Experimental and kinetic model evaluation of HONO production from surface nitrate photolysis

Wang, Youfeng; Wang, Jianshu; Wang, Yaru; Zhang, Yingjie; Woodward-Massey, Robert; Zhang, Chong; Yu, Keming; Zhu, Jiasong; Shang, Jing; Li, Xin; Zeng, Limin; Lin, Weili; Ye, Chunxiang

doi:10.1016/j.atmosenv.2022.119568

Cited by 11 publications

(17 citation statements)

References 58 publications

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“…Cooking events can lead to an immediate increase in indoor HONO mixing ratios, peaking at around 100 ppbv ( 127 – 130 ). Indoor surfaces, including materials like gypsum, kaolinite, painted walls ( 131 , 132 ), and even the presence of grimes ( 18 , 133 ) and microbial films ( 134 ) covering these surfaces, facilitate the development of conducive environments for photo-enhanced heterogeneous reactions involving NO 2 ( 135 ), as well as the photolysis of pNO 3 - ( 136 ). As a result, HONO is continuously released over an extended period ( 137 ).…”

Section: Discussionmentioning

confidence: 99%

Unveiling the underestimated direct emissions of nitrous acid (HONO)

Zhang,

Liu,

Wang

et al. 2023

Proc. Natl. Acad. Sci. U.S.A.

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Gaseous nitrous acid (HONO) is a critical source of hydroxyl radicals (OH) in the troposphere. While both direct and secondary sources contribute to atmospheric HONO, direct emissions have traditionally been considered minor contributors. In this study, we developed δ 15 N and δ 18 O isotopic fingerprints to identify six direct HONO emission sources and conducted a 1-y case study on the isotopic composition of atmospheric HONO at rural and urban sites. Interestingly, we identified that livestock farming is a previously overlooked direct source of HONO and determined its HONO to ammonia (NH 3 ) emission ratio. Additionally, our results revealed that spatial and temporal variations in atmospheric HONO isotopic composition can be partially attributed to direct emissions. Through a detailed HONO budget analysis incorporating agricultural sources, we found that direct HONO emissions accounted for 39~45% of HONO production in rural areas across different seasons. The findings were further confirmed by chemistry transport model simulations, highlighting the significance of direct HONO emissions and their impact on air quality in the North China Plain. These findings provide compelling evidence that direct HONO emissions play a more substantial role in contributing to atmospheric HONO than previously believed. Moreover, the δ 15 N and δ 18 O isotopic fingerprints developed in this study may serve as a valuable tool for further research on the atmospheric chemistry of reactive nitrogen gases.

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Section: Discussionmentioning

confidence: 99%

Unveiling the underestimated direct emissions of nitrous acid (HONO)

Zhang,

Liu,

Wang

et al. 2023

Proc. Natl. Acad. Sci. U.S.A.

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“…During the 1-week HONO production experiment, HONO in the ambient and both chambers were simultaneously measured using a customized homemade LOPAP, which is characterized by wet chemical sampling and photometric detection. The detailed description of LOPAP can be found in Wang et al(2023). Comprehensive ambient parameters concerning O 3 photochemistry, including j values (Metcon CCD-Spectrograph), CO (Thermo Scientific, Model 48i), NO (Thermo Scientific, Model 42i-Y), and VOCs and OVOCs (GC-MS, TH-PKU 300B, Wuhan Tianhong Instrument Co., Ltd., China), were luckily available during the 1-week HONO production experiment.…”

Section: S25 Determination Of Gas Residence Time In Chambersmentioning

confidence: 99%

Supplementary material to "Optimizing a twin-chamber system for direct ozone production rate measurement"

