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

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

Turbulence Reynolds number and the turbulent kinetic energy balance in the atmospheric surface layer

The relation between the turbulence Reynolds numberR and a Reynolds numberz* based on the friction velocity and height from the ground is established using direct measurements of the r.m.s. longitudinal velocity and turbulent energy dissipation in the atmospheric surface layer. Measurements of the relative magnitude of components of the turbulent kinetic energy budget in the stability range 0 >z/L 0.4 indicate that local balance between production and dissipation is maintained. Approximate expressions, in terms of readily measured micrometeorological quantities, are proposed for the Taylor microscale and the Kolmogorov length scale .     

Improving the diagnostic relation for the nocturnal boundary-layer height

A one-dimensional model of the nocturnal boundary layer (NBL) has been used to investigate the time variation of the NBL height for stationary and horizontally homogeneous synoptic conditions. The time variation of the well known quantity = hflu _* has been shown to be related to the wind variation at the top of the NBL. For the simple simulated conditions, this variation depends only on the roughness length and the Coriolis parameter. The value of averaged over the whole night is a function of the friction velocity. An expression is proposed for which is compared with observations. Under stationary external conditions, the new relation improves the determination of the NBL height if compared with the classical relation using a constant value of .     

Arctic hazes in summer over Greenland and the North American Arctic: II. Nature and concentrations of accumulation-mode and giant particles

Airborne measurements made during August 1985 over Greenland and its environs show that both accumulation-mode (0.1 m D2.0 m) and giant (D2 m) particles were present in relatively high concentrations in arctic haze layers and that the accumulation-mode particles dominated light scattering. Particles with diameters (D) between 1 and 4 m consisted predominately of mixed materials, small and dense inclusions, and probably organic compounds containing sulfur. Many of the particles from 0.1 to 1 m in diameter were also of mixed composition, with sulfuric acid, ammonium sulfate and organics probably the dominant constituents.     

Re-analysis of the nuclear winter phenomenon

Summary An analysis of the report of the (U.S.) National Academy of Sciences (NAS) on atmospheric effects of a nuclear exchange leads to conclusions that differ from those of the NAS and of the earlier TTAPS and AMBIO studies. Any cooling of the earth's surface is likely to beshort-lived because of rapid removal of the smoke clouds originating from nuclear burst-initiated fires, andminor because of appreciable green-house effects due to several distinct physical causes. (One of these, neglected in prior analyses, is the infrared absorption from cirrus clouds produced directly by the nuclear bursts.) Taken together, these effects may even induce slight surface warming (nuclear summer) instead of cooling (nuclear winter). The consequences to atmospheric ozone are similarly ambiguous; depending on the detailed nuclear scenario, the net ozone content may increase-rather than decrease as argued by TTAPS. Experiments could settle some uncertainties.With 2 Figures     

An Alternative Function For The Wind And Temperature Gradients In Unstable Surface Layers

The function ()=(1+|z/L|^2/3)^1/2,where z is the height, L the Obukhov length, and a constant,is proposed for the nondimensional wind speed and temperaturegradients (flux-profile relationships) in anunstable surface layer. This function agrees quite well withboth wind speed and temperature data,has the theoretically correct behaviour in convective conditions,and leads to simple results when integrated to produce the mean profiles.     

Reactions of alkoxy radicals under atmospheric conditions: The relative importance of decomposition versus reaction with O2

The reactions of alkoxy radicals determine to a large extent the products formed during the atmospheric degradations of emitted organic compounds. Experimental data concerning the decompositions, 1,5-H shift isomerizations and reactions with O₂ of several classes of alkoxy radicals are inconsistent with literature estimations of their absolute or relative rate constants. An alternative, although empirical, method for assessing the relative importance under atmospheric conditions of the reactions of alkoxy radicals with O₂ versus decomposition was derived. This estimation method utilizes the differences in the heats of reaction, (H)=(H_{decomposition}–H_{O 2 reaction}), between these two reactions pathways. For (H)[22–0.5(H_{O 2 reaction})], alkoxy radical decomposition dominates over the reaction with O₂ at room temperature and atmospheric pressure of air, while for (H)[25-0.5(H_{O 2 reaction})], the O₂ reaction dominates over decomposition (where the units of H are in kcal mol^–1). The utility and shortcomings of this approach are discussed. It is concluded that further studies concerning the reactions of alkoxy radicals are needed.     

