Analysis of radical propagation efficiency to assess ozone sensitivity to hydrocarbons and NO x : 2. Long‐lived species as indicators of ozone concentration sensitivity
Analysis of radical propagation efficiency to assess ozone sensitivity to hydrocarbons and NO x : 2. Long‐lived species as indicators of ozone concentration sensitivity
复制标题
DOI：
10.1029/1999jd900372
复制
发表时间：
2000-04
影响因子：
--
通讯作者：
G. Tonnesen;R. Dennis
中科院分区：
文献类型：
--
作者：
G. Tonnesen;R. Dennis
我们在一个简单的轨迹模型中对自由基传播效率和OH链长度进行了分析，提出了长寿命物种的组合，以区分臭氧浓度（[O3]）受nox限制和自由基限制的条件。我们在三维网格模型中进一步检查了这些指标。我们提出了几个新的指标，包括[H2O2]/([O3]+[NO2]), [O3]/[NOx]，以及使用NO2和碳氢化合物的OH速率常数加权浓度的测量。我们的分析还支持使用其他研究人员先前提出的几个指标，包括[O3]/[HNO3]和[H2O2]/[HNO3]。我们发现[HCHO]/[NO2]比之前提出的[HCHO]/[NOy]更有用。我们发现，这些指标很容易区分极端氮氧化物限制或极端自由基限制制度，但不能可靠地区分更接近这两种制度之间过渡的条件。我们建议，利用光化学模型模拟和大量的[O3]敏感性指标和对VOC和NOx的局部奇氧生成（P(Ox)）敏感性指标进行组合分析，可以提供最完整和有用的[O3]敏感性描述。指标的时间序列，至少从上午到下午晚些时候，提供了关于白天[O3]敏感性演变的有用信息。指标值的变化取决于[O3]水平，部分原因是各种OH和HO2终止反应的影响以及HC混合物的组成对P（Ox）的影响。需要使用建模研究、测量和NOx或VOC排放变化的测试案例来进一步评估这些指标，以确定它们区分NOx和自由基限制条件的可靠性。
We used an analysis of radical propagation efficiency and OH chain length in a simple trajectory model to propose combinations of long-lived species that distinguish conditions in which O3 concentration ([O3]) is NOx-limited and radical-limited. We further examined these indicators in a three-dimensional grid model. We proposed several new indicators including [H2O2]/([O3]+[NO2]), [O3]/[NOx], and a measure using the OH rate constant weighted concentrations of NO2 and hydrocarbons. Our analysis also supports the use of several indicators previously proposed by other researchers, including [O3]/[HNO3] and [H2O2]/[HNO3]. We found that [HCHO]/[NO2] was more useful than the previously proposed [HCHO]/[NOy]. We found that the indicators easily distinguished extremely NOx-limited or extremely radical-limited regimes but did not reliably distinguish conditions closer to the transition between these two regimes. We propose that a combined analysis using photochemical model simulations and a large set of indicators of both [O3] sensitivity and local odd oxygen production (P(Ox)) sensitivity to VOC and NOx provides the most complete and useful description of [O3] sensitivity. Time series of the indicators, at least from mid-morning to late afternoon, provide useful information about the evolution of [O3] sensitivity during the day. Values of the indicators change depending on the [O3] level due in part to the effects of miscellaneous OH and HO2 termination reactions and to the effects of the composition of the HC mixture on P(Ox). Further evaluation of these indicators using modeling studies, measurements, and test cases with NOx or VOC emissions changes are needed to determine how reliably they distinguish NOx-and radical-limited conditions.