Wang,

Chen,

Chi

et al. 2023

Preprint

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“…(c) Heterogeneous conversion of NO 2 on various surfaces (Liu et al, 2023a;Yu et al, 2022a;Yang et al, 2021a), Finlayson-Pitts et al (2003) reported that NO 2 could be converted to HONO on humid surfaces with first order in NO 2 , Xu et al (2015) highlighted the HONO source had a large variability with heterogeneous conversion of NO 2 at ground face, Aubin and Abbatt (2007) found that the heterogeneous conversion of NO 2 on hydrocarbon surfaces was an effective pathway to generate HONO. (d) photolysis of nitric acid and nitrate in particles at daytime, which were considered as important sources of HONO in both experiments and field observations (Wang et al, 2023b;Ye et al, 2019;Yang et al, 2018;Ye et al, 2017). And for the sinks of HONO, diurnal photolysis is the main consumption way (Keller-Rudek et al, 2013), the reaction of HONO with OH radical is also one sink that needs to be paid attention to (Cox et al, 1976).…”

Section: Introductionmentioning

confidence: 99%

Characterization of nitrous acid and its potential effects on secondary pollution in warm-season of Beijing urban areas

Li,

Lian,

Liu

et al. 2024

Preprint

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Abstract. Benefiting from a series of pollution prevention initiatives, fine particle (PM2.5) pollution was effectively controlled in 2018–2020, but ground-level ozone pollution during warm season has become a major issue for the continuous air quality improvement in Beijing. As a key source of hydroxyl (OH) radical, nitrous acid (HONO) has attracted much attention for its important role in the atmospheric oxidant capacity (AOC) increase; the elucidation of the pollution characteristics, unknown sources and the contribution to secondary pollution of HONO has become a research hotspot. In this study, we made a comparative study on the ambient levels, variation patterns, sources and formation pathway in warm season (from June to October in 2021) on a basis of a continuous intensive observation in an urban site of Beijing. The monthly average mixing ratio of HONO were 1.26 ppb, 1.28 ppb, 1.01 ppb, 0.96 ppb, 0.89 ppb, respectively, showing a larger contribution to OH radical relative to ozone at daytime with a mean OH production rate of 2.70, 2.91, 2.00, 2.25, and 0.93 ppb/h, respectively. The emission factor from the vehicle emissions, Pemis, was estimated to be 0.017, higher than most studies conducted in Beijing, the observation site and traffic control policies could affect this phenomenon. The homogeneous production of HONO via reaction of NO + OH, PnetOH+NO, in each month were 0.050, 0.045, 0.033, 0.052, and 0.17 ppb/h, respectively. The average nocturnal NO2 to HONO conversion frequency CHONO in each month were 0.011 h−1, 0.0096 h−1, 0.013% h−1, 0.0081 h−1, and 0.0017 h−1, respectively. In warm seasons, the missing source of HONO, Punknown, around noontime were 0.29–2.37 ppb/hr. Punknown in each month might be various. According to the observation results, relatively low humidity and strong solar illumination were conductive to HONO formation in June, which might be due to light-induced heterogeneous reactions of NO2. In July in Beijing, high humidity condition was beneficial to the heterogeneous reaction of NO2, and due to the increase of precipitation, more HONO would enter the liquid phase (the high Henry coefficient of HONO). For days with high humidity and strong sunlight in June and August, photolysis of nitrate was also one important HONO source. For August and September, light-induced reactions of NO2 on non-aerosol surfaces under relatively low humidity and strong light conditions could be an important HONO source. In addition, the presence of Cl ions and sulfate could enhance the photolysis of nitrate, and this was obvious in July and October; the presence of organic compounds also could have this effect, which was obvious in June and October. Not only the HONO concentration but also the HONO source has temporal patterns, even within a season, it varies from month to month. This work highlights the importance of HONO for AOC in warm season, while encouraging long-term HONO observation to assess the contribution of HONO sources over time compared to the capture of pollution processes.

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Experimental and kinetic model evaluation of HONO production from surface nitrate photolysis

Cited by 11 publications

References 58 publications

Unveiling the underestimated direct emissions of nitrous acid (HONO)

Unveiling the underestimated direct emissions of nitrous acid (HONO)

Supplementary material to "Optimizing a twin-chamber system for direct ozone production rate measurement"

Characterization of nitrous acid and its potential effects on secondary pollution in warm-season of Beijing urban areas

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