Determination of similarity functions of the resistance laws for the planetary boundary layer using surface-layer similarity functions

Functional forms of the universal similarity functions A, B (for wind components parallel and normal to the surface stress), and C (for potential temperature difference) are determined based on the generalized theory of the resistance laws for the Planetary Boundary Layer (PBL). The similarity-profile functions for the surface layer are matched with the velocity and temperature-defect profiles that are assumed to have shapes modified by certain powers of nondimensional height z/h, where h is the PBL height. The powers of the outer-layer profile functions are determined, so that the functions become negligible in the surface layer. To close the temperature defect law, an assumption that the temperature gradient across the top of the PBL is continuous with the stratification of the overlying atmosphere is used. The result of this assumption is that nondimensional momentum and temperature profiles in the PBL can be described in terms of four basic ratios: (1) roughness ratio = /h (2) scale-height ratio =|f|h/u_*, (3) ambient stratification parameter =h/_*, and (4) stability parameter =h/L, where L is the Monin-Obukhov length, z₀ is the surface roughness, is the upper-air stratification, u _* is the friction velocity, and _* is the temperature scale at the surface. For stable conditions, the scale-height ratio can be related to the atmospheric stability and the upperair stratification, and the generalized similarity and Rossby number similarity theories become identical. Under appropriate boundary conditions, function A is explicitly dependent on the stability parameter , while B is a function of scale-height ratio , which in turn depends on the stability. Function C is shown to be dependent on the stability and the upper-air stratification, due to the closure assumption used for the temperature profile.The suggested functional forms are compared with other empirical approximations by several authors. The general framework used to determine the functional forms needs to be tested against good boundary-layer measurements.     

The validation of various schemes for parameterizing evaporation from bare soil for use in meteorological models: A numerical study using in situ data

Parameterization of evaporation from a non-plant-covered surface is very important in the hierarchy strategy of modelling land surface processes. One of the representations frequently used in its computation is the resistance formulation. The performance of the evaporation schemes using the , , and their combination resistance approaches to parameterize evaporation from bare soil surfaces is discussed. For that purpose, the nine schemes, based on a different dependence of and on volumetric soil moisture content and its saturated value, are used.The tests of performances of the considered schemes are based on time integrations by the land surface module (BARESOIL) using observed data. The 23 data sets at a bare surface experimental site in Rimski anevi, Yugoslavia on chernozem soil, were used for the resistance algorithm evaluation. The quality of the schemes was compared with the observed values of the latent heat flux using several statistical parameters.     

Bioaccumulation of Cobalt in Parmelia sulcata

Six locations across mainland Portugal were selected for exposing Parmelia sulcata, for a one-year period (8 months for one site), with simultaneous measurement of total (dry + wet) deposition (one-month periods). The exposed lichens and the total (dry + wet) deposition were analysed for cobalt contents by INAA (instrumental neutron activation analysis) and ICP-MS (inductively coupled plasma mass spectroscopy), respectively. The designated wet deposition was evaluated through the collected water volume; the designated dry deposition was assessed after the (dried) residual mass of the wet deposition. An excellent agreement between Co contents in exposed lichens and the cumulative (1) Co contents in the dry deposition, (2) dry deposition, and (3) wet deposition has been found for the locations with alternate drought and precipitation months, high dry deposition, and high Co contents in the latter. Continuous rainfall was found to hinder the Co accumulation in the lichen due to its release from the lichen and/or lower Co contents in the dry deposition. At three locations, P. sulcata Co contents, after subtraction of the background (before exposure), equalled or exceeded the Co contents in the cumulative dry deposition at the end of the exposure time. The optimal exposure period for this species likely depends on the exposure conditions.     

Gas and Particulate Products Distribution from the Photooxidation of α-Humulene in the Presence of NOx, Natural Atmospheric Air and Sunlight

The photooxidation of -humulene in the presence of NO_x, natural sunlight, and rural background air was investigated using a combination of gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC). Identification and quantification of gas and particulate reaction products were reported over the course of the reaction. The daytime photooxidation was carried out in a large outdoor smog chamber (190 m³). A wide range of ring retaining and ring opening products in the gas and particle phase are reported. On average, measured gas and particle phase products accounted for 44% of the reacted -humulene carbon. Measurements show that a number of reaction products with low vapor pressures (e.g. 3-seco--humulone aldehyde, 7-seco--humulone aldehyde, -humulal aldehyde, -humulene 3-oxide or -humulene 7-oxide, -humulaic/alic acid isomers, and 3-seco--14-hydroxyhumulone aldehyde) were found in the early stage of the reaction and may play an important role in the early formation of secondary organic aerosol. A detailed mechanism is proposed to account for most products observed in this investigation.     

