Monoterpene concentrations in and above a forest of scots pine

Diurnal and vertical ambient air measurements of the monoterpenes have been made in and above a Scots pine (Pinus sylvestris) forest of central Sweden, within the boreal northern coniferous biome. Sampling was done with Tenax TA, and analysis by GC and ion trap detection. Daytime mixing ratios were on the order of tenths of a ppbv from the forest floor to the top of the forest, and a factor of 2 or 3 lower above the forest. Mixing ratios at night were at the ppbv level, highest near the forest floor and the crown, and decreased with height above the forest. The highest total concentration observed was 8 ppbv inside the forest at 3 am (GMT). The average terpene composition was 3-carene 32%, -pinene 29%, limonene 18%, -pinene 10%, -phellandrene 7%, camphene 5%, and sabinene at less than 2%. The 3-carene/-pinene ratio varied with wind direction and speed, relative humidity, and wet/dry vegetation, but not with ozone or NO₂ concentration, solar radiation, or temperature. Variations in the observed terpene composition at the sampling site are mainly caused by the influence of other vegetation in the vicinity of the site. It would seem that wet Scots pine emits more 3-carene relative to -pinene than does dry pine.     

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.     

Exponential-linear stability correction functions for weak to moderate instability near the ground

Stability correction functions which combine the exponent of z/L, and a linear term in z/L, are proposed for the unstable case. The functions provide a reasonably close fit to the _m and _h results of Dyer and Hicks (1970) for 0 < –z/L 1, but they cannot be extended to cases of strong instability. Attractive features are the ability to integrate the expressions directly in terms of z/L, and a particularly close fit of the integrated result to experimentally derived _m values.     

Modelling radiation quantities and photolysis frequencies in the troposphere

STAR (System for Transfer of Atmospheric Radiation) was developed to calculate accurately and efficiently the irradiance, the actinic flux, and the radiance in the troposphere. Additionally a very efficient calculation scheme to computer photolysis frequencies for 21 different gases was evolved. STAR includes representative data bases for atmospheric constituents, especially aerosol particles. With this model package a sensitivity study of the influence of different parameter on photolysis frequencies in particular of O₃ to Singlet D oxygen atoms, of NO₂, and of HCHO was performed. The results show the quantitative effects of the influence of the solar zenith angle, the ozone concentration and vertical profile, the aerosol particles, the surface albedo, the temperature, the pressure, the concentration of NO₂, and different types of clouds on the photolysis frequencies.Notation I _A(, ) actinic flux - I _H(, ) irradiance - L(, , , ) radiance - wavelength - azimuth angle - cosine of zenith angle - _s cosine of solar zenith angle - optical depth - _s scattering coefficient - _c extinction coefficient - _o single scattering albedo - p _mix mixed phase function - g _mix mixed asymmetry factor - J _gas photolysis frequency     

Numerical integration errors in calculated tropospheric photodissociation rate coefficients

Tropospheric photodissociation rate coefficients (J values) were calculated for NO₂, O₃, HNO₂, CH₂O, and CH₃CHO using high spectral resolution (0.1 mm wavelength increments), and compared to the J values obtained with numerically degraded resolution (=1, 2, 4, 6, 8, and 10 nm, and several commonly used nonuniform grids). Depending on the molecule, substantial errors can be introduced by the larger increments. Thus for =10 nm, errors are less than 1% for NO₂, less than 2% for HNO₂, +6.5% to -16% for CH₂O, -6.9% to +24% for CH₃CHO, and -24% to +110% for O₃. The errors for CH₂O arise from the fine structure of its absorption spectrum, and are prevalently negative (underestimate of J). The errors for O₃, and to a lesser extent for CH₃CHO, arise mainly from under-resolving the overlap of the molecular action spectrum and the tropospheric actinic flux in the wavelength region of stratospheric ozone attenuation. The sign of those errors depends on whether the actinic flux is averaged onto the grid before or after the radiative transfer calculation. In all cases studied, grids with 2 nm produced errors no larger than 5%.     

A review of flux-profile relationships

Flux-profile relationships in the constant flux layer are reviewed. The preferred relationships are found to be those of Dyer and Hicks (1970), namely, _H = _W =(1–16(z/L))^–1/2, _M =(1–16(z/L))^–1/4 for the unstable region, and _H = _W = _M = 1+5(z/L) for the stable region.The carefully determined results of Businger et al. (1971) remain a difficulty which calls for considerable clarification.     

