopy with limited fetch conditions. The influence was quantified by derivation of local scaling functions for sensible heat flux and momentum (_h and _m) and analysed as a function of atmospheric stability and fetch. For heat, the influences of the roughness sublayer and the internal boundary layer were in agreement with previous studies. For momentum, the strong vertical gradient of the flow just above the canopy top for some wind sectors led to an increase in _m, a feature that has not previously been observed. For a fetch of 500 m over the beech forest during neutral atmospheric conditions, there is no height range at the site where profiles can be expected to be logarithmic with respect to the local surface. The different influence of the roughness sublayer on _h and _m is reflected in the aerodynamic resistance for the site. The aerodynamic resistance for sensible heat is considerably smaller than the corresponding value for momentum.     

Free convection frequency spectra of atmospheric turbulence over the sea

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

Scavenging Efficiency of ‘Aerosol Carbon’ and Sulfate in Supercooled Clouds at Mt. Sonnblick (3106 m a.s.l., Austria)

Cloud water and interstitial aerosol samples collected at Mt. Sonnblick (SBO) were analyzed for sulfate and aerosol carbon to calculate in-cloud scavenging efficiencies. Scavenging efficiencies for sulfate (_SO) ranged from 0.52 to 0.99 with an average of 0.80. Aerosol carbon was scavenged less efficiently with an average value (_AC) of 0.45 and minimum and maximum values of 0.14 and 0.81, respectively. Both _SO and _AC showed a marked, but slightly different, dependence on the liquid water content (LWC) of the cloud. At low LWC, _SO increased with rising LWC until it reached a relatively constant value of 0.83 above an LWC of 0.3 g/m³. In the case of aerosol carbon, we obtained a more gradual increase of _AC up to an LWC of 0.5 g/m³. At higher LWCs, _{_} remained relatively constant at 0.60. As the differences between _SO and _A varied across the LWC range observed at SBO, we assume that part of the aerosol carbon was incorporated into the cloud droplets independently from sulfate. This hypothesis is supported by size classified aerosol measurements. The differences in the size distributions of sulfate and total carbon point to a partially external mixture. Thus, the different chemical nature and the differences in the size and mixing state of the aerosol particles are the most likely candidates for the differences in the scavenging behavior.     

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.     

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.     

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.     

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%.     

Radiative Heat Transfer and Hydrostatic Stability in Nocturnal Fog

We have performed a one-dimensional and transient radiative heat transfer analysis in order to investigate interaction between atmospheric radiation and convective instability within a nocturnal fog. The radiation element method using the Ray Emission Model (REM²), which is a generalized numerical method, in conjunction with a line-by-line (LBL) method, is employed to attain high spectral resolution calculations for anisotropically scattering fog. The results show that the convective instability has a strong dependence on radiative properties of the fog. For the condition of a 20-m droplet diameter and liquid water content of 0.1 × 10^–3 kg m^–3;, the temperature profile within the fog becomes S shaped, and a convective instability layer forms in the middle or lower level of the fog. However, for the same water content and a 40-m diameter droplet, no strong convective instability layer forms, whereas for a 10-m diameter droplet a strong convective instability is observed.     

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     

Correlations between microphysical properties of large-scale semi-transparent cirrus and the state of the atmosphere

By making use of TOVS Path-B satellite retrievals and ECMWF reanalyses, correlations between bulk microphysical properties of large-scale semi-transparent cirrus (visible optical thickness between 0.7 and 3.8) and thermodynamic and dynamic properties of the surrounding atmosphere have been studied on a global scale. These clouds constitute about half of all high clouds. The global averages (from 60°N to 60°S) of mean ice crystal diameter, D_e, and ice water path (IWP) of these clouds are 55 μm and 30 g m⁻², respectively. IWP of these cirrus is slightly increasing with cloud-top temperature, whereas D_e of cold cirrus does not depend on this parameter. Correlations between D_e and IWp of large-scale cirrus seem to be different in the midlatitudes and in the tropics. However, we observe in general stronger correlations between D_e and IWP and atmospheric humidity and winds deduced from the ECMWF reanalyses: D_e and IWP increase both with increasing atmospheric water vapour. There is also a good distinction between different dynamical situations: In humid situations, IWP is on average about 10 gm⁻² larger in regions with strong large-scale vertical updraft only that in regions with strong large-scale horizontal winds only, whereas the mean D_e of cold large-scale cirrus decreases by about 10 μm if both strong large-scale updraft and horizontal winds are present.     

