Ambient photolysis frequency of NO<sub>2</sub> determined using chemical actinometer and spectroradiometer at an urban site in Beijing

doi:10.1007/s11783-016-0885-3

Front. Environ. Sci. Eng.

2016, Vol. 10

Issue (6) : 13 https://doi.org/10.1007/s11783-016-0885-3

RESEARCH ARTICLE

Ambient photolysis frequency of NO₂ determined using chemical actinometer and spectroradiometer at an urban site in Beijing

Qi Zou,Keding Lu(

),Yusheng Wu,Yudong Yang,Zhuofei Du,Min Hu

State Key Joint Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing 100871, China

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Abstract

• Chemical actinometer (CA) was built for NO₂ photolysis frequency, j(NO₂), analysis.

• CA data (10% accuracy) were compared with spectroradiometer (SR) data.

• Long-term j(NO₂) measurement was validated by comparison of CA and SR.

• Dis-benefit of aerosol on j(NO₂) due toparticulate matter (PM_2.5) control on O₃.

The photolysis frequency of NO₂, j(NO₂), is an important analytical parameter in the study of tropospheric chemistry. A chemical actinometer (CA) was built to measure the ambient j(NO₂) based on a high precision NO_x instrument with 1 min time resolution. Parallel measurements of the ambient j(NO₂) by using the CA and a commercial spectroradiometer (SR) were conducted at a typical urban site (Peking University Urban Environmental Monitoring Station) in Beijing. In general, good agreement was achieved between the CA and SR data with a high linear correlation coefficient (R² = 0.977) and a regression slope of 1.12. The regression offset was negligible compared to the measured signal level. The j(NO₂) data were calculated using the tropospheric ultraviolet visible radiation (TUV) model, which was constrained to observe aerosol optical properties. The calculated j(NO₂) was intermediate between the results obtained with CA and SR, demonstrating the consistency of all the parameters observed at this site. The good agreement between the CA and SR data, and the consistency with the TUV model results, demonstrate the good performance of the installed SR instrument. Since a drift of the SR sensitivity is expected by the manufacturer, we propose a regular check of the data acquired via SR against those obtained by CA for long-term delivery of a high quality series of j(NO₂) data. Establishing such a time series will be invaluable for analyzing the long-term atmospheric oxidation capacity trends as well as O₃ pollution for urban Beijing.

Keywords Photolysis frequency of nitrogen dioxide Chemical actinometer Spectroradiometer Tropospheric ultraviolet visible radiation model

Corresponding Author(s): Keding Lu

Issue Date: 14 November 2016

Cite this article:

Qi Zou,Keding Lu,Yusheng Wu, et al. Ambient photolysis frequency of NO₂ determined using chemical actinometer and spectroradiometer at an urban site in Beijing[J]. Front. Environ. Sci. Eng., 2016, 10(6): 13.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-016-0885-3
https://academic.hep.com.cn/fese/EN/Y2016/V10/I6/13

Fig.1 Schematic of setup of the actinometry (a) and spectroradiometry (b) instruments at Peking University Urban Environmental Monitoring Station

Fig.2 j(NO₂) data from actinometer, obtained on April 26thusing NO and NO_x signals under different conditions (red dots denote the measuring mode; black dots denote the background mode, where the photolysis cell was covered with aluminum foil)

Fig.3 j(NO₂) observed by CA (red dots) and SR (blue dots) from April 24 th to May 1st 2014. TUV model data for j(NO₂) are also indicated by black line

Fig.4 Regression analysis of the 10 min average j(NO₂) values observed in parallel using CA and SR. linear square fitting was performed with the “fitexy” procedure [26] to account for errors on both x and y axes. Linear regression results are shown as red line and the 1:1 ratio as blue dashed line. The error bar indicates 1s standard deviation of j(NO₂) data acquired with CA and SR instruments within the 10 min time window used for the regression analysis

Fig.5 Relative deviation of observed j(NO₂) from CA and SR analyses versus solar zenith angle (SZA)

Fig.6 Comparison of experimental and modeled values of j(NO₂) for data acquired on April 26th. Experimental data are indicated by red line (for CA) and blue line (for SR). TUV model data constrained by detailed observation of aerosol properties are shown as black line (TUV-detail). TUV model data constrained by daytime average aerosol properties are shown as violet line (TUV-mean). The TUV model results with standard set up, representing clean environment, are shown as pink line (TUV-clean)

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