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1.
Summary Non-uniform mixing of gas-phase trace species may limit the accuracy of the predictions of Eulerian transport/transformation models if the chemical reactions are rapid enough to be diffusion limited. If a reaction is diffusion limited, its average reaction rate might not be accurately represented by those models that assume instantaneous uniform mixing. One possible consequence of this artificial dilution is the overprediction of ozone and hydroxyl radicals. We have determined which reactions in the Regional Acid Deposition Model Gas-Phase Chemical Mechanism (Stockwell et al., 1990) are diffusion limited for a typical atmospheric condition through the calculation of Damköhler numbers. Damköhler numbers are defined to be the ratio of the diffusion mixing time to the chemical reaction time for a given chemical reaction (McRae et al., 1982; Hill, 1976). The reactions of hydroxyl radicals and the reactions of peroxy radicals with NO are diffusion limited under typical atmospheric conditions. Both sets of reactions are especially significant because NOx and organic species strongly affect ozone and hydroxyl radical concentrations. It is suggested that Damköhler numbers could be used to help determine the placement of Eulerian model boundaries and to determine model grid structure.With 2 Figures  相似文献   

2.
A second-order modelling technique is used to investigate the influence of turbulence on chemical reactions. The covariance and variance equations for the NO-O3-NO2 system are developed as a function of the ratio of the timescale of turbulence ( t ) and the timescale of chemistry (Ch): the first Damköhler number ( t /Ch). Special attention is given to the calculation of the covariance between NO and O3 normalized by the product of their means, the so-called intensity of segregation (I S ). This parameter quantifies the state of mixing of two chemical species.The intensity of segregation is calculated as a function of the flux of NO and the first Damköhler number. The model results presented illustrate the importance of taking the effect of turbulence on chemical reactions into account for higher values of the NO flux, for values of the ratio O3/NO larger than 12.5 and for values of the ratio t /CH larger than 0.1. For such cases, the effective reaction rates are slower than if the chemical species are assumed to be uniformly mixed.  相似文献   

3.
We have discussed the behavior of a non-conserved scalar in the stationary, horizontally homogeneous, neutral surface-flux layer and, on the basis of conventional second-order closure, derived analytic expressions for flux and for mean concentration of a gas, subjected to a first-order removal process. The analytic flux solution showed a clear deviation from the constant flux, characterizing a conserved scalar in the surface-flux layer. It decreases with height and is reduced by an order of magnitude of the surface flux at a height equal to about the typical mean distance a molecule can travel before destruction. The predicted mean concentration profile, however, shows only a small deviation from the logarithmic behavior of a conserved scalar. The solution is consistent with assuming a flux-gradient relationship with a turbulent diffusivity corrected by the Damköhler ratio, the ratio of a characteristic turbulent time scale and the scalar mean lifetime. We show that if we use only first-order closure and neglect the effect of the Damköhler ratio on the turbulent diffusivity we obtain another analytic solution for the profiles of the flux and the mean concentration which, from an experimental point of view, is indistinguishable from the first analytic solution. We have discussed two cases where the model should apply, namely NO which, by night, is irreversibly destroyed by interaction with mainly O3 and the radioactive 220Rn. Only in the last case was it possible to find data to shed light on the validity of our predictions. The agreement seemed such that a falsification of our model was impossible. It is shown how the model can be used to predict the surface flux of 220Rn from measured concentration profiles.  相似文献   