On the temperature coefficient of PCO 2 in seawater

The commonly reported temperature coefficient of P. the equilibrium partial pressure of CO₂, is (P/T) _A,C ,which is about 15 ppm/°C, or 5% of the atmospheric partial pressure of CO₂. This coefficient, however, applies only to deep water, not to surface water which can exchange CO₂ with the atmosphere. The coefficient (P/T) _A,C ,, where designates constancy of the sum of atmospheric and surface-ocean CO₂, is the appropriate value for air-sea exchange. Numerical values are mass-dependent because the depth of the exchanging ocean layer must be specified. For a 100-m surface layer, the value is ca. 1.5 ppm/°C, or 0.5% of ambient CO₂. Editor's Note:In view of the interdisciplinary importance of the carbon dioxide-climate problem, this note on seawater chemistry should be of interest to specialists beyond the discipline of ocean chemistry.     

Atmospheric ionic species in PM2.5 and PM1 aerosols in the ambient air of eastern central India

This study elucidates the characteristics of ambient PM_2.5 (fine) and PM₁ (submicron) samples collected between July 2009 and June 2010 in Raipur, India, in terms of water soluble ions, i.e. Na⁺, NH ₄ ⁺ , K⁺, Mg²⁺, Ca²⁺, Cl^?, NO ₃ ^? and SO ₄ ^2? . The total number of PM_2.5 and PM₁ samples collected with eight stage cascade impactor was 120. Annual mean concentrations of PM_2.5 and PM₁ were 150.9?±?78.6 μg/m³ and 72.5?±?39.0 μg/m³, respectively. The higher particulate matter (PM) mass concentrations during the winter season are essentially due to the increase of biomass burning and temperature inversion. Out of above 8 ions, the most abundant ions were SO ₄ ^2? , NO ₃ ^? and NH ₄ ⁺ for both PM_2.5 and PM₁ aerosols; their average concentrations were 7.86?±?5.86 μg/m³, 3.12?±?2.63 μg/m³ and 1.94?±?1.28 μg/m³ for PM_2.5, and 5.61?±?3.79 μg/m³, 1.81?±?1.21 μg/m³ and 1.26?±?0.88 μg/m³ for PM₁, respectively. The major secondary species SO ₄ ^2? , NO ₃ ^? and NH ₄ ⁺ accounted for 5.81%, 1.88% and 1.40% of the total mass of PM_2.5 and 11.10%, 2.68%, and 2.48% of the total mass of PM₁, respectively. The source identification was conducted for the ionic species in PM_2.5 and PM₁ aerosols. The results are discussed by the way of correlations and principal component analysis. Spearman correlation indicated that Cl^? and K⁺ in PM_2.5 and PM₁ can be originated from similar type of sources. Principal component analysis reveals that there are two major sources (anthropogenic and natural such as soil derived particles) for PM_2.5 and PM₁ fractions.     

Models of eddy viscosity for numerical simulation of horizontally inhomogeneous,neutral surface-layer flow

Modification of a turbulent flow due to a change from a smooth to a rough surface has been studied by means of a stream function-vorticity model. Results of four models of eddy viscosity (or turbulent exchange coefficient) K _mhave been compared. The models are: (1) K _m = l²S, where l is the mixing length and S is the deformation of mean flow; (2) K _m E/S, which is based on the assumption that turbulent momentum flux is proportional to turbulent kinetic energy E; (3) K _m lE^1/2, the so called Prandtl-Kolmogoroff approach; and (4) K _m E²/, the E — closure, where is the dissipation of turbulent kinetic energy.It is found that net-production, i.e., the difference of production and dissipation of turbulent kinetic energy counteracts the influence of mean shear on turbulent shear stress and diminishes turbulent shear stress. The reduction of mixing-length, being predicted by Model 4 only, adds to this attenuation. As a consequence, in Models 2 and 4, loss of horizontal mean momentum is concentrated close to the ground, which results in an inflexion point in the logarithmic, vertical profile of horizontal mean velocity. By contrast, in Models 1 and 3, modification of turbulent shear stress reaches larger heights causing deeper internal boundary layers. Concerning the existence of an inflexion point in U(lnz), the depth of the internal boundary layer for mean velocity, and the modification of bottom shear stress, Model 4 comes closest to experimental data.A remarkable difference of Models 1, 2, 3 and Model 4 is that only Model 4 predicts a very slow relaxation of eddy viscosity which can be attributed to the reduction of mixing-length.     

Model of convective heat exchange due to isolated thermals in the atmospheric boundary layer

A numerical model of convective heat transfer due to isolated thermals in the atmospheric boundary layer is used to describe the temperature profile transformation in undisturbed conditions as a result of intensive dry free convection. Based on some assumptions, the heat transfer Equation (2) is transformed to the form (14) in which the coefficients and the function F are expressed by (d/dz)(ln ) and by parameters of thermals. Equation (14) has been solved numerically with the help of Equation (15) obtained from the statics equation because of Equation (8). The size distribution function f(z, r, t) of the thermals is discrete (Table I), according to Vulf'son (1961). On Figures 1 and 2 are plotted successive temperature profiles for a ground inversion, transformed due to free convection and turbulence (Figures 1a and 2a), and due to turbulence only (Figures 1b and 2b). The profiles are computed from Equation 14 (Figures 1a and 2a) and Equation 16 (Figures 1b and 2b) for k _z= 1 m² s^–1 (Figure 1) and k _z= 10 m² s^–1 (Figure 2). On Figure 3 the real temperature profiles in Sofia for June 22nd 1976 are compared with the profiles computed using the real initial profile for 4.30 h local time. Good qualitative agreement can be seen.     