Application of a “Big-Tree” model to regional climate modeling: a sensitivity study

Summary ¶In order to better understand land-atmosphere interactions and increase the predictability of climate models, it is important to investigate the role of forest representation in climate modeling. Corresponding to the big-leaf model commonly employed in land surface schemes to represent the effects of a forest, a so called big-tree model, which uses multi-layer vegetation to represent the vertical canopy heterogeneity, was introduced and incorporated into the National Center for Atmospheric Research (NCAR) regional climate model RegCM2, to make the vegetation model more physically based. Using this augmented RegCM2 and station data for China during 1991 Meiyu season, we performed 10 experiments to investigate the effects of the application of the big-tree model on the summer monsoon climate.With the big-tree model incorporated into the regional climate model, some climate characteristics, e.g. the 3-month-mean surface temperature, circulation, and precipitation, are significantly and systematically changed over the model domain, and the change of the characteristics differs depending on the area. Due to the better representation of the shading effect in the big-tree model, the temperature of the lower layer atmosphere above the plant canopy is increased, which further influences the 850hPa temperature. In addition, there are significant decreases in the mean latent heat fluxes (within 20–30W/m²) in the three areas of the model domain.The application of the big-tree model influences not only the simulated climate of the forested area, but also that of the whole model domain, and its impact is greater on the lower atmosphere than on the upper atmosphere. The simulated rainfall and surface temperature deviate from the originally simulated result and are (or seem to be) closer to the observations, which implies that an appropriate representation of the big-tree model may improve the simulation of the summer monsoon climate.We also find that the simulated climate is sensitive to some big-tree parameter values and schemes, such as the shape, height, zero-plane displacement height and mixing-length scheme. The simulated local/grid differences may be very large although the simulated areal-average differences may be much lower. The area-average differences in the monthly-mean surface temperature and heat fluxes can amount to 0.5°C and 4W/m², respectively, which correspond to maximum local/grid differences of 3.0°C and 40W/m² respectively. It seems that the simulated climate is most sensitive to the parameter of the zero-plane displacement among the parameters studied.     

A Comparative Analysis of Transpiration and Bare Soil Evaporation

Transpiration E^v and bare soil evaporation E^b processes are comparatively analysed assuming homogeneous and inhomogeneous areal distributions of volumetric soil moisture content . For a homogeneous areal distribution of we use a deterministic model, while for inhomogeneous distributions a statistical-deterministic diagnostic surface energy balance model is applied. The areal variations of are simulated by Monte-Carlo runs assuming normal distributions of .The numerical experiments are performed for loam. In the experiments we used different parameterizations for vegetation and bare soil surface resistances and strong atmospheric forcing. According to the results theE^v()-^Eb() differences are great, especially in dry conditions. In spite of this, the available energy flux curves of vegetation A^v() and bare soil A^b() surfaces differ much less than the E^v() and ^Eb() curves. The results suggest that E^v is much more non-linearly related to environmental conditions than ^Eb. Both E^v and ^Eb depend on the distribution of , the wetness regime and the parameterization used. With the parameterizations, ^Eb showed greater variations than E^v. These results are valid when there are no advective effects or mesoscale circulation patterns and the stratification is unstable.     

On the similarity in atmospheric fluctuations of carbon dioxide,water vapor and temperature over vegetated fields

This paper describes the similarity between atmospheric fluctuations of carbon dioxide, water vapor and temperature using data which cover a wide range of instability (0.02 < < 10). The is the Monin-Obukhov stability parameter including the humidity effect.The spectral analysis shows that the coherency between fluctuations of carbon dioxide and water vapor or temperature is very close to unity, and the phase difference is basically out of phase for whole frequency ranges analyzed. The stability dependence of the normalized standard deviation of carbon dioxide is very similar to those of water vapor and temperature. The normalized standard deviation is about 2.5 under near neutral conditions, and it decreases with increasing instability following the -1/3; power law as (-)^-1/3. The skewness factors of carbon dioxide, water vapor and temperature show a systematic departure with increasing instabilities for 0.02 < s- < 1, and level off at high instabilities for 1 < -\s < 10. The stability dependence of the flatness factors is not so clear as that noted in the standrard deviation and skewness factors. Dissipation rates of carbon dioxide, water vapor and temperature variance are well related to the spectral peak wavelength. This seems to be real since the local production and local dissipation rates are the main terms, almost balancing one another in the variance budget equations for scalar entities.     

