Trace gas exchange at the air/water interface: Measurements of mass accommodation coefficients

A liquid jet of 90 m diameter and variable length has been utilized to determine absorption rates and, hence, mass accommodation coefficients , of atmospheric trace gases. The compounds investigated are HCl (0.01), HNO₃ (0.01), N₂O₅ (0.005), peroxyacetyl nitrate (>0.001), and HONO (0.005). It is concluded that the absorption of these trace gases by liquid atmospheric water is not significantly retarded by interfacial mass transport. The strengths and limitations of the liquid jet technique for measuring mass accommodation coefficients are explored.     

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 .     

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.     

Turbulence mechanisms at an agricultural site

An extensive set of turbulence data from the 3- and 12-m heights taken over an agricultural site (Marsta, Sweden) are analyzed and compared with data from ideal sites.In unstable air, Monin-Obukhov similarity is found to be valid for the non-dimensional gradients of wind, _m , temperature, _h , and humidity, _e , for (only a few data), for _T /|T _*|,/ _E /|E _*| and for the non-dimensionalized inertial subrange spectra of temperature and humidity. Where comparison is possible, the unstable data also agree with those found in the Kansas study, with one remarkable exception, the inertial subrange constant of the temperature spectrum, ₁, being only 0.39, compared to the value 0.80 found at the Kansas site.On the stable side, most similarity predictions break down, with most of the data differing systematically from the corresponding Kansas results, the only exception being . The inertial subrange constants for temperature, ₁, and for humidity, ₁ are found to have the same values, 0.39 and 0.30, respectively, as they do on the unstable side. Remarkable similarity is found for the shape of the stable u- and - and e-spectra. In addition, this shape is found to be identical with that found in Kansas. The peak wavelength of the stable u-, and -spectra is found to be about four times larger than it is for the corresponding Kansas spectra. This is interpreted to be a result of the increased macro-roughness at the Marsta site as compared with that at the Kansas site. A possible explanation for the low ₁-value is discussed, suggesting that ₁ is not a universal constant, but instead dependent on the turbulent structure.     

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.     

Radiometrically determined skin temperature and scalar roughness to estimate surface heat flux part II: Performance of parameterized scalar roughness for the determination of sensible heat

Several formulations and proposals to determine the value of the radiometric scalar roughness for sensible heatz _0h,r are tested with respect to their performance in the estimation of the sensible heat flux by means of the profile equations derived from Monin-Obukhov similarity theory. The equations are applied to the data set of spatially averaged surface skin temperature and profiles of wind speed and temperature observed in a pasture field during a growing season. The use of a physical model developed for a dense canopy to estimate scalar roughness for sensible heatz _0h,r produced sensible heat fluxH with a correlation coefficientr=0.884, the ratio of means being H _s /H=1.19 in a comparison with reference values ofH _s . In comparison, a proposal for a fixed value ofz _0h yieldedr=0.887, H _s /H=0.879. In both cases, the validity ofz _0h =z _0h,r was assumed. All expressions derived to estimatez _0h,r from a multiple linear regression with such predictors as leaf area index, solar radiation and the ratio of solar radiation to extraterrestrial radiation, were found to produce a better result, withr better than 0.90 and H _s /H around 1.0. However, when the constantsc andf of a linear regression equationHs=cH+f are used to evaluate the equations, a marked difference in performance of each formulation appeared. In general, equations with smaller numbers of predictors tend to produce a biased result, i.e., an overestimation ofH at largeH _s . These values ofH are used in conjunction with the energy balance equation to derive values of the latent heat fluxLE, which are shown to be in good agreement with the reference valuesLE _s , withr greater than 0.97.     

A note on the analogy between momentum transfer across a rough solid surface and the air-sea interface

The aerodynamic classification of the resistance laws above solid surfaces is based on the use of a so-called Reynolds roughness number Re _s =h _s u _*/, whereh _s is the effective roughness height, -viscosity,u _*-friction velocity. The recent experimental studies reported by Toba and Ebuchi (1991), demonstrated that the observed variability of the sea roughness cannot be explained only on the basis of the classification of aerodynamic conditions of the sea surface proposed by Kitaigorodskii and Volkov (1965) and Kitaigorodskii (1968) even though the latter approach gains some support from recent experimental studies (see for example Geernaertet al. 1986). In this paper, an attempt is made to explain some of the recently observed features of the variability of surface roughness (Toba and Ebuchi, 1991; Donelanet al., 1993). The fluctuating regime of the sea surface roughness is also described. It is shown that the contribution from the dissipation subrange to the variability of the sea surface can be very important and by itself can explain Charnock's (1955) regime.     