4.
We study the interactions of chemistry and turbulent mixing of tracersin the convective boundary layer with a second-order closure model,including higher order chemistry terms. In order to limit the number of predictive equations we prescribe the profiles for ¯w¯, ¯w¯ ¯ and the lengthscale l. However, for model validation we treat temperature and humidity asinert tracers, and compare the results with profiles observed during theAir Mass Transformation Experiment, and with similarity expressions for thesurface layer. We find good agreement of the mean profiles, but the (co-)variances are slightly underpredicted. Furthermore, the model usesdiagnostic equations expressing third moments of concentration in terms ofsecond moments and their vertical derivatives. They are compared withlarge-eddy model results, showing good agreement and, therefore, thesimplifications are justified. The model is applied to the transport of two gases subject to one bimolecular reaction. The importance of concentration correlations on themean transformation rate is studied. For two gases diffusing in oppositedirections we find for moderate and fast chemistry a 50% and90% decreased transformation rate due to the negatively correlatedconcentrations. These values are similar to large-eddy results of Schumannand Sykes et al. For two bottom-up tracers we find that the covariance ofboth reactive species is either positive or negative, increasing or reducingthe effective transformation rate depending on the Damköhler number (the ratio of the turbulent and the chemistry timescale). A significantdirect influence of chemistry on the flux divergence is found in bothcases. According to the model the effective transport to mid-levels of theboundary layer is increased when two reactive tracers diffuse in oppositedirections, and decreased in the case of two bottom-up tracers.  相似文献   

5.
It is shown that K-theory has to be modified for chemical systems that react with time scales similar to the turbulence time scale. In such systems, the value of the exchange coefficient depends not only on the turbulence parameters, but also on the chemical reaction rates. As an example, the NO-O3-NO2 chemical system is studied. Using second-moment equations, new flux-gradient relationships for the neutral atmospheric surface layer are obtained which depend on the time scale ratios of turbulence ( t ) and chemical reactions ( ch), i.e., reactive K-theory. Within the framework of this reactive K-theory, the flux of a chemical species is both a function of the concentration gradients of the three chemical species involved and of the ratio of the time scale of turbulence to the time scale of chemistry. In the special case of slow chemistry ( t ch) inert K-theory is applicable.The reactive exchange coefficients are implemented in a surface-layer model that calculates the flux and concentration profiles of the three chemical species. The results of the calculations of the effective exchange coefficients are different for reactive K-theory and inert K-theory; the differences are largest for nitric oxide, but smaller for ozone and nitrogen dioxide.  相似文献   

6.
We have carried out a theoretical study of the simplest possible, second-order, chemical destruction process in the atmospheric surface layer. The model describes the destruction of two gases emanating from the surface with the same molecular flux. Although this situation seems artificial with no counterpart in the real atmosphere, the results shed light on some fundamental problems. For example, it is possible to specify boundary conditions, with the concentrations and the fluxes at a given height away from the surface, which lead to unrealistic solutions with infinite surface fluxes. A method to describe and separate the consistent solutions for this process was developed. It is in general of particular interest from an experimental point of view since it is not possible to measure fluxes right at the surface: if a measurement of flux and concentration in a given height requires infinite surface fluxes there is something wrong with the data. We expect that such problems will be inherent in more complex reactions schemes, such as the NO-NO2-O3 triad. Just as in first-order destruction processes, the Damköhler ratio will enter the turbulent diffusivity, but where this ratio is concentration independent for first-order processes, the present second-order model implies that the Damköhler ratio is proportional to the concentration. In the study of first-order processes it was found that the Damköhler correction to the turbulent diffusivity is of minor importance from an experimental point of view. We arrive at the same conclusion in this particularly simple study of second-order destruction. In other words, this work may be considered a further development of a previous study of the first-order destruction of a passive scalar. The model and the method we develop to solve the corresponding nonlinear differential equations are considered a preliminary study for developing tools to deal with more complicated atmospheric processes. Also, the results obtained may serve as a “calibration case” for more elaborate simulations.  相似文献   