Nitrate in the atmospheric boundary layer of the tropical South Pacific: Implications regarding sources and transport

Weekly bulk aerosol samples collected at Funafuti, Tuvalu (8°30S, 179°12E), American Samoa (14°15S, 170°35W), and Rarotonga (21°15S, 159°45W), from 1983 through most of 1987 have been analyzed for nitrate and other constituents. The mean nitrate concentration is about 0.11 g m^–3 at each of these stations: 0.107±0.011 g m^–3 at Funafuti; 0.116±0.008 at American Samoa; and 0.117±0.010 at Rarotonga. Previous measurements of mineral aerosol and trace metal concentrations at American Samoa are among the lowest ever recorded for the near-surface troposphere and indicate that this region is minimally affected by transport of soil material and pollutants from the continents. Consequently, the nitrate concentration of 0.11 g m^–3 can be regarded as the natural level for the remote marine boundary layer of the tropical South Pacific Ocean. In contrast, over the tropical North Pacific which is significantly impacted by the transport of material from Asia and North America, the mean nitrate concentrations are about three times higher, 0.29 and 0.36 g m^–3 at Midway and Oahu, respectively. The major sources of the nitrate over the tropical South Pacific are still very uncertain. A very significant correlation between the nitrate concentrations at American Samoa and the concentrations of ²¹⁰Pb suggests that transport from continental sources might be important. This continental source could be lightning, which occurs most frequently over the tropical continents. A near-zero correlation with ⁷Be indicates that the stratosphere and upper troposphere are probably not the major sources. A significant biogenic source would be consistent with the higher mean nitrate concentrations, 0.16 to 0.17 g m^–3, found over the equatorial Pacific at Fanning Island (3°55N, 159°20W) and Nauru (0°32S, 166°57E). The lack of correlation between nitrate and nss sulfate at American Samoa does not necessarily preclude an important role for marine biogenic sources.     

Gas and Particle Products Distribution from the Reaction of β-Caryophyllene with Ozone

Gas and particulate reaction products from the ozonolysis of -caryophyllene (I) in the presence of atmospheric air were investigated using a combination of gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC). A Scanning Mobility Particle Sizer system (3936, TSI) and a Condensation Particle Counter (3025A, TSI) were used to study secondary organic aerosol formation. The nighttime oxidation was carried out in a large outdoor smog chamber (190 m³). A wide range of ring retaining and ring opening products in the gas and particle phase are reported over the course of the reaction. On average, measured gas and particle phase products accounted for 64% of the reacted -caryophyllene (I) carbon. Measurements show that a number of reaction products with low vapor pressure (e.g., -caryophyllone aldehyde (IV), -norcaryophyllone aldehyde (V), -caryophyllonic acid (VIII), -14-hydroxycaryophyllonic acid (XIV)) were found in the sample taken during the first 20 min of the reaction and may play an important role in the early formation of secondary organic aerosol. A detailed mechanism is proposed to account for most products observed in this investigation.     

Measurements of solar radiation and estimation of optical depth in the high Andes of Peru

Summary During an expedition to the high Andes of Southern Peru in June–July 1977, measurements of direct solar radiation in four spectral bands (0.270–0.530–0.630–0.695–2.900 ) were conducted at six sites in elevations ranging from sea level to 5645 m. These measurements were evaluated in Langley plots to determine total optical depths () and irradiances at the top of the atmosphere. In addition, water vapor optical depths (_wv) were calculated from the mean radiosounding over Lima during the expedition, and Rayleigh (_ray) and ozone (_oz) optical depths were obtained from published tabulations. Subtracting _ray, _oz, and _wv from yielded estimates of aerosol optical depth _aer. The components _ray and _oz decrease from the shorter towards the longer wavelength bands and from the lower towards the higher elevation sites; _aer also decreases towards the higher elevations. Particularly pronounced is the decrease of _aer and from the lowlands of the Pacific coast to the highlands of the interior, reflecting the effect of a persistent lower-tropospheric inversion and the contrast from the marine boundary layer to the clear atmosphere of the high Andes.With 4 Figures     

