基于腔衰荡光谱技术（CRDS）对大气总活性氮氧化物（NO<sub><em>y</em></sub>）的实时测量

doi:10.3964/j.issn.1000-0593(2020)06-1661-07

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Abstract Nitrogen oxide, being one of an important trace gas in the atmosphere, may affect the oxidation of the atmosphere, harm the physiological health of the human beings and the animals, and cause photochemical smog, haze, acid depositions and other environmental problems. In recent years, with the rapid development of the economy and the continuous increase of energy consumption in our country, the nitrogen oxide emissions have been remaining at a high level. Therefore, it is of great significance to study the content and chemical properties of the nitrogen oxides in the atmosphere. The methods for determining NO_x has tended to become diversified. However, the methods for determining the total reactive nitrogen oxide (NO_y) have always been dominated by the catalytic conversion chemiluminescence (CL). In this paper, a method of simultaneous measurement of NO₂ and NO_y concentration in the ambient air by the thermal dissociation cavity ring down spectrometer (TD-CRDS) is introduced. The performance of the pyrolysis device was optimized, the effective absorption cross section of NO₂ was determined, the interferences which may possibly exist in the system (H₂O, glyoxal, NH₃, N₂O and etc. ) was analyzed, and the detection limit (NO₂ chamber: 8.72×10⁸ molecules·cm^-3; NO_y chamber: 9.71×10⁸ molecules·cm^-3) and the errors (NO₂ measurement: 5%；NO_y measurement: 12%) were discussed. In order to verify the performance of the system, the concentration of NO₂ was determined by comparing the CRDS and the long-path differential optical absorption spectroscopy (LP-DOAS) synchronously, with a linear correlation factor r=0.960. The concentration of NO_y in the atmosphere was determined through comparing with the model Model 42i-NO_y analyzer synchronously, with a linear correlation factor r=0.968. Both consistencies is good. A field experiment was performed for a week at Hefei Science Island. During the measurement, the average concentrations of NO₂ and NO_y were 4.11×10¹² molecules·cm^-3 and 7.73×10¹² molecules·cm^-3, respectively. According to the average daily variation diagram, it is found that there is a similar trend in the concentration of NO₂ and NO_y, and it usually starts to decline at 10:00 and the lowest value occurs at 15:00. Because of its high sensitivity and high time resolution, the CRDS has become a new and simple method for determining the total reactive nitrogen oxide in the ambient air.

Key words：Cavity ring down spectrometer; Thermal dissociation; NO₂; NO_y; Catalytic conversion chemiluminescence

Received: 2019-04-03 Accepted: 2019-08-09

ZTFLH:

O433.1

Corresponding Authors: HU Ren-zhi E-mail: rzhu@aiofm.ac.cn

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https://www.gpxygpfx.com/EN/10.3964/j.issn.1000-0593(2020)06-1661-07 OR https://www.gpxygpfx.com/EN/Y2020/V40/I06/1661

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