7.
Although a large volume of monitoring and computer simulation data exist for global coverage of HF, study of HF in the troposphere is still limited to industry whose primary interest is the safety and risk assessment of HF release because it is a toxic gas. There is very limited information on atmospheric chemistry, emission sources, and the behavior of HF in the environment. We provide a comprehensive review on the atmospheric chemistry of HF, modeling the reactions and transport of HF in the atmosphere, the removal processes in the vertical layer immediately adjacent to the surface (up to approximately 500 m) and recommend research needed to improve our understanding of atmospheric chemistry of HF in the troposphere. The atmospheric chemistry, emissions, and surface boundary layer transport of hydrogen fluoride (HF) are summarized. Although HF is known to be chemically reactive and highly soluble, both factors affect transport and removal in the atmosphere, the chemistry can be ignored when the HF concentration is at a sufficiently low level (e.g., 10 ppmv). At a low concentration, the capability for HF to react in the atmosphere is diminished and therefore the species can be mathematically treated as inert during the transport. At a sufficiently high concentration of HF (e.g., kg/s release rate and thousands of ppm), however, HF can go through a series of rigorous chemical reactions including polymerization, depolymerization, and reaction with water to form molecular complex. As such, the HF species cannot be considered as inert because the reactions could intimately influence the plume’s thermodynamic properties affecting the changes in plume temperature and density. The atmospheric residence time of HF was found to be less than four (4) days, and deposition (i.e., atmosphere to surface transport) is the dominant mechanism that controls the removal of HF and its oligomers from the atmosphere. The literature data on HF dry deposition velocity was relatively high compared to many commonly found atmospheric species such as ozone, sulfur dioxide, nitrogen oxides, etc. The global average of wet deposition velocity of HF was found to be zero based on one literature source. Uptake of HF by rain drops is limited by the acidity of the rain drops, and atmospheric particulate matter contributes negligibly to HF uptake. Finally, given that the reactivity of HF at a high release rate and elevated mole concentration cannot be ignored, it is important to incorporate the reaction chemistry in the near-field dispersion close to the proximity of the release source, and to incorporate the deposition mechanism in the far-field dispersion away from the release source. In other words, a hybrid computational scheme may be needed to address transport and atmospheric chemistry of HF in a range of applications. The model uncertainty will be limited by the precision of boundary layer parameterization and ability to accurately model the atmospheric turbulence.  相似文献   

8.
A large-eddy simulation is modified to include multiple scalars emitted by a plant canopy. Each of these scalars is subjected to varying rates of chemical loss. Presented is a detailed comparison between conservedspecies and species undergoing first- and second-order chemical loss.Profiles of mean mixing ratio, mixing-ratio variance and vertical mixing-ratio flux reveal the influence of chemical reactivity. Distribution of thescalar source through the depth of the canopy is shown to locally reducethe reaction rate for second-order species. Transport efficiencies, diffusioncoefficients, and mean source heights also exhibit chemical dependencies.Budgets of mixing-ratio variance and flux elucidate the mechanisms throughwhich chemistry modifies each. Instantaneous fields show the existence ofintermittently occurring coherent structures that are thought to enhancespecies segregation.  相似文献   

9.
Measurements of atmospheric composition have been made over a remote rainforest landscape. A box model has previously been demonstrated to model the observed daytime chemistry well. However the box model is unable to explain the nocturnal measurements of relatively high [NO] and [O3], but relatively low observed [NO2]. It is shown that a one-dimensional (1-D) column model with simple O3-NOx chemistry and a simple representation of vertical transport is able to explain the observed nocturnal concentrations and predict the likely vertical profiles of these species in the nocturnal boundary layer (NBL). Concentrations of tracers carried over from the end of the night can affect the atmospheric chemistry of the following day. To ascertain the anomaly introduced by using the box model to represent the NBL, vertically-averaged NBL concentrations at the end of the night are compared between the 1-D model and the box model. It is found that, under low to medium [NOx] conditions (NOx?<?1 ppbv), a simple parametrisation can be used to modify the box model deposition velocity of ozone, in order to achieve good agreement between the box and 1-D models for these end-of-night concentrations of NOx and O3. This parametrisation would could also be used in global climate-chemistry models with limited vertical resolution near the surface. Box-model results for the following day differ substantially if this effective nocturnal deposition velocity for ozone is implemented; for instance, there is a 9% increase in the following days peak ozone concentration. However under medium to high [NOx] conditions (NOx > 1 ppbv), the effect on the chemistry due to the vertical distribution of the species means no box model can adequately represent chemistry in the NBL without modifying reaction rate coefficients.  相似文献   