Numerische Integrationen einer Gleichung für die turbulente Diffusion in der Atmosphäre

Zusammenfassung Es werden numerische Integrationen der dreidimensionalen Fickschen Diffusionsgleichung mit höhenabhängigen Diffusionskoeffizienten und Windgeschwindigkeit für den stationären Fall und eine kontinuierlich emittierende Punktquelle durchgeführt. Für die drei typischen Ausbreitungsverhältnisse Starke Durchmischung, Bodeninversion und Inversion über der Quelle, charakterisiert durch die Diffusionskoeffizienten und die Windgeschwindigkeit, werden die Einflüsse unterschiedlicher Quellhöhe, Sinkgeschwindigkeit und Ablagerungsgeschwindigkeit studiert.

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Summary Numerical integrations of the threedimensional Fickean diffusion equation with height dependent diffusion coefficients and wind velocity are performed in the stationary case with a continuous point source. For the three typical cases strong mixing, surface inversion and inversion above the source characterized by the diffusion coefficients and wind velocity, the effects of source height, sinking velocity and deposition velocity are discussed.

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Résumé Les auteurs ont procédé à l'intégration numérique de l'équation à trois dimensions de la diffusion, équation établie par Fick. Ils ont, pour cela, utilisé des coefficients de diffusion variant avec l'altitude et la vitesse du vent et distingué l'état stationnaire et le cas d'une source d'émission ponctuelle et continue. Ils étudient en outre les influences de hauteurs différentes de la source, de la rapidité de subsidence et de la vitesse de sédimentation. Ils ont tenu compte pour cela des trois conditions typiques de diffusion mélange très accentué, inversion au sol et inversion au-dessus de la source.

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Mit 7 Textabbildungen     

Equatorial disturbances,monsoons, and 1982–1983 ENSO

Summary Interannual modes are described in terms of three-month running mean anomaly winds (u,v), outgoing longwave radiation (OLR), and sea surface temperature (T _* ). Normal atmospheric monsoon circulations are defined by long-term average winds (u _n,v _n) computed every month from January to December. Daily winds are grouped into three frequency bands, i.e., 30–60 day filtered winds (u _L,v _L); 7–20 day filtered winds (u _M,v _M); and 2–6 day filtered winds (u _S,v _S). Three-month running mean anomaly kinetic energy (signified asK _L , K _M , andK _S , respectively) is then introduced as a measure of interannual variation of equatorial disturbance activity. Interestingly, all of theseK _L , K _M , andK _S perturbations propagate slowly eastward with same phase speed (0.3 ms^–1) as ENSO modes. Associated with this eastward propagation is a positive (negative) correlation between interannual disturbance activity (K _L , K _M , K _S ) and interannualu (OLR) modes. Namely, (K _L , K _M , K _S ) becomes more pronounced than usual nearly simultaneously with the arrival of westerlyu and negativeOLR (above normal convection) perturbutions. In these disturbed areas with (K _L , K _M , K _S >0), upper ocean mixing tends to increase, resulting in decreased sea surface temperature, i.e.T _* 0. Thus, groups (not individual) of equatorial disturbances appear to play an important role in determiningT _* variations on interannual time scales. HighestT _* occurs about 3 months prior to the lowestOLR (convection) due primarily to radiational effects. This favors the eastward propagation of ENSO modes. The interannualT _* variations are also controlled by the prevailing monsoonal zonal windsu _n, as well as the zonal advection of sea surface temperature on interannual time scales. Over the central Pacific, all of the above mentioned physical processes contribute to the intensification of eastward propagating ENSO modes. Over the Indian Ocean, on the other hand, some of the physical processes become insignificant, or even compensated for by other processes. This results in less pronounced ENSO modes over the Indian Ocean.With 10 FiguresContribution No. 89-6, Department of Meteorology, University of Hawaii, Honolulu, Hawaii.     

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.     

