Determination of Dominant Pathways in Chemical Reaction Systems: An Algorithm and Its Application to Stratospheric Chemistry

The analysis of complex chemical reaction systems is frequently complicatedbecause of the coexistence of fast cyclic reaction sequences and slower pathways that yield a net production or destruction of a certain species of interest.An algorithm for the determination of both these types of reaction sequences (in a given reaction system) is presented. Under the assumption that reaction rates are known, it finds the mostimportant pathways by solving a linear optimization problem for each of them.This algorithm may be used as a tool for the interpretation of chemical model runs.For illustration, it is applied to examples in stratospheric chemistry, including the determination of catalytic ozone destruction cycles.     

Estimates of the Chemical Budget for Ozone at Waliguan Observatory

Waliguan Observatory (WO) is an in-land Global Atmosphere Watch (GAW) baseline station on the Tibetan plateau. In addition to the routine GAW measurement program at WO, measurements of trace gases, especially ozone precursors, were made for some periods from 1994 to 1996. The ozone chemical budget at WO was estimated using a box model constrained by these measured trace gas concentrations and meteorological variables. Air masses at WO are usually affected by the boundary layer (BL) in the daytime associated with an upslope flow, while it is affected by the free troposphere (FT) at night associated with a downslope flow. An anti-relationship between ozone and water vapor concentrations at WO is found by investigating the average diurnal cycle pattern of ozone and water vapor under clear sky conditions. This relationship implies that air masses at WO have both the FT and BL characteristics. Model simulations were carried out for clear sky conditions in January and July of 1996, respectively. The chemical characteristics of mixed air masses (MC) and of free tropospheric air masses (FT) at WO were investigated. The effects of the variation in NO_x and water vapor concentrations on the chemical budget of ozone at WO were evaluated for the considered periods of time. It was shown that ozone was net produced in January and net destroyed in July for both FT and MC conditions at WO. The estimated net ozone production rate at WO was –0.1 to 0.4 ppbv day^–1 in FT air of January, 0.0 to 1.0 ppbv day^–1 in MC air of January, –4.9 to –0.2 ppbv day^–1 in FT air of July, and –5.1 to 2.1 ppbv day^–1 in MC air of July.     

青藏高原夏季臭氧低谷形成的机理-臭氧输送和化学过程

利用三维化学输送模式(OSLO CTM2)模拟青藏高原夏季臭氧低谷。结果表明：在青藏高原夏季臭氧低谷的形成和变化过程中，动力输送过程起着最主要作用，化学过程部分补偿了输送过程引起的臭氧减少。在动力输送过程中，水平输送在5月份是造成臭氧减少的主要原因，可在6月和7月成为使臭氧增加；垂直平流的作用不断增强，在6月和7月成为臭氧减少的主要因素；对流输送的作用在7月份大幅增加，其引起的臭氧减少可以与净的变化相比，其作用也不可忽视。气相的化学过程引起的臭氧增加的量值有时超过了臭氧的净变化的大小，因此它也起着重要作用。     

关中盆地近地面风场和大气输送特征分析

利用2017年151个地面气象站的逐时观测数据和相关高空资料分析关中盆地近地面风场与输送特征。首先分析盆地内代表性站点的风速和风向观测事实,然后用CALMET风场诊断模式和轨迹计算模式获取当地逐小时风场和每日逐小时传输轨迹,分析风场类型。结果表明:关中盆地内日平均风速约1～3 m s?1,夏季风速高、秋冬季低;盆地中央的主导风向以沿地形走向的东北风和西南风为主,盆地四周测站的主导风向表现出顺着地形向盆地中央汇流的趋势。各站主导风向的季节变化不大。盆地内风场分为系统控制型、弱天气背景型和局地环流型3类,全年出现日数比例分别占8%、17.3%和74.7%。以山谷风日夜循环为特征的局地环流型风场最多。以西安城区为源点的大气输送轨迹显示,系统控制型风场以偏东北方向的输送为主,弱天气背景型和局地环流型风场的轨迹输送都大致以偏东北和偏西（以及偏西南）沿盆地走向以及偏东南朝向秦岭山地这三个方向为主。局地环流型的轨迹影响范围小,集中于盆地中央和南侧山地之间,表明这是一种不利于污染扩散的风场类型。     

The Effect of Temperature and Humidity on the Reaction of Ozone with Combustion Soot: Implications for Reactivity near the Tropopause

The effect of temperature (296–238 K) on the reaction of combustion soot (n-hexane) with ozone at low concentration (6–8 ppm) has been measured. Long optical path FTIR spectroscopy has revealed the rate law for ozone loss beyond initial stages, second order in O₃, to be the same over this range of conditions. The reaction rate is 3.5 times lower at 238 K than at 296 K, and reveals an activation energy of 12.9 ± 0.5 kJ mol^–1. The effect of humidity on the reaction has been estimated using its recently determined rate law dependence (p^0.2). These data, differing from O₃ reaction kinetics obtained from other types of carbonaceous particles used as surrogates for atmospheric soot, have implications for the role of combustion soot in atmospheric chemistry. Any involvement of aircraft soot in ozone depletion near the tropopause, for example, should be estimated using these temperature and humidity dependences.     

The Measurement of Active Chlorine in the Atmosphere by Chemical Amplification

Chemical amplification, CA, a method commonly used for the detection of peroxy radicals, HO₂ and RO₂, was found to be sensitive towards ClOx (Cl+ClO+OClO) as well. ClOx is reduced by NO to Cl atoms which react with carbon monoxide in the presence of O₂. The reaction sequence thus initiated oxidizes CO to CO₂ and NO to NO₂, with a chain length of 300 ± 60. This allows the atmospheric ClOx content to be measured under ambient conditions with a detection limit of better than 1 ppt. In parallel peroxy radicals are indicated with a chain length of 160 ± 15. Chemical amplification is not specific and does not indicate which radical chain it is seeing. Identification relies solely on plausibility. During the ARCtic Tropospheric Ozone Chemistry (ARCTOC) campaign in spring 1995 and 1996 the CA technique was used at Ny-Ålesund. ClOx at mixing ratios of up to 2 ppt were found in the boundary layer under certain conditions. The low concentrations of ClOx indicate that the arctic boundary ozone depletion is mainly driven by bromine.     

Laboratory Studies of Bromide Oxidation in the Presence of Ozone: Evidence for a Glass-Surface Mediated Reaction

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.     

The Role of Multiphase Chemistry in the Oxidation of Dimethylsulphide (DMS). A Latitude Dependent Analysis

A kinetic model for the OH-initiated homogeneous gas phase oxidation of dimethylsulfide (DMS) in the atmosphere (Saltelli and Hjorth, 1995), has been extended here to include the liquid phase chemistry. The updated model has then been employed to predict the temperature dependency of the MSA/nss-SO42- ratio. Model predictions have been compared with observational data reported in Bates et al. (1992). Sensitivity and uncertainty analysis has been performed in a Monte Carlo fashion to identify which are the important uncertainties on the input parameters and which are the possible combinations of parameter values that could explain the field observations. Results of the analysis have indicated that the temperature dependencies of the interactions between gas phase and liquid phase chemistry may to a large extent explain the observed T-dependence of the MSA/nss- SO42- ratio. The potential role of multi-phase atmospheric chemistry, not only in the case of SO2 but also of other oxidation products of DMS and, particularly, of DMS itself, has been highlighted.