化学学报 ›› 2024, Vol. 82 ›› Issue (3): 323-335.DOI: 10.6023/A23100460 上一篇    下一篇

综述

大气烷基硝酸酯的实地测量

李春萌a, 毕哲a, 王海潮b,*(), 陆克定c,d,*()   

  1. a 中国计量科学研究院 环境计量中心 北京 100029
    b 中山大学大气科学学院 珠海 519082
    c 北京大学环境科学与工程学院 环境模拟与污染控制国家重点联合实验室 北京 100871
    d 国家环境保护大气臭氧污染防治重点实验室 北京 100871
  • 投稿日期:2023-10-23 发布日期:2024-01-04
  • 作者简介:

    李春萌, 中国计量科学研究院环境计量中心博士后, 研究方向为大气痕量物种标准物质研发和以有机硝酸酯为代表的大气化学研究.

    毕哲, 中国计量科学研究院环境计量中心副研究员, 研究方向包括气体计量、仪器开发和校准, 致力于开发用于臭氧/PM2.5前体监测的挥发性有机化合物气体标准, 并逐步开展温室气体、室内空气质量和呼出气体监测等相关领域的研究.

    王海潮, 中山大学大气科学学院副教授, 研究方向为大气测量技术和大气污染成因研究.

    陆克定, 研究员、博士生导师. 主要研究方向为大气环境化学和减污降碳协同防控策略, 基于自由基及其关键前体物的直接观测和动力学模拟等研究手段, 关注典型城市环境中大气自由基的来源和转化以及相应大气化学机理的研发. 曾获得国家自然科学基金优秀青年科学基金(2015)、北京市科技新星(2015)、国家环境保护专业技术青年拔尖人才(2016)、长江学者青年项目(2017)、北京市杰出青年基金项目(2019)及国家杰出青年基金项目(2023), 获得教育部自然科学奖一等奖(2017)和中国环境学会青年科学家奖金奖(2019)等.

  • 基金资助:
    国家自然科学基金(21976006); 国家自然科学基金(42175111); 广东省基础与应用基础研究基金(2020B0301030004); 中国计量科学研究院探索性创新项目(AKYCX2313)

Field Measurement of Alkyl Nitrates in the Atmosphere

Chunmeng Lia, Zhe Bia, Haichao Wangb(), Keding Luc,d()   

  1. a Center for Environmental Metrology, National Institute of Metrology, Beijing 100029
    b School of Atmospheric Sciences, Sun Yat-sen University, Zhuhai, 519082
    c State Key Joint Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing 100871
    d State Key Laboratory of Environmental Protection Atmospheric Ozone Pollution Control, Beijing 100871
  • Received:2023-10-23 Published:2024-01-04
  • Contact: *E-mail: wanghch27@mail.sysu.edu.cn;k.lu@pku.edu.cn
  • Supported by:
    National Natural Science Foundation of China(21976006); National Natural Science Foundation of China(42175111); Guangdong Major Project of Basic and Applied Basic Research(2020B0301030004); Exploratory Innovation Project of National Institute of Metrology, China(AKYCX2313)

烷基硝酸酯(ANs)是对流层大气中重要的污染物, 其收支过程对大气氮、碳的分布, 光化学循环以及二次有机气溶胶生成等具有重要影响. 大气ANs种类繁多, 浓度低且化学性质活泼, 因此ANs的准确测量是大气监测领域的巨大挑战. 概述了大气ANs化学机理, 系统梳理并总结了ANs单物种和总量的实地测量技术进展, 主要包括气相色谱电子捕获技术、质谱技术、荧光光谱技术和吸收光谱技术. 研究表明吸收光谱技术具有结构简单易维护的特征, 是具有较大发展潜力的ANs总量测量方法, 质谱技术在ANs分物种测量方面具有其独特优势, 但物种化的标准源和标定技术是亟待突破的关键瓶颈. 最后, 系统归纳了不同环境类型的ANs浓度分布特征, 并对ANs化学研究难点和发展趋势进行展望.

关键词: 烷基硝酸酯, 化学机理, 单物种测量, 总量测量, 实地测量

Alkyl nitrates (ANs), chemicals with the formula RONO2, are important oxidation products during the reaction between atmospheric nitrogen oxides (NOx) and volatile organic compounds (VOCs). The generation of ANs removes NOx from the atmosphere, and inhibits atmospheric oxidation by terminating the HOx cycle. Some ANs are easily taken up by particulate, as important precursors of secondary organic aerosols, thereby affecting atmospheric air quality and global climate change. Atmospheric model simulations and field campaigns have shown that ANs are important for local complex pollution and nitrogen cycling. However, as ANs are widely distributed in the atmosphere, with a wide variety and active chemical properties, it makes the field measurements of ANs very scarce due to the lack of measurement methods and standard substances. In this study, firstly, the atmospheric chemical mechanism focused on ANs is introduced, and then the measurement techniques for single species and total ANs are summarized, which mainly include gas chromatography electron capture (GC-ECD), mass spectrometry (MS), thermal dissociation laser-induced fluorescence (TD-LIF) and absorption spectrometry. Overall, mass spectrometry is an important development direction for single-species measurement methods of ANs, while absorption spectroscopy is an emerging total measurement method with great development potential. Field measurements of ANs were carried out mainly in Europe and the United States. However, the atmospheric environment of high NOx and high anthropogenic VOCs in China is different from that of low NOx and high biogenic VOCs in Europe and the United States, and thus there are differences in the atmospheric distributions of ANs, which introduces challenge for field measurements of ANs. Finally, the distribution characteristics of ANs in the environments of ocean, forest, city, and free atmosphere in the troposphere are summarized, and an outlook on the difficulties and development trends of ANs chemistry at present is given, which will provide a reference for the development of the measurement technology and the research on the chemical mechanism of ANs in China.

Key words: alkyl nitrate (AN), chemical mechanism, single-species measurement, total measurement, field measurement