A Common Representative Intermediates (CRI) mechanism for VOC degradation. Part 1: Gas phase mechanism development
A Common Representative Intermediates (CRI) mechanism for VOC degradation. Part 1: Gas phase mechanism development
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DOI：
10.1016/j.atmosenv.2008.07.028
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发表时间：
2008-10-01
影响因子：
5
通讯作者：
Shallcross, D. E.
中科院分区：
文献类型：
--
作者：
Jenkin, M. E.;Watson, L. A.;Shallcross, D. E.
一个简化的机制，描述臭氧形成的对流层降解的甲烷和115排放的非甲烷碳氢化合物和氧化挥发性有机化合物已经开发，使用主化学机制版本3.1（MCM v3.1）作为参考基准。通用代表性中间体机制版本2（CRI v2）是在化合物的基础上建立的，通过与MCM v3.1进行比较，使用一系列五天箱模型模拟，依次优化了每种化合物的化学性能。由此产生的机制包含434种化学物质的1183个反应，即，约MCM v3.1中降解同一组VOC的反应和物种数量的10%。类似于CRI vl（Jenkin等人，2002 a），CRI Q构建方法中的一个关键假设是，给定挥发性有机化合物（VOC）形成臭氧的可能性与反应性（即，C-C和C-H）键。该指数允许定义一系列通用中间体，每个中间体都被用作具有相同指数的大量物种的“共同代表”，如在详细机制（如MCM）中形成的。CRI Q的性能被证明可以与MCM 0.1的性能进行很好的比较，在广泛的环境条件下，考虑在人为和生物源VOC的VOC/NOx排放比分别在32和400的范围内变化，在箱模型模拟;在英国南部使用光化学轨迹模型对2003年火炬运动进行的模拟中，它考虑了氮氧化物和挥发性有机化合物的相对和绝对排放量的显著范围，以及人为和生物物种对挥发性有机化合物总量的相对贡献。CRI Q是一种中间复杂度的简化机制，可追溯到MCM v3.1，并为进一步的系统化简化提供了基础。两个配套文件考虑通过排放集总和相关SOA模块的开发和评估进一步降低CRI Q。(c)2008爱思唯尔有限公司保留所有权利。
A reduced mechanism describing ozone formation from the tropospheric degradation of methane and 115 emitted non-methane hydrocarbons and oxygenated volatile organic compounds has been developed, using the Master Chemical Mechanism version 3.1 (MCM v3.1) as a reference benchmark. The Common Representative Intermediates mechanism version 2 (CRI v2) has been built up on a compound-by-compound basis, with the performance of its chemistry optimised for each compound in turn by comparison with that of MCM v3.1, using a series of five-day box model simulations. The resultant mechanism contains 1183 reactions of 434 chemical species, i.e., ca. 10% of the number of reactions and species to degrade the same set of VOCs in MCM v3.1. Similarly to CRI v1 (Jenkin et al., 2002a), a key assumption in the CRI Q construction methodology is that the potential for ozone formation from a given volatile organic compound (VOC) is related to the number of reactive (i.e., C-C and C-H) bonds it contains. This index allows a series of generic intermediates to be defined, with each being used as a "common representative" for a large set of species possessing the same index, as formed in detailed mechanisms such as the MCM. The performance of CRI Q is shown to compare well with that of MCM 0.1 for a wide range of ambient conditions, which consider variations in VOC/NOx emissions ratio over ranges of 32 and 400 for anthropogenic and biogenic VOCs, respectively, in box model simulations; and in simulations of the TORCH 2003 campaign in the southern UK using a photochemical trajectory model, which considers notable ranges in the relative and absolute emissions of NOx and VOCs, and in the relative contributions of anthropogenic and biogenic species to the VOC total. CRI Q is a reduced mechanism of intermediate complexity, which is traceable to MCM v3.1, and which provides the basis for further systematic reduction. Two companion papers consider further reduction of CRI Q through emissions lumping and development and assessment of an associated SOA module. (c) 2008 Elsevier Ltd. All rights reserved.