10.
A one-dimensional cumulus cloud chemistry model(1CCCM)is developed to simulate cloudphysical processes and chemical processes during the evolution of a convective cloud.The cloudphysical submodel includes a detailed microphysical parameterized scheme of 20 processes.Thechemistry submodel is composed of three parts:gas phase chemistry,aqueous phase chemistry andscavenging of soluble gases.The gas phase reaction mechanism contains 85 reactions among 45species including 13 organics.The aqueous phase reaction mechanism contains 54 reactions among40 species and 12 ion equilibria.Mass of 19 gases is transported between the gas phase and theaqueous phase.With this model,studies may be made to analyze the interactions among processesduring lifetime of a cumulus cloud.  相似文献   

11.
粤东复杂地形上空的大气湍流强度及扩散参数   总被引：3，自引：0，他引：3  
在具有复杂下垫面的粤东梅州市采用追踪平衡球的双经纬仪观测和美制ＧＩＬＬ三轴风速仪观测，分别测定了该地区拉格朗日系统和欧拉系统的湍流脉动量。然后用不同参照系的泰勒公式，分别计算出大气的水平和垂直的湍流强度及扩散参数，并与ＰＧ法之计算值和ＢＮＬ实验结果比较，发现距地面１００ｍ以上高空在各类稳定度层结条件下大气扩散参数均比ＰＧ值和ＢＮＬ值偏大。  相似文献   

12.
从湍流经典理论到大气湍流非平衡态热力学理论   总被引：2，自引：0，他引：2  
湍流是日常生活中一种普遍的自然现象,也是经典物理学仍未完全解决的难题。湍流更是大气运动的最基本特征。本文系统地回顾了大气湍流经典理论发展简史,进一步详细介绍了大气湍流非平衡态热力学理论。大气湍流非平衡态热力学理论在熵平衡方程中引入动力过程,进而统一推导出大气湍流输送的Fourier定律、Flick定律和Newton定律,证明了Dufour效应、Soret效应、可逆动力过程与热力不可逆湍流输送过程之间的交叉耦合效应,以及湍流强度定理。这些定律和定理中得到了观测的事实验证,同时它们的唯象系数也由观测资料所确定。湍流强度定理揭示,湍流发展的宏观原因是速度和温度的剪切效应,Reynolds湍流和Rayleigh-Bénard湍流共存于大气湍流中。热力过程和动力过程间耦合效应现象的发现突破了传统湍流输送理论,即Fourier定律、Flick定律和Newton定律的观点——一个宏观量的输送通量等价于这个宏观量的梯度湍流输送通量。热力和动力过程间的耦合原理认为,一个宏观量的输送通量包括这个量的梯度湍流输送通量和速度耦合输送通量两部分。因此,能量和物质的垂直输送通量除了相应物理量梯度造成的湍流输送外,还应包括垂直速度耦合效应,即辐散或辐合运动造成的耦合效应。在一个很宽的尺度范围内,地表面的空间特征是非均匀的。下垫面非均匀性造成的对流运动将引起大气的辐散或辐合运动。这可能是导致地表能量收支不平衡的重要原因之一。垂直速度对垂直湍流输送的交叉耦合效应为非均匀下垫面大气边界层理论的发展,并为克服地表能量收支不平衡问题及非均匀下垫面大气边界层参数化遇到的困难提供了可能的线索。  相似文献   

