The dispersion of chemically reactive species in the atmospheric boundary layer

Summary The role of turbulence in the dispersion of atmospheric pollutants that react with linear (decay) and nonlinear (second-order) chemical reactions is examined. The most relevant processes that drive the reactivity of species emitted in a surface area or released by a point source are studied by deriving the dimensionless scaling numbers from equations for the atmospheric turbulent reacting flow. The first number is the ratio of the time scale of turbulence to the time scale of the chemical reaction, namely the Damköhler number. The second number is the ratio of the concentrations of the species present in the chemical transformations. In this paper, model results and experimental studies of turbulent reacting flows in the atmospheric boundary layer are presented to show the modifications and control exerted by turbulence on the atmospheric chemistry as a function of these numbers and processes. We also discuss how the chemical transformation is affected when species are in a state of chemical equilibrium.By studying the plume dispersion of a reactant, that decays with a simple chemical reaction, one can analyse the dependence of concentration fluctuations on the Damköhler number. The study is extended to plumes that react nonlinearly. In such reacting systems, the large gradients and segregation of species result in a significant reduction in the reaction rates. Because of this modification, the chemistry of species related to NO_x and HO_x can be very different from the chemistry in conditions where the species are uniformly mixed. The lack of complete observational evidence is hampering our understanding of these processes and our evaluation of numerical modelling results. Finally, we discuss briefly how to represent, in the form of a parameterization, the effect that turbulence can have on the reactivity of species emitted by a point source or an area source.     

Ozone in the Marine Boundary Layer at Cape Grim: Model Simulation

A photochemical box model has been used to simulate the mixing ratio ofozone under conditions reflecting those encountered in the marine boundarylayer at Cape Grim, Tasmania, where a decade-long record of ozone mixingratio is available. The model is based on the proposition that ozone loss byphotolysis, atmospheric reaction with hydroperoxy and hydroxyl radicals, andsurface deposition is balanced by ozone gain via entrainment from the lowerfree troposphere with a small additional source in summer from photolysis ofnitrogen dioxide. This model simulates very well the observed ozone records,reproducing both the small diurnal cycle in ozone mixing ratio observedduring the summer months, and the factor of two seasonal ozone cycle showinga distinct winter maximum and summer minimum. The model result confirms thatunder the low-NO_x conditions of the clean marine boundarylayer net photochemical loss of ozone occurs at all times of year.     

Second-order closure study of the covariance between chemically reactive species in the surface layer

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.     

The dependence of the concentration of OH on its precursors under moderately polluted conditions: A model study

Oxidation of trace gases emitted into the atmosphere is frequently promoted by free radicals. During daytime, the most important radical is the hydroxyl radical, since it reacts with almost all pollutants thereby initializing their ultimate removal from the atmosphere. Since the reaction with OH is in many cases the rate-determining step, the ambient OH concentration is a measure for the atmosphere's oxidation capacity. This paper investigates the influence of the chemical precursors and the photolysis frequencies on the atmospheric OH abundance under moderately polluted and rural conditions. The dominant controlling parameter are the photolysis of ozone and the concentrations of the nitrogen oxides.     

First-Order Chemistry in the Surface-Flux Layer

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.     

云对云中大气臭氧影响因子的分析

应用一个较详细的气相光化学和液相化学耦合的箱体模式, 研究了云层对云中大气臭氧的影响过程。这一过程可分解为三个因子来考虑： 因子Ａ （云的辐射效应）, 由于云的存在改变太阳光辐射通量, 使得对流层光化学反应减弱或增强, 从而降低或增加臭氧浓度; 因子Ｂ（云的吸收效应）, 云层中液态水对大气臭氧及其前体物 （ＮＯｘ、ＮＭＨＣ、自由基等） 的直接吸收作用; 因子Ｃ（云的液相化学效应）, 吸收进入云中的物质发生液相化学反应从而改变大气臭氧浓度。数值研究结果表明： 上述三因子对云中臭氧浓度影响的程度差别很大, 并且与云层的物理结构有密切关系。讨论了云的吸收及液相化学效应影响臭氧浓度的主要原因     

OH-initiated degradation of several hydrocarbons in the atmosphere simulation chamber SAPHIR