Estimates of sensible heat flux from observations of temperature fluctuations

Comparisons between sensible heat flux measured using eddy correlation instrumentation and estimated using the temperature fluctuation method are presented for four types of surface in West Africa. Agreement between measured and estimated values is good. Regression of estimated on measured sensible heat flux gave a mean slope of 0.98 with a mean r ² of 0.94 for bare soil, mature millet, fallow savannah and tiger bush. Estimates of heat flux from temperature fluctuations measured by an instrument mounted beneath a tethered balloon are also shown to be in close agreement with eddy correlation measurements made at the surface (regression slope = 0.98, r ² = 0.84). The results provide evidence that the ratio /_×is indeed a universal function of z/L for all the surface types considered.     

Flux determination over a smooth surface under strongly unstable conditions

Careful micrometeorological measurements on an empty parking lot allowed determination of the surface fluxes of sensible heatH and of momentum by applying profile equations derived from Monin-Obukhov similarity theory with two sets of the stability correction function for momentum _m and sensible heat _h . These fluxes were compared with reference values ofH independently determined by means of an eddy correlation technique. In general, better agreement was found betweenH values derived from profiles with the stability functions of Brutsaert (1992) and referenceH values, than when the Businger-Dyer functions were used to deriveH. The disagreement in the latter comparison was especially serious under strongly unstable conditions, with the value ofy=–z/L (wherez is the height andL is the Obukhov length) larger than 10. A closer look at the procedure for calculatingH from the profiles revealed that the large differences between theH values derived with these two different versions of the stability correction functions were caused by the small differences of the _h values, and not by the larger differences of the _m values. This result stems from the strong sensitivity of the resultingH values on the choice of _h .     

On the Significance of the Webb Correction to Fluxes

For establishing correct mass or energy balances at the Earth's surface, detailed and correct measurements of air constituent fluxes are needed. Flux measurements obtained from the eddy covariance technique have to pass several corrections of different relevance in order to give correct flux data. One of these corrections, the Webb correction, is analysed herein from latent heat flux and CO₂ flux data recorded during two field experiments. The significance of this correction for the latent heat flux data varies with the air humidity and the Bowen ratio. The correction changes the latent heat flux values only a little, but significantly (by 2 to 3%). For other air constituents (like CO₂), the Webb correction is much more important (20 to 30% of the flux).     

Comparison of flux measurements with open- and closed-path gas analyzers above an agricultural field and a forest floor

Comparison was made of the flux measurements of a closed-path CO₂/H₂O analyzer and an open-path H₂O analyzer above a clover field and the forest floor of a Douglas-fir stand. The attenuation of the gas concentration fluctuations caused by the sampling tube of the closed-path analyzer resulted in underestimation of the H20 flux above both surfaces. The degree of underestimation above the clover field depended on wind speed, but was smaller than that calculated from the transfer function for laminar flow in a circular tube and the scalar cospectrum in the neutral and unstable surface layer. Above the forest floor CO₂ fluctuations led those of H₂O by 0.7s. The implications of this are discussed regarding the determination of the time delay caused by the sampling tube of the closedpath analyzer. The day-time CO₂ efflux from the forest floor, averaged over three days, was 0.043 mg/(m²s).     

A Spectrum-Independent Procedure for Correcting Eddy Fluxes Measured with Separated Sensors

We investigate flux underestimates in eddy correlation measurements that are caused by horizontal separation of the sensors. A common eddy correlation setup consists of a sonic anemometer and a humidity sensor which, because of its bulk, must be placed some distance away from the sonic path, leading to a flux loss (of latent heat). Utilizing an additional fast temperature sensor placed near the humidity sensor, we develop a procedure for correcting for this loss. The procedure simultaneously corrects the sensible heat flux for the difference between true temperature and sonic temperature. Our correction procedure, which does not depend on the shape of the cospectrum, is then compared to the widely-used procedure following Moore (1986), which assumes a cospectral model ('Kansas Model). Both correction methods are applied to data collected within the internal boundary layer over a rice paddy, downwind of arid land. Under conditions of good fetch, they were found to agree well. Under poor fetch conditions, the model-based correction tended to be too small, while the spectrum-independent combined correction was robust. The latter is thus recommended for situations where the cospectral shape can be expected to deviate from the 'Kansas shape.     

A numerical model study of the structure and similarity scaling of the nocturnal boundary layer (NBL)

A one-dimensional numerical model based on the equations of mean motion and turbulent kinetic energy (TKE), with Delage's (1974) mixing-length parameterization has been used to simulate the mean and turbulent structure of the evolving stably stratified nocturnal boundary layer (NBL). The model also includes a predictive equation for the surface temperature and longwave radiational cooling effects.In the absence of advective and gravity wave effects, it is found that the model-simulated structure, after a few hours of evolution, could be ordered fairly well by a similarity scaling (u _*0, _*0, L ₀, and h) based on surface fluxes and the NBL height. Simple expressions are suggested to describe the normalized profiles of momentum and heat fluxes, TKE, eddy-viscosity and energy dissipation. A good ordering of the same variables is also achieved by a local scaling (u _*0, _* and L) based on the height-dependent local fluxes. The normalized TKE, eddy viscosity and energy dissipation are unique functions of z/L and approach constant values as z/L , where L is the local Monin-Obukhov length. These constants are close to the values predicted for the surface layer as z/L , thus suggesting that the Monin-Obukhov similarity theory can be extended to the whole NBL, by using the local (height-dependent) scales in place of surface-layer scales. The observed NBL structure has been shown to follow local similarity (Nieuwstadt, 1984).     