13.
The reaction of sodium bromide particles in the presence of ozone was studied in a flow system both under dark conditions and with 254 nm radiation. We found that there was significant formation of gaseous bromine (probably Br2) in the presence of ozone in the dark, and that bromide deposited to the walls of the Pyrex reaction flask was its source. The observed rate of gaseous bromine formation in these experiments was approximately 100–1000 times faster than expected based on the knownrate constant for aqueous reaction of bromide with ozone. While the mechanism responsible for this enhanced reactivity was not identified, based on previous reports we suggest that the glass surface converted ozone to more reactive species, such as hydroxyl radical, which in turn oxidized bromide. In the presence of 254 nm radiation, rates of gaseous bromine collection were further enhanced, likely as a result of increased radical production in the system, and wall-deposited bromide was also the source of the gaseous bromine. In these `light' experiments, there was a significant decline in ozone mixing ratios, consistent with bromine radical chemistry. These results suggest the possibility that ozone reacting with internally mixed silicate/sea-salt particles might be a significant mechanism for the oxidation of particulate halides, and subsequent release of photoactive halogen species, in the marine boundary layer.  相似文献   

14.
The joint concentration probability density function of two reactive chemical species is modelled using a bivariate Gamma distribution coupled with a three-dimensional fluctuating plume model able to simulate the diffusion and mixing of turbulent plumes. A wind-tunnel experiment (Brown and Bilger, J Fluid Mech 312:373–407, 1996), carried out in homogeneous unbounded turbulence, in which nitrogen oxide is released from a point source in an ozone doped background and the chemical reactions take place in non-equilibrium conditions, is considered as a test case. The model is based on a stochastic Langevin equation reproducing the barycentre position distribution through a proper low-pass filter for the turbulence length scales. While the meandering large-scale motion of the plume is directly simulated, the internal mixing relative to the centroid is reproduced using a bivariate Gamma density function. The effect of turbulence on the chemical reaction (segregation), which in this case has not yet attained equilibrium, is directly evaluated through the covariance of the tracer concentration fields. The computed mean concentrations and the O3–NO concentration covariance are also compared with those obtained by the Alessandrini and Ferrero Lagrangian single particle model (Alessandrini and Ferrero, Physica A 388:1375–1387, 2009) that entails an ad hoc parametrization for the segregation coefficient.  相似文献   

15.
A bifurcation phenomenon with relevance to atmospheric chemistry is discussed. The gasphase reactions in the troposphere exhibit two types of temporal evolution which are controlled by the strength of the source,Q, of nitric oxide, NO, via the nonlinear chemical coupling between the hydrogen oxides and nitrogen oxides chemistry. IfQ remains below a threshold value, all short-lived species, including NO, approach steady-state concentrations, while above the threshold bifurcation to another state with increasing (nonstationary) NO concentrations accompanied by a depletion of the OH and HO2 abundances takes place.  相似文献   

16.
Reported are the results from a comparison of OH,H2O2CH3OOH, and O3 observationswithmodel predictions based on current HOx–CH4reaction mechanisms. The field observations are thoserecorded during the NASA GTE field program, PEM-Tropics A. The major focus ofthis paper is on thosedata generated on the NASA P-3B aircraft during a mission flown in the marineboundary layer (MBL) nearChristmas Island, a site located in the central equatorial Pacific (i.e.,2° N, 157° W). Taking advantage of thestability of the southeastern trade-winds, an air parcel was sampled in aLagrangian mode over a significantfraction of a solar day. Analyses of these data revealed excellent agreementbetween model simulated andobserved OH. In addition, the model simulations reproduced the major featuresin the observed diurnalprofiles of H2O2 and CH3OOH. In the case ofO3, the model captured the key observational feature whichinvolved an early morning maximum. An examination of the MBL HOxbudget indicated that the O(1D) + H2Oreaction is the major source of HOx while the major sinks involveboth physical and chemical processes involving the peroxide species,H2O2 and CH3OOH. Overall, the generally goodagreement between modeland observations suggests that our current understanding ofHOx–CH4 chemistry in the tropical MBL isquite good; however, there remains a need to critically examine this chemistrywhen both CH2O and HO2are added to the species measured.  相似文献   

