Photochemical indicators of ozone sensitivity: application in the Pearl River Delta, China

doi:10.1007/s11783-016-0887-1

Front. Environ. Sci. Eng.

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Issue () : 15 https://doi.org/10.1007/s11783-016-0887-1

RESEARCH ARTICLE

Photochemical indicators of ozone sensitivity: application in the Pearl River Delta, China

Lyumeng Ye¹,Xuemei Wang²(

),Shaofeng Fan³,Weihua Chen¹,Ming Chang¹,Shengzhen Zhou²,Zhiyong Wu¹,Qi Fan²

¹. School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275, China
². School of Atmospheric Sciences, Sun Yat-Sen University, Guangzhou 510275, China
³. Guangzhou Research Institute of Environmental Protection, Guangzhou 510620, China

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Abstract

The distribution of NO_x- and VOC-sensitive regimes in the PRD are identified.

The effectiveness of six popular chemical indicators for discriminating O₃ sensitivity regimes is evaluated.

Threshold levels for HCHO/NO_y, H₂O₂/HNO₃, O₃/NO_y, O₃/NO_z, O₃/HNO₃ were derived and verified.

The indicators H₂O₂/HNO₃ and H₂O₂/NO_z performed best and maintained relatively stable threshold levels.

Surface O₃ production has a highly nonlinear relationship with its precursors. The spatial and temporal heterogeneity of O₃-NO_x-VOC-sensitivity regimes complicates the control- decision making. In this paper, the indicator method was used to establish the relationship between O₃ sensitivity and assessment indicators. Six popular ratios indicating ozone-precursor sensitivity, HCHO/NO_y, H₂O₂/HNO₃, O₃/NO_y, O₃/NO_z, O₃/HNO₃, and H₂O₂/NO_z, were evaluated based on the distribution of NO_x- and VOC-sensitive regimes. WRF-Chem was used to study a serious ozone episode in fall over the Pearl River Delta (PRD). It was found that the south-west of the PRD is characterized by a VOC-sensitive regime, while its north-east is NO_x-sensitive, with a sharp transition area between the two regimes. All indicators produced good representations of the elevated ozone hours in the episode on 6 November 2009, with H₂O₂/HNO₃ being the best indicator. The threshold sensitivity levels for HCHO/NO_y, H₂O₂/HNO₃, O₃/NO_y, O₃/NO_z, O₃/HNO₃, and H₂O₂/NO_z were estimated to be 0.41, 0.55, 10.2, 14.0, 19.1, and 0.38, respectively. Threshold intervals for the indicators H₂O₂/HNO₃, O₃/NO_y, O₃/NO_z, O₃/HNO₃, and H₂O₂/NO_z were able to identify more than 95% of VOC- and NO_x-sensitive grids. The ozone episode on 16 November 16 2008 was used to independently verify the results, and it was found that only H₂O₂/HNO₃ and H₂O₂/NO_z were able to differentiate the ozone sensitivity regime well. Hence, these two ratios are suggested as the most appropriate indicators for identifying fall ozone sensitivity in the PRD. Since the species used for indicators have seasonal variation, the utility of those indicators for other seasons should be investigated in the future work.

Keywords Ozone Pearl River Delta (PRD) Sensitivity regime Photochemical indicator Threshold levels

Corresponding Author(s): Xuemei Wang

Issue Date: 25 November 2016

Cite this article:

Lyumeng Ye,Xuemei Wang,Shaofeng Fan, et al. Photochemical indicators of ozone sensitivity: application in the Pearl River Delta, China[J]. Front. Environ. Sci. Eng., 0, (): 15.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-016-0887-1
https://academic.hep.com.cn/fese/EN/Y0/V/I/15

Tab.1 Verification statistics for meteorological elements and pollutants

Fig.1 (a) The model domain; (b) Monitoring sites. Meteorological stations are marked as solid black dots, and air quality monitoring stations are marked as solid red triangles

Tab.2 Experimental settings for sensitivity testing of anthropogenic emission sources

Fig.2 Predicted surface ozone response to 25 % reduction in emissions of anthropogenic VOCs (green circles), and anthropogenic NO_x (orange crosses): (a) HCHO/NO_y; (b) H₂O₂/HNO₃; (c) O₃/NO_y; (d) O₃/NO_z; (e) O₃/HNO₃; and (f) H₂O₂/NO_z

Fig.3 Predicted surface ozone response to 25 % increase in emissions of anthropogenic VOCs (green circles), and anthropogenic NO_x (orange crosses): (a) HCHO/NO_y; (b) H₂O₂/HNO₃; (c) O₃/NO_y; (d) O₃/NO_z; (e) O₃/HNO₃; and (f) H₂O₂/NO_z

Fig.4 Distributions of surface 3-km grid cells under NO_x-sensitive and VOC-sensitive conditions for the period 13–16 LST, November 6, 2009: (a) HCHO/NO_y; (b) H₂O₂/HNO₃; (c) O₃/NO_y; (d) O₃/NO_z; (e) O₃/HNO₃; and (f) H₂O₂/NO_z

Tab.3 Uncertainty estimation for chemical indicators used to identify NO_x- and VOC-sensitive surface grids

Fig.5 Surface O₃ sensitivity over the Pearl River Delta (PRD) for the period 13–16 LST, November 9, 2009, based on: (a) Model sensitivity test results; (b) H₂O₂/HNO₃indicator ratio with a threshold of 0.55

Tab.4 Distribution of six indicator ratios for NO_x- and VOC-sensitive conditions

Fig.6 Surface O₃ sensitivity regimes, based on the chemical indicator threshold levels in Table 5, and model sensitivity, resulting from a 25 % reduction over the Pearl River Delta (PRD) for the period 13–16 LST, November 16, 2008: (a) H₂O₂/HNO₃; (b) O₃/NO_y; (c) O₃/NO_z; (d) O₃/HNO₃; (e) H₂O₂/NO_z; and (f) model sensitivity

Tab.5 Uncertainty estimation for five chemical indicator ratios using the threshold data in Table 4 to identify NO_x- and VOC-sensitive surface cells, for the period 13–16 LST, November 16, 2008

Fig.7 Distributions of surface 3-km grid cells under NO_x-sensitive and VOC-sensitive conditions for the period 13–16 LST on November 6, 2009, and November 16, 2008: (a) H₂O₂/HNO₃; (b) O₃/NO_y; (c) O₃/NO_z; (d) O₃/HNO₃; (e) H₂O₂/NO_z

Fig.8 Trends in NO₂ and O₃ for (a) the Pearl River Delta (PRD); and (b) Foshan city

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