Nitrogen compound emission from biomass burning in tropical African savanna FOS/DECAFE 1991 experiment (Lamto,Ivory Coast)

Gaseous nitrogen compounds (NO _x , NO _y , NH₃, N₂O) were measured at ground level in smoke plumes of prescribed savanna fires in Lamto, in the southern Ivory Coast, during the FOS/DECAFE experiment in January 1991. During the flaming phase, the linear regression between [NO _x ] and [CO₂] (differences in concentration between smoke plumes and atmosheric background) results volumic emission ratio [NO _x ]/[CO₂]=1.37×10^–3 with only slight differences between heading and backing fires. Nearly 90% of the nitrogen oxides are emitted as NO. Average emission ratios of other compounds are: 1.91, 0.047, and 0.145×10^–3 for NO _y , NH₃ and N₂O, respectively. The emission ratios obtained during this field experiment are compred with corresponding values measured during former experiments with the same plant species in combustion chambers. An accurate determination of both the biomass actually burned and of the plant nitrogen content, allows an assessment of emission fluxes of N-compounds from Guinean savanna burns. Preliminary results dealing with the influence of fire on biogenic emissions from soils are also reported.     

On the log-linear wind profile and the relationship between shear stress and stability characteristics over the sea

Wind and stability characteristics in the atmospheric surface boundary layer at a height,Z, less than 20 m above the sea were examined in nine oceanic investigations. The analysis lends further support to the utility of the log-linear wind-profile law in the stability region of –0.4Z/L0.9, whereL is the Monin-Obukhov length. However, it is also shown that, inasmuch as better than 90% of the measurements fall within the range of ¦Z/L¦ 0.25, and inasmuch as this correction to the drag coefficient under neutral conditions amounts to less than 10%, the familiar logarithmic wind law may be used rather than the log-linear form. A wind-stress drag coefficient,C _d (=1.2×10^–3 between 1.0 m Z 18.3 m), is thus recommended for general deepwater oceanic applications. The situation over shallow water, which is different, is discussed briefly.     

Turbulent fluxes of momentum,heat and water vapor in the atmospheric surface layer at sea during ATEX

The vertical turbulent fluxes have been determined during the Atlantic Trade Wind Experiment (ATEX) both by direct and profile methods. The drag coefficient obtained from direct measurements was c _D = 1.39 × 10^–3. A distortion of the wind profile due to wave action could be demonstrated, this produced an increased drag coefficient estimated by the profile method. The dissipation technique using the downwind spectrum gave a lower drag coefficient of 1.26 × 10^–3, probably due to non-isotropic conditions (the ratio of vertical to downwind spectrum at high frequencies scattered considerably with an average of 1 instead of 4/3).From direct measurements, the sensible heat flux showed a poor correlation with the bulk parameter product U, contrary to the heat flux obtained from profiles. It is shown that this is due to the higher frequency part of the cospectrum, say above 0.25 Hz, which contributes more than 50 % of the total flux. Determination of the heat flux from temperature fluctuations by the dissipation method would be in agreement with the direct determination only if the corresponding Kolmogoroff constant were 2.1 instead of 0.8.For the vertical flux of water vapor obtained from profiles, the bulk transfer coefficient was 1.28 × 10^–3.This work was supported by the Deutsche Forschungsgemeinschaft, Schwerpunktprogramm Meeresforschung and later the Sonderforschungsbereich Meeresforschung Hamburg.     