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     

Characterisation of the carbonate content of atmospheric aerosols

A programme of aerosol sampling by dichotomous sampler has been undertaken with analysis of soluble ions plus carbonate. The technique for carbonate involved release of CO₂ by HCl vapour and quantitative measurement of the CO₂ by FTIR spectroscopy. The method is suitable for amounts down to below 10g CO₃ ^2- per filter. The prevailing atmospheric levels in an urban area were found to be below 1g m^-3. Information on the particle size from the dichotomous sampler was supplemented by use of a cascade impactor. Although CaCO₃ is clearly the dominant species initial analyses demonstrated higher carbonate levels than could be accounted for on the basis of the concentrations of calcium and magnesium ions which are the most likely cations in mineral carbonates. Analysis with and without heating to 100°C in a vacuum oven demonstrates the presence of carbonate in volatile form. This could be due to carbon dioxide adsorbed onto particulate matter such as soot.     

Characteristics of organic and elemental carbon in PM2.5 samples in Shanghai, China

Shanghai is the largest industrial and commercial city in China, and its air quality has been deteriorating for several decades. However, there are scarce researches on the level and seasonal variation of fine particle (PM_2.5) as well as the carbonaceous fractions when compared with other cities in China and around the world. In the present paper, abundance and seasonal characteristics of PM_2.5, organic carbon (OC) and elemental carbon (EC) were studied at urban and suburban sites in Shanghai during four season-representative months in 2005–2006 year. PM_2.5 samples were collected with high-vol samplers and analyzed for OC and EC using thermal-optical transmittance (TOT) protocol. Results showed that the annual average PM_2.5 concentrations were 90.3–95.5 μg/m³ at both sites, while OC and EC were 14.7–17.4 μg/m³ and 2.8–3.0 μg/m³, respectively, with the OC/EC ratios of 5.0–5.6. The carbonaceous levels ranked by the order of Beijing > Guangzhou > Shanghai > Hong Kong. The carbonaceous aerosol accounted for  30% of the PM_2.5 mass. On seasonal average, the highest OC and EC levels occurred during fall, and they were higher than the values in summer by a factor of 2. Strong correlations (r = 0.79–0.93) between OC and EC were found in the four seasons. Average level of secondary organic carbon (SOC) was 5.7–7.2 μg/m³, accounting for  30% of the total OC. Strong seasonal variation was observed for SOC with the highest value during fall, which was about two times the annual average.     

Chemical Assessment of Oceanic and Terrestrial Sulfur in the Marine Boundary Layer over the Northern North Pacific during Summer

Dimethylsulfide (DMS) in surface seawater and the air, methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO₄ ²–) in aerosol, and radon-222 (Rn-222) were measured in the northern North Pacific, including the Bering Sea, during summer (13 July – 6 September 1997). The mean atmospheric DMS concentrations in the eastern region (21.0 ± 5.8 nmole/m³ (mean ± S.D.), n=30) and Bering Sea (19.9 ± 9.8 nmole/m³, n=10) were higher than that in the western region (11.1 ± 6.4 nmole/m³, n=31) (p<0.05), although these regions did not significantly differ in the mean DMS concentration in surface seawater. Mean sea-to-air DMS flux in the eastern region (21.0 ± 10.4 mole/m²/day, n=19) was larger than those in the western region (11.3 ± 16.9 mole /m²/day, n=22) and Bering Sea (11.2 ± 7.8 mole/m²/day, n=7) (p<0.05). This suggests that the longitudinal difference in atmospheric DMS was produced by that in DMS flux owing to wind speed, while the possible causes of the higher DMS concentrations in the Bering Sea include (1) later DMS oxidation rates, (2) lower heights of the marine boundary layer, and (3) more inactive convection. The mean MSA concentrations in the eastern region (1.18 ± 0.84 nmole/m³, n=35) and Bering Sea (1.17 ± 0.87 nmole/m³, n=13) were higher than that in the western region (0.49 ± 0.25 nmole/m³, n=28) (p < 0.05). Thus the distribution of MSA was similar to that of DMS, while the nss-SO₄ ²– concentrations were higher near the continent. This suggests that nss-SO₄ ²– concentrations were regionally influenced by anthropogenic sulfur input, because the distribution of nss-SO₄ ²– was similar to that of Rn-222 used as a tracer of continental air masses.