Estimation of Scalar Source/Sink Distributions in Plant Canopies Using Lagrangian Dispersion Analysis: Corrections for Atmospheric Stability and Comparison with a Multilayer Canopy Model

Source/sink distributions of heat, water vapour andCO₂ within a rice canopy were inferred using aninverse Lagrangian dispersion analysis and measuredmean profiles of temperature, specific humidity andCO₂ mixing ratio. Monin–Obukhov similarity theorywas used to account for the effects of atmosphericstability on _w(z), the standard deviation ofvertical velocity and _L(z), the Lagrangian timescale of the turbulence. Classical surface layer scaling was applied in the inertial sublayer (z > z_ruf)using the similarity parameter = (z - d)/L, where z is height above ground, d is the zero plane displacementheight for momentum, L is the Obukhov length,and z_ruf 2.3h_c, where h_c iscanopy height. A single length scale h_c, was usedfor the stability parameter 3 = h_c/L in the height range 0.25 < z/h_c < 2.5. This choice is justified by mixing layer theory, which shows that within the roughness sublayer there is one dominant turbulence length scaledetermined by the degree of inflection in the windprofile at the canopy top. In the absence of theoretical or experimental evidence for guidance,standard Monin–Obukhov similarity functions, with = h_c/L, were used to calculate the stabilitydependence of _w(z) and _L(z) in the roughness sublayer. For z/h_c < 0.25 the turbulence length and time scales are influenced by the presence of the lowersurface, and stability effects are minimal. With theseassumptions there was excellent agreement between eddycovariance flux measurements and deductions from theinverse Lagrangian analysis. Stability correctionswere particularly necessary for night time fluxes whenthe atmosphere was stably stratified.The inverse Lagrangian analysis provides a useful toolfor testing and refining multilayer canopy models usedto predict radiation absorption, energy partitioningand CO₂ exchanges within the canopy and at thesoil surface. Comparison of model predictions withsource strengths deduced from the inverse analysisgave good results. Observed discrepancies may be dueto incorrect specification of the turbulent timescales and vertical velocity fluctuations close to theground. Further investigation of turbulencecharacteristics within plant canopies is required toresolve these issues.     

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     

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.     

Further Studies Of Atmospheric Turbulence In Layers Near The Surface: Scaling The Tke Budget Above The Roughness Sublayer

The second of two experimental studies of the TKE budget conducted on sites of different roughness is described, and results are compared. The first took place within a shallow layer above a small field of mostly bare, cultivated soil; the second was carried out above a roughness sublayer of significant depth on an extensive plain of tall dry grass. Budget terms observed in the second study were scaled with a modified u which compensated for effects of an unusually large stress gradient and ensured that the _m functions would be collinear. By showing that the modification becomes negligible in smaller gradients, it is demonstrated that in normal conditions, budgets observed above significant roughness sublayers should be normalized by scaling in terms of the unreduced Reynolds stress at the sublayer's upper surface. This procedure is shown to be consistent with the expectation that TKE budgets in layers near the surface all scale in fundamentally the same way.Other findings include: (1) the fact that most _m functions previously reported are not quite collinear is attributed to a type of overspeeding known to affect three-cup anemometers; (2) revised _m functions, collinear and largely free of the effects of overspeeding, are determined from a well-established characteristic of the linear _m relation for the stable case; (3) data that define collinear _m functions can also be represented with single hyperbolic curves; (4) dissipation is found to be 10 to 15% too small to balance total TKE production in unstable and neutral conditions and to decrease with increasing z/L in thestable regime; and (5) new relations for based on the observed behaviour of the dissipation deficit provide an improved closure for the set of equations that express the budget terms as functions of _m and z/L.     

Flux-profile Relationships for Wind Speed and Temperature in the Stable Atmospheric Boundary Layer

Wind and temperature profiles in the stable boundary layer were analyzed in the context of MoninObukhov similarity. The measurements were made on a 60-m tower in Kansas during October 1999 (CASES-99). Fluxprofile relationships, obtained from these measurements in their integral forms, were established for wind speed and temperature. Use of the integral forms eliminates the uncertainty and accuracy issues resulting from gradient computations. The corresponding stability functions, which were nearly the same for momentum and virtual sensible heat, were found to exhibit different features under weakly stable conditions compared to those under strongly stable conditions. The gradient stability functions were found to be linear, namely _m = 1+ 5.8 and _h = 1 + 5.4 up to a limit of the MoninObukhov stability parameter = 0.8; this is consistent with earlier findings. However, for stronger stabilities beyond a transition range, both functions were observed gradually to approach a constant, with a value of approximately 7. To link these two distinct regimes, a general but pliable functional form with only two parameters is proposed for the stability functions, covering the entire stability range from neutral to very stable conditions.     