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

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

Airflow above changes in surface heat flux,temperature and roughness; an extension to include the stable case

A numerical model of airflow above changes in surface roughness and thermal conditions is extended to include cases with stable thermal stratification within the internal boundary-layer. The model uses a mixing-length approach with empirical forms for M and H.Results are presented for some basic cases and an attempt is then made to compare results given by the model with the experimental results of Rider, Philip and Bradley. Tolerable agreement is achieved. The importance of roughness change and thermal stability effects in the diffusion of heat and moisture near a leading edge is emphasised.Notation A Refers to Taylor (1970) - B Businger-Dyer constant (= 16.0) in forms for _M and _H - C Constant in form for in stable case - c _p Specific heat at constant pressure - E Scaled absolute humidity - g Acceleration due to gravity - H Upward vertical heat flux - H ₀, H ₁ Surface heat fluxes for x <0, x0 - H _E Upward latent heat flux - k Von Kármán's constant (= 0.4) - K _H K _W Eddy transfer coefficients for heat and water vapour - L Monin-Obukhov length - L _H Latent heat of evaporation for water - m Ratio of roughness lengths ( = z ₁/z ₀) - RPB Refers to Rider et al. (1964) - RL* Non-dimensional parameter (see Equations (9), (20a), (22a), (24a)) - R* Net radiation less ground heat flux (see Equations (15), (16)) - T Scaled temperature - T ₁ Downstream scaled surface temperature - u ₀ u ₁(x) Surface friction velocities for x <0, x0 - U, W Horizontal and vertical mean velocities - x, z Horizontal and vertical co-ordinates - Z _i Local roughness length - z ₀, z _i Roughness lengths for x < 0, x 0 - Temperature - ₀, ₁ Surface temperatures for x<0, x0 - _E Non-dimensional absolute humidity gradient - _H Non-dimensional temperature gradient of heat flux - _M Non-dimensional wind shear - = _M = _H = _E an assumption used in stable conditions - Air density - Absolute humidity - _w Density of water - Kinematic shear stress - Logarithmic height scale (= ln(z+z ₁)/z ₁)     

Turbulent transport of carbon dioxide over a paddy field

Turbulent fluctuations in CO₂ concentrations over a paddy field are measured by a fastresponse device with an open sensing path. This IR device coupled with a sonic anemometer constitutes an eddy correlation instrument to measure CO₂ fluxes. Three experiments were conducted in the surface layer over paddy 90 cm high. The stability (z – d)/L ranged from -0.14 to 0.20, where L denotes the Monin-Obukhov length.CO₂ power spectra show the range of applicability of the -2/3 power law to be between f = 0.2 and f = 2, where f is the frequency normalized by wind speed and height. The cospectral estimate between CO₂ and vertical component of wind speed ranging from f = 0.005 to f = 2 shows a peak at about f = 0.15 under near-neutral stratification.Hourly means of CO₂ flux measured by the eddy correlation method increase with intensity of net radiation. The maximum value of downward flux of CO₂ rises to 0.6 mg cm^-2 hr^-1 over the paddy field at the stage of ear emergence.Some turbulence statistics relating to the CO₂ transport are evaluated: the correlation coefficient between CO₂ and vertical velocity is about -0.3, and that between CO₂ and humidity attains -0.7 ~ -0.8 under unstable stratification; nondimensional gradients _c for CO₂ and _m for wind speed are 0.89 and 0.99, respectively.     

Modelling of the vertical fluxes of nitric acid,ammonia, and ammonium nitrate

Results from numerical investigations regarding the exchange of HNO₃, NH₃, and NH₄NO₃ between the atmosphere and the biosphere are presented. The investigations were performed with a modified inferential method which is based on the generally accepted micrometeorological ideas of the transfer of momentum, sensible heat and matter near the Earth's surface and the chemical reactions among these nitrogen compounds. This modified inferential method calculates the micrometeorological quantities (such as the friction velocity and the fluxes of sensible and latent heat), the height-invariant fluxes of the composed chemically conservative trace species with group concentrationsc ₁=[HNO₃]+[NH₄NO₃] (total nitrate),c ₂=[NH₃]+[NH₄NO₃] (total ammonia), andc ₃=[HNO₃]-[NH₃] as well as the fluxes of the individual nitrogen compounds. The parameterization of the fluxes is based on the flux-gradient relationships in the turbulent region of the atmospheric surface layer. The modified inferential method requires only the data of wind velocity, temperature, humidity and concentrations (HNO₃, NH₃, and NH₄NO₃) measured at a reference height by stations of a monitoring network.     

ModellingNO conversion by using probability density functions

An expression for concentration fluctuations in a smoke plume is derived from airborne measurements ofNO _X. A linear relation between the standard deviation of the fluctuations around a Gaussian concentration profile and the average gradient in the concentrations is assumed. With this relation the probability density function of expectedNO ₂ concentrations at 3 km from a source ofNO _X is modelled under the assumption of photostatic equilibrium, and is compared with measurements. A parametrisation for the concentration fluctuations of std(C)= 26(+/–7)*dc/dr is proposed (r in metres). CalculatedNO ₂ distributions are in reasonable agreement with the measurements and the averageNO ₂ concentration appeared not to be affected by the concentration fluctuations in theNO _X concentration. The spatial resolution of all measurements was 40 m.