17.
Measurements of atmospheric turbulence made over the Arctic pack ice during the Surface Heat Budget of the Arctic Ocean experiment (SHEBA) are used to determine the limits of applicability of Monin–Obukhov similarity theory (in the local scaling formulation) in the stable atmospheric boundary layer. Based on the spectral analysis of wind velocity and air temperature fluctuations, it is shown that, when both the gradient Richardson number, Ri, and the flux Richardson number, Rf, exceed a ‘critical value’ of about 0.20–0.25, the inertial subrange associated with the Richardson–Kolmogorov cascade dies out and vertical turbulent fluxes become small. Some small-scale turbulence survives even in this supercritical regime, but this is non-Kolmogorov turbulence, and it decays rapidly with further increasing stability. Similarity theory is based on the turbulent fluxes in the high-frequency part of the spectra that are associated with energy-containing/flux-carrying eddies. Spectral densities in this high-frequency band diminish as the Richardson–Kolmogorov energy cascade weakens; therefore, the applicability of local Monin–Obukhov similarity theory in stable conditions is limited by the inequalities Ri < Ri cr and Rf < Rf cr. However, it is found that Rf cr  =  0.20–0.25 is a primary threshold for applicability. Applying this prerequisite shows that the data follow classical Monin–Obukhov local z-less predictions after the irrelevant cases (turbulence without the Richardson–Kolmogorov cascade) have been filtered out.  相似文献   

18.
The average dispersion of a plume in the atmospheric boundary layer is strongly influenced by atmospheric turbulence. Atmospheric turbulence determines also concentration fluctuations due to turbulent meandering by large scale turbulent eddies and in-plume fluctuations, due to smaller scale eddies. Conversion of NO to NO2 in a plume is influenced by micro-scale mixing, due to the concentration fluctuation correlation % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaWaa0aaaeaaca% qGobGaae4tamaaCaaaleqabaGaaeymaaaakiaab+eadaqhaaWcbaGa% ae4maaqaaiaabgdaaaaaaaaa!3AF4!\[\overline {{\rm{NO}}^{\rm{1}} {\rm{O}}_{\rm{3}}^{\rm{1}} } \] and macro-scale mixing, the mixing in of ambient air containing O3 into the plume.The study of turbulent meandering, in-plume fluctuations, microscale and macro-scale mixing will contribute to a better understanding of concentration fluctuations in general.  相似文献   

19.
We report on a novel approach for the Reynolds-averaged Navier-Stokes (RANS) modelling of the neutral atmospheric boundary layer (ABL), using the standard k-ek-{\varepsilon} turbulence model. A new inlet condition for turbulent kinetic energy is analytically derived from the solution of the k-ek-{\varepsilon} model transport equations, resulting in a consistent set of fully developed inlet conditions for the neutral ABL. A modification of the standard k-ek-{\varepsilon} model is also employed to ensure consistency between the inlet conditions and the turbulence model. In particular, the turbulence model constant C μ is generalized as a location-dependent parameter, and a source term is introduced in the transport equation for the turbulent dissipation rate. The application of the proposed methodology to cases involving obstacles in the flow is made possible through the implementation of an algorithm, which automatically switches the turbulence model formulation when going from the region where the ABL is undisturbed to the region directly affected by the building. Finally, the model is completed with a slightly modified version of the Richards and Hoxey rough-wall boundary condition. The methodology is implemented and tested in the commercial code Ansys Fluent 12.1. Results are presented for a neutral boundary layer over flat terrain and for the flow around a single building immersed in an ABL.  相似文献   

20.
Non-stationarity is a common feature in geophysical flows, though it still remains an open question on how the non-stationarity of flow affects its statistical structure. Using the telegraph approximation (TA) method, we quantified how non-stationarity in the measured atmospheric turbulent vertical velocity time series affects its clustering properties—one of the two main components of intermittency in turbulence. We compare different TA results between stationary and non-stationary atmospheric turbulent vertical velocity records, and find that the non-stationary data possess different cluster and intermittency exponents from stationary data. The inter-pulse period of the non-stationary records takes a near power-law distribution while the inter-pulse period of the stationary records exhibits a stretched exponential distribution. These results suggest that non-stationarity of the underlying processes can affect the statistical structure of turbulence, especially the clustering properties.  相似文献   

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