Degradation of isoprene, m-xylene, n-octane, propene, and methacrolein by hydroxyl radicals has been studied in the simulation chamber SAPHIR under burden of trace gases as they are typical for the moderately polluted planetary boundary layer. Measured time series of the hydrocarbon mixing ratios and the OH concentrations were used to determine the rate constants. The hydrocarbons were measured with gas chromatography and proton transfer reaction mass spectrometry. OH was measured with the Jülich DOAS (differential optical absorption spectroscopy) instrument. In all cases except methacrolein good agreement was found with the reference rate constants taken from the Master Chemical Mechanism (MCM3.1). The data for methacrolein are consistent with the results of Karl et al. (J. Atmos. Chem 55, 2006, doi:) who reported a 12% smaller value. The degradation of hydrocarbons provides an independent method to analyse precision and accuracy of the OH measurements. A precision of better than 4% over a period of nearly 4 months was found. The accuracy is within the limitations given by the light absorption cross section of OH. Both results are consistent with earlier results by Hausmann et al. (J. Geophys. Res. 102:16011–16022, 1997).     

Differences in the variability of measured and simulated tropospheric ozone mixing ratios over the Paso del Norte Region

The objective of this study is to present differences in the variability of observed and ozone-mixing ratios simulated by a three-dimensional atmospheric chemical model using two chemical mechanisms. In this study the Comprehensive Air Quality Model with Extensions is used to make ozone simulations with the Carbon Bond mechanism, versions 4 and 5. The Paso del Norte region is used as a test-bed for these simulations. The shared variance between the simulations and measurements is typical for air quality models ranging from 0.51 to 0.86 for both mechanisms. The smallest mean normalized gross error is about 31 % with CB4 but the normalized bias is over 30 % as well. Boundary conditions, emissions and other factors affect the levels of ozone of the simulated mixing ratios and therefore error and bias but these factors have a much less affect on the simulated ozone variability. The differences in the ozone variability of the measurements and the simulations are very large and different for the two chemical mechanisms. There are many more instances of low ozone mixing ratios in the measurements than in the simulated ozone. One possible explanation is that these differences are due to problems associated with comparing point measurements with grid averages. A more disturbing possibility is that the bias could be due to the procedures used in the development and testing of air quality modeling systems. Air quality mechanisms are evaluated against environmental chamber data where the chemistry occurs at high concentrations and this may lead to a systematic positive bias in ozone simulations.     

Atmospheric chemistry of hydrogen fluoride

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.     

Downward transport and modification of tropospheric ozone through moist convection

This study estimated the largely unstudied downward transport and modification of tropospheric ozone associated with tropical moist convection using a coupled meteorology-chemistry model. High-resolution cloud resolving model simulations were conducted for deep moist convection events over West Africa during August 2006 to estimate vertical transport of ozone due to convection. Model simulations realistically reproduced the characteristics of deep convection as revealed by the estimated spatial distribution of temperature, moisture, cloud reflectivity, and vertical profiles of temperature and moisture. Also, results indicated that vertical transport reduced ozone by 50% (50 parts per billion by volume, ppbv) in the upper atmosphere (12–15 km) and enhanced ozone by 39% (10 ppbv) in the lower atmosphere (<2 km). Field observations confirmed model results and indicated that surface ozone levels abruptly increased by 10–30 ppbv in the area impacted by convection due to transport by downdrafts from the upper troposphere. Once in the lower troposphere, the lifetime of ozone decreased due to enhanced dry deposition and chemical sinks. Ozone removal via dry deposition increased by 100% compared to non-convective conditions. The redistribution of tropospheric ozone substantially changed hydroxyl radical formation in the continental tropical boundary layer. Therefore, an important conclusion of this study is that the redistribution of tropospheric ozone, due to deep convection in non-polluted tropical regions, can simultaneously reduce the atmospheric loading of ozone and substantially impact the oxidation capacity of the lower atmosphere via the enhanced formation of hydroxyl radicals.     

