对流层大气NO3与N2O5的实地测量

王海潮; 陈军; 陆克定

doi:10.7536/PC141230

化学进展 ›› 2015, Vol. 27 ›› Issue (7) :963-976 DOI: 10.7536/PC141230

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对流层大气NO₃与N₂O₅的实地测量

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Measurement of NO₃ and N₂O₅ in the Troposphere

Wang Haichao¹, Chen Jun², Lu Keding*¹

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摘要

大气硝基(NO₃)自由基和五氧化二氮(N₂O₅)是对流层大气化学反应的核心物种,对于理解大气氧化性、二次有机气溶胶生成、活性卤素化学和全球硫素循环等对流层大气化学研究的关键问题具有重要意义。大气NO₃自由基和N₂O反应活性高、大气寿命短、浓度低,其定量分析非常具有挑战性。本文总结了大气NO₃自由基与N₂O₅的实地测量方法,并对差分光学吸收光谱(DOAS)、腔衰荡光谱(CRDS)、腔增强光谱(CEAS)、激光诱导荧光光谱(LIF)、电子顺磁共振谱(MIESR)和化学离子化质谱(CIMS)等六类技术方法的准确度、精确度、时间分辨率、测量干扰、标定方法和系统稳定性等方面进行了系统比较。综合分析认为吸收光谱法是对流层NO₃自由基与N₂O₅测量技术的发展方向,其中近期发展起来的腔技术(CRDS和CEAS)显示出较好的应用潜力。但是我国实际大气环境中普遍存在高浓度的颗粒物污染,如何在高颗粒物条件下实现NO₃自由基与N₂O₅的精密准确测量具有挑战性。本文进一步归纳了NO₃自由基与N₂O₅在城市、森林、自由大气和海洋海岸等典型大气环境条件下的浓度水平和主要科学发现,探讨了一些亟待解决的问题和可能的重点研究方向。

Abstract

Nitrate radical (NO₃) and dinitrogen pentoxide (N₂O₅) are key species of the tropospheric chemistry, that play a central role in the tropospheric chemical issues such as atmospheric self cleansing capacity, secondary aerosol formations, reactive halogen chemistry, global sulfur cycles, etc. Nevertheless, the accurate and precise determination of both NO₃ and N₂O₅ is still a challenging task due to their low ambient concentrations, high reactivity and short life time. In this paper, we summarize all kinds of measurement techniques used in the field observations of NO₃ and N₂O₅, including differential optical absorption spectroscopy(DOAS), cavity ring-down spectroscopy (CRDS), cavity enhance absorption spectroscopy (CEAS), laser-induced fluorescence(LIF), matrix isolation electron spin resonance spectroscopy(MIESR), and chemical ionization mass spectrometry(CIMS). The advantages and disadvantages of those techniques are reviewed on the aspects of measurement accuracy, precision, time resolution, interference, calibration and operation stability. The absorption spectroscopy is the best technical approach, especially the subcategories——CRDS and CEAS developed in the last decade are the techniques with high potential of good performance in field applications. However, because high aerosol loadings are always presented in the atmosphere of the mega-city regions in China, the aerosol extinction could be a significant barrier to come over for the techniques based on absorption spectroscopy. Moreover, the observed NO₃ and N₂O₅ concentrations and the major scientific findings of corresponding measurement campaigns conducted in typical tropospheric conditions as urban, forest, free troposphere and marine environments, etc. are outlined. Finally, we discuss the unresolved issues of the NO₃ and N₂O₅chemistry and possible new directions for future studies in chemically complex environments.

Contents
1 Introduction
2 Measurement techniques of tropospheric nitrate radical (NO₃) and dinitrogen pentoxide (N₂O₅)
2.1 Absorption spectroscopy
2.2 Fluorescence methods
2.3 Mass spectrometric methods
2.4 Paramagnetic resonance spectroscopy
2.5 Calibrations
3 Field measurement of nitrate radical and dinitrogen pentoxide
4 Conclusion and outlook

Graphical abstract

关键词

大气硝基自由基 / 五氧化二氮 / 实地测量 / 测量技术 / 化学机理

Key words

nitrate radical (NO₃) / dinitrogen pentoxide (N₂O₅) / field measurement / measurement techniques / chemical mechanism

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王海潮, 陈军, 陆克定. 对流层大气NO₃与N₂O₅的实地测量[J]. 化学进展, 2015, 27(7): 963-976 DOI:10.7536/PC141230

Wang Haichao, Chen Jun, Lu Keding. Measurement of NO₃ and N₂O₅ in the Troposphere[J]. Progress in Chemistry, 2015, 27(7): 963-976 DOI:10.7536/PC141230

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