Potential refractivity as a similarity variable

The validity of a common radiometeorological application of Monin-Obukhov (M-O) similarity theory to potential refractivity (), which is a nonlinear combination of and q, is determined by whether the properly nondimensionalized gradient is a universal function of z/L. We develop expressions for the flux of (and its scaling parameter, *) in terms of temperature and moisture fluxes, and an M-O similarity expression for the vertical gradient. Results show that even if and q are accepted as exactly following M-O similarity expressions, when the surface layer is stable, does not obey such an expression. That is, when properly nondimensionalized, the vertical gradient of does not collapse to a single universal function of z/L. The assumption that behaves as a similarity variable is approximately correct for well-mixed surface layers under unstable and near-neutral conditions.The gradient of is an important factor in determining microwave propagation conditions. We demonstrate the error induced in a simple algorithm when is assumed to obey M-O similarity theory. An alternative methodology, consistent with the application of similarity theory to and q, is then developed without requiring that itself satisfy similarity theory.     

Experiments On Buoyant Plume Dispersion In A Laboratory Convection Tank

Plume dispersion in the convective boundary layer (CBL) is investigated experimentally in a laboratory convection tank. The focusis on highly-buoyant plumes that loft near or become trapped in the CBL capping inversion and resistdownward mixing. Such plumes are defined by dimensionless buoyancy fluxes F_* 0.1, where F_* = F_b/(U w_* ² z_i), F_b is the stack buoyancy flux,U is the mean wind speed, w_* is the convective velocity scale, and z_i is the CBL depth. The aim is to obtain statistically-reliable mean (C) and root-mean-square (rms, _c) concentration fields as a function of F_* and the dimensionless distance X = w_*x/(U z_i), where x is the distance downstream of the source.The experiments reveal the following mainresults: (1) For 3 X 4and F_* 0.1, the crosswind-integrated concentration (CWIC) fields exhibit distinctly uniform profiles below z_i with a CWIC maximum aloft, in contrast to the nonuniform profiles obtained earlier by Willis and Deardorff. (2) The lateral dispersion (_y) variation with X is consistent with Taylor's theory for _* 0.1 and a buoyancy-enhanced dispersion, _y/z_i F_* ^1/3X^2/3, forF_* = 0.2 and 0.4. (3) The entrapment, the plume fraction above z_i, has a mean (E) that follows a systematic variationwith X and F_*, and a variability (_e/E) that is broad ( 0.3 to 2) near the source but subsides to 0.25 far downstream. (4) Vertical profiles of the concentration fluctuation intensity (c/C) are uniform for z < z_i and X > 1.5, but exhibit significant increases: (a) at the surface and close to the source (X 1.5), and(b) in the entrainment zone. (5) The cumulative distribution functions (CDFs) of the scaled concentration fluctuations (c/_c) separate into mixed-layer and entrainment-layer CDFs for X 2, with the mixed-layer group collapsing to a single distribution independent of z.These are the first experiments to obtain all components of the lateral and vertical dispersion parameters (rms meander, relative dispersion, total dispersion) for continuous buoyant releases in a convection tank. They also are the first tank experiments to demonstrate agreement with field observations of: (1) the scaled ground-level concentration along the plume centreline, and (2) the dimensionless lateral dispersion _y/z_i of buoyant plumes.     

A study of the sensitivity of bare soil evaporation schemes to soil surface wetness,using the coupled soil moisture and surface temperature prediction model,BARESOIL

Summary The performance of evaporation schemes with and approach and their combination within resistance representation of evaporation from bare soil surface is discussed. For this purpose nine schemes, based on different functions of or , on the ratio of the volumetric soil moisture content and its saturated value are used.The quality of the chosen schemes has been evaluated using the results of time integration by the coupled soil moisture and surface temperature prediction model, BARESOIL, using in situ data. A sensitivity analysis was made using two sets of data derived from the volumetric soil moisture content of the top soil layer. One with values below the wilting point (0.17 m³m^–3) and the second with values above 0.20m³m^–3. Data sets were obtained at the experimental site Rimski anevi, Yugoslavia, from the bare surface of a chernozem soil.With 4 Figures