The Oxidation of Organic Compounds in the Troposphere and their Global Warming Potentials

Oxidation by hydroxyl radicals is the main removal process for organic compounds in the troposphere. This oxidation acts as a source of ozone and as a removal process for hydroxyl and peroxy radicals, thereby reducing the efficiency of methane oxidation and promoting the build-up of methane. Emissions of organic compounds may therefore lead to the build-up of two important radiatively-active trace gases: methane and ozone. Emission pulses of 10 organic compounds were followed in a global 3-D Lagrangian chemistry-transport model to quantify their indirect greenhouse gas impacts through changes induced in the tropospheric distributions of methane and ozone. The main factors influencing the global warming potentials of the 10 organic compounds were found to be their spatial emission patterns, chemical reactivity and transport, molecular complexity and oxidation products formed. The indirect radiative forcing impacts of organic compounds may be large enough that ozone precursors should be considered in the basket of trace gases through which policy-makers aim to combat global climate change.     

Evaluation of the Salicylic Acid—Liquid Phase Scrubbing Technique to Monitor Atmospheric Hydroxyl Radicals

A novel method has been examined for monitoring tropospheric hydroxyl radicals (OH), the most important oxidant in tropospheric chemistry. Aqueous phase salicylic acid reacts with atmospheric OH to produce 2,5-dihydroxy benzoic acid (2,5-DHBA) and other products. High Performance Liquid Chromatography (HPLC) is used to separate the post-reaction solution and the products are quantified using fluorescence detection. Unlike other methods, it has been reported to be inexpensive, portable and relatively simple. Although the sensitivity was sufficient to measure typical daytime OH concentrations of 0.04–0.4 ppt., the method was hindered by numerous interferences. Successive identification and elimination of these still resulted in a signal that was much larger than expected. Tests showed that this was not likely to be due to ozone, HO₂, NOx, H₂O₂, aerosols, light or bacteria. Experimental and numerical studies suggest that the interference could be due to methyl peroxy radicals. The effect of many other components in the atmosphere, both individual and combined, must also be tested before the method can be used reliably in the field. The validity of previous reports of ambient hydroxyl measurements using this technique is therefore brought into question.     

An Algorithm for the Determination of All Significant Pathways in Chemical Reaction Systems

When the output of a complex chemical model is analysed, a typical topic isthe determination of pathways, i.e., reaction sequences, that produce ordestroy a chemical species of interest.A representative example is the investigation of catalytic ozone destruction cycles in the stratosphere.An algorithm for the automatic determination of pathways in any given reactionsystem is presented. Under the assumption that reaction rates are known, it finds all significant pathways, i.e., all pathways with a rate above a prescribed threshold.The algorithm forms pathways step by step, starting from single reactions.The chemical species in the system are consecutively considered as `branching points'.For every branching-point species, each pathway producing it is connected witheach pathway consuming it.Rates proportional to `branching probabilities' are calculated.Pathways with a rate that is smaller than a prescribed threshold arediscarded.If a newly formed pathway contains sub-pathways, e.g., null cycles, it is split into these simpler pathways.In order to demonstrate the performance of the algorithm, it has been applied to the determination of catalytic ozone destruction cycles and methaneoxidation pathways in the stratosphere.     

Role of ozone in the sodium and hydroxyl nightglow

One-dimensional photochemical diffusion model which includes oxygen-hydrogen-sodium atmosphere has been used to examine the relation between sodium and hydroxyl nightglow and the role of ozone in it. It is found that both emissions can be obtained on the basis of photochemistry. The following reactionsNa + O3→NaO + O2 and H + O3 → OH* + O2 play key role in sodium and hydroxyl emission respectively. Further it is found that variations in both emissions are controlled by the variation in the concentration of ozone.     

Urban Atmospheric Chemistry During the PUMA Campaign 2: Radical Budgets for OH,HO<Subscript>2</Subscript> and RO<Subscript>2</Subscript>