The Influence of O3, Relative Humidity, NO and NO2 on the Oxidation of α-Pinene and Δ3-Carene

Upto 13% of -pinene and ³-carene had reacted after 213 s in this dark experimental set-up, where O₃, NO and NO₂ were mixed with terpenes at different relative humidities (RHs). The different experiments were planned according to an experimental design, where O₃, NO₂, NO, RH and reaction time were varied between high and low settings (25 and 75 ppb, 15 and 42%, 44 and 213 s). An increased amount of -pinene and ³-carene reacted in the chamber was observed, when the level of O₃, NO and reaction time was increased and RH was decreased. In the study, it was found that different interactions affected the amount of terpene reacted as well. These interactions were between O₃ and NO, O₃ and reaction time, NO and RH, and between NO and reaction time.     

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

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

Effects of heat and water vapor transport on eddy covariance measurement of CO2 fluxes

Flux densities of carbon dioxide were measured over an arid, vegetation-free surface by eddy covariance techniques and by a heat budget-profile method, in which CO₂ concentration gradients were specified in terms of mixing ratios. This method showed negligible fluxes of CO₂, consistent with the bareness of the experimental site, whereas the eddy covariance measurements indicated large downward fluxes of CO₂. These apparently conflicting observations are in quantitative agreement with the results of a recent theory which predicts that whenever there are vertical fluxes of sensible or latent heat, a mean vertical velocity is developed. This velocity causes a mean vertical convective mass flux (= _cw for CO₂, in standard notation). The eddy covariance technique neglects this mean convective flux and measures only the turbulent flux _c w. Thus, when the net flux of CO₂ is zero, the eddy covariance method indicates an apparent flux which is equal and opposite to the mean convective flux, i.e., _c w = – _c w. Corrections for the mean convective flux are particularly significant for CO₂ because _cw and _c w are often of similar magnitude. The correct measurement of the net CO₂ flux by eddy covariance techniques requires that the fluxes of sensible and latent heat be measured as well.     

Markov-chain simulation of particle dispersion in inhomogeneous flows: The mean drift velocity induced by a gradient in Eulerian velocity variance

The Langevin equation is used to derive the Markov equation for the vertical velocity of a fluid particle moving in turbulent flow. It is shown that if the Eulerian velocity variance _wE is not constant with height, there is an associated vertical pressure gradient which appears as a force-like term in the Markov equation. The correct form of the Markov equation is: w(t + t) = aw(t) + b _wE + (1 – a)T _L ( _wE ²)/z, where w(t) is the vertical velocity at time t, a random number from a Gaussian distribution with zero mean and unit variance, T _L the Lagrangian integral time scale for vertical velocity, a = exp(–t/T _L), and b = (1 – a ²)^1/2. This equation can be used for inhomogeneous turbulence in which the mean wind speed, _wE and T _L vary with height. A two-dimensional numerical simulation shows that when this equation is used, an initially uniform distribution of tracer remains uniform.     

Ab initio study on carbon Kinetic Isotope Effect (KIE) in the reaction of CH4+Cl•

Recent studies suggest that the destruction of methane by Cl in the marine boundary layer could be accounted for as another major sink besides the methane destruction by OH. High level ab initio molecular orbital calculations have been carried out to study the CH₄+Cl reaction, the carbon Kinetic Isotope Effect (KIE) is calculated using Conventional Transition-State Theory (CTST) plus Wigner and Eckart semiclassical tunneling corrections. The calculated KIE is around 1.026 at 300 K and has a small temperature variation. This is by far the largest KIE among different processes involving atmospheric methane destruction (e.g., OH, soil). A calculated mass balance of atmospheric methane including the KIE for the CH₄+Cl reaction is found to favor those methane budgets with enhanced biological methane sources, which have relatively lighter carbon isotope composition.