A detailed photochemical box model was used to investigate the key reaction pathways between OH, HO₂ and RO₂ radicals during the summer and winter PUMA field campaigns in the urban city-centre of Birmingham in the UK. The model employed the most recent version of the Master Chemical Mechanism and was constrained to 15-minute average measurements of long-lived species determined in situ at the site. The results showed that in the summer, OH initiation was dominated by the reactions of ozone with alkenes, nitrous acid (HONO) photolysis and the reaction of excited oxygen atoms atoms with water. In the winter, ozone+alkene reactions were the primary initiation route, with a minor contribution from HONO photolysis. Photolysis of aldehydes was the main initiation route for HO₂, in both summer and winter. RO₂ initiation was dominated by the photolysis of aldehydes in the summer with a smaller contribution from ozone+alkenes, a situation that was reversed in the winter. At night, ozone+alkene reactions were the main radical source. Termination, under all conditions, primarily involved reactions with NO (OH) and NO₂ (OH and RCO₃). These results demonstrate the importance of ozone+alkene reactions in urban atmospheres, particularly when photolysis reactions were less important during winter and at nighttime. The implications for urban atmospheric chemistry are discussed.     

Turbulent mixing of reactive gases in the convective boundary layer

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.     

In-situ Formation of Light-Absorbing Organic Matter in Cloud Water

Current climate models seem to underestimate the flux of solar energy absorbed by the global troposphere. All of these models are constrained with the assumption that cloud droplets consist of pure water. Here we demonstrate in a simple laboratory experiment that aromatic hydroxy-acids which are found in continental fine aerosol can react with hydroxyl radicals under typical conditions prevalent in cloud water influenced by biomass burning. The reactions yield colored organic species which do absorb solar radiation. We also suggest that the products of such reactions may be humic-like substances whose presence in continental aerosol has been confirmed but their source mechanisms are still much sought after. We also attempt to give a first order estimate of the enhancement of water absorption at a visible wavelength under atmospheric conditions.     

Comparison of the EMEP, RADM2 and RACM Mechanisms

A comparison of the atmospheric chemistry mechanisms EMEP (Co-operative Programme for Monitoring and Evaluation of the Long-Range Transmission of Air Pollutants in Europe), RADM2 (Regional Acid Deposition Model, version 2) and RACM (Regional Atmospheric Chemistry Mechanism) has been conducted. Each mechanism was used to simulate the PLUME case of Kuhn et al. (1998) and to simulate an additional 150 and 81 scenarios with and without emissions, respectively. These simulations covered scenarios that ranged from relatively clean, through rural and polluted urban conditions. Ozone isopleths and scatter plots were generated from the simulations. The mechanisms were compared primarily on the basis of calculated ozone and ozone precursor concentrations. For the gas-phase ozone precursors the differences between the mechanisms were rather small under clean conditions and more significant under polluted conditions. The differences were especially significant for the concentrations of NO₂ and organic peroxy radicals. In general the EMEP mechanism yielded the most ozone and the RADM2 mechanism yielded the least. Furthermore the results suggest that a broad range simulation conditions should be used to compare mechanisms and not just a few selected scenarios.     

我国对流层大气臭氧的数值模拟

本文建立了一个用于对流层大气臭氧模拟的三维欧拉模式,针对影响臭氧光化学转化的各种因素及我国城市光化学污染的特点,模式中简化了光化学项的计算。根据实际观测资料,提出了模拟云雾对臭氧影响的参数化方法,并确定了云雾作用系数,通过模式的数值模拟,得出了我国对流层大气臭氧,特别是近地面层大气臭氧的分布状况、我国城市光化学污染的分布特征以及它们的季节变化规律.     

Tropospheric Ozone in a Global-Scale Three-Dimensional Lagrangian Model and Its Response to NOX Emission Controls

A three-dimensional Lagrangian tropospheric chemistry modelis used toinvestigate the impact of human activities on the tropospheric distributionofozone and hydroxyl radicals. The model describes the behaviour of 50 speciesincluding methane, carbon monoxide, oxides of nitrogen, sulphur dioxide andnineorganic compounds emitted from human activities and a range of other sources.Thechemical mechanism involves about 100 chemical reactions of which 16 arephotochemical reactions whose diurnal dependence is treated in full. The modelutilises a five minute chemistry time step and a three hour advection timestepfor the 50,000 air parcels. Meteorological data for the winds, temperatures,clouds and so on are taken from the UK Meteorological Office global model for1994 onwards. The impacts of a 50% reduction in European NO_Xemissions onglobal ozone concentrations are assessed. Surface ozoneconcentrations decrease in summertime and rise in wintertime, but to differentextents.