NH3-promoted hydrolysis of NO2 induces explosive growth in HONO

Abstract. The study of atmospheric nitrous acid (HONO), which is the primary source of OH radicals, is crucial to atmospheric photochemistry and heterogeneous chemical processes. The heterogeneous NO2 chemistry under haze conditions was pointed out to be one of the missing sources of HONO on the North China Plain, producing sulfate and nitrate in the process. However, controversy exists between various proposed mechanisms, mainly debating on whether SO2 directly takes part in the HONO production process and what roles NH3 and the pH value play in it. In this paper, never before seen explosive HONO production (maximum rate: 16 ppb/hour) was reported and evidence was found for the first time in field measurements during fog episodes (usually with pH > 5) and haze episodes under high relative humidity (usually with pH

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Consistency and applicability of parameterization schemes for the size-resolved aerosol activation ratio based on field measurements in the North China Plain

Atmospheric Environment ◽

10.1016/j.atmosenv.2017.11.021 ◽

2018 ◽

Vol 173 ◽

pp. 316-324 ◽

Cited By ~ 4

Author(s):

Jiangchuan Tao ◽

Chunsheng Zhao ◽

Nan Ma ◽

Ye Kuang

Keyword(s):

North China Plain ◽

North China ◽

Field Measurements ◽

Parameterization Schemes ◽

The North ◽

The North China Plain ◽

Activation Ratio ◽

Aerosol Activation

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Atmospheric reactivity and oxidation capacity during summer at a suburban site between Beijing and Tianjin

Atmospheric Chemistry and Physics ◽

10.5194/acp-20-8181-2020 ◽

2020 ◽

Vol 20 (13) ◽

pp. 8181-8200

Author(s):

Yuan Yang ◽

Yonghong Wang ◽

Putian Zhou ◽

Dan Yao ◽

Dongsheng Ji ◽

...

Keyword(s):

North China Plain ◽

North China ◽

Transport Model ◽

Oh Radicals ◽

Chemical Transport Model ◽

Oxidation Capacity ◽

The North ◽

The North China Plain ◽

Atmospheric Reactivity ◽

Suburban Site

Abstract. Hydroxyl (OH) radicals, nitrate (NO3) radicals and ozone (O3) play central roles in the troposphere because they control the lifetimes of many trace gases that result from anthropogenic and biogenic origins. To estimate the air chemistry, the atmospheric reactivity and oxidation capacity were comprehensively analyzed based on a parameterization method at a suburban site in Xianghe in the North China Plain from 6 July 2018 to 6 August 2018. The total OH, NO3 and O3 reactivities at the site varied from 9.2 to 69.6, 0.7 to 27.5 and 3.3×10-4 to 1.8×10-2 s−1 with campaign-averaged values of 27.5±9.7, 2.2±2.6 and 1.2±1.7×10-3 s−1 (± standard deviation), respectively. NOx (NO+NO2) was by far the main contributor to the reactivities of the three oxidants, with average values of 43 %–99 %. Alkenes dominated the OH, NO3 and O3 reactivities towards total nonmethane volatile organic compounds (NMVOCs), accounting for 42.9 %, 77.8 % and 94.0 %, respectively. The total OH, NO3 and O3 reactivities displayed similar diurnal variations with the lowest values during the afternoon but the highest values during rush hours, and the diurnal profile of NOx appears to be the major driver for the diurnal profiles of the reactivities of the three oxidants. A box model (a model to Simulate the concentrations of Organic vapors, Sulfuric Acid and Aerosols; SOSAA) derived from a column chemical transport model was used to simulate OH and NO3 concentrations during the observation period. The calculated atmospheric oxidation capacity (AOC) reached 4.5×108 moleculescm-3s-1, with a campaign-averaged value of 7.8×107 moleculescm-3s-1 dominated by OH (7.7×107 moleculescm-3s-1, 98.2 %), O3 (1.2×106 moleculescm-3s-1, 1.5 %) and NO3 (1.8×105 moleculescm-3s-1, 0.3 %). Overall, the integration of OH, NO3 and O3 reactivities analysis could provide useful insights for NMVOC pollution control in the North China Plain. We suggest that further studies, especially direct observations of OH and NO3 radical concentrations and their reactivities, are required to better understand trace gas reactivity and AOC.

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Seasonal effects of additional HONO sources and the heterogeneous reactions of N2O5 on nitrate in the North China Plain

10.5194/egusphere-egu2020-1476 ◽

2020 ◽

Author(s):

Yu Qu ◽

Junling An

Keyword(s):

North China Plain ◽

North China ◽

Heterogeneous Reaction ◽

Heterogeneous Reactions ◽

Seasonal Effects ◽

Weather Research And Forecasting ◽

The North ◽

The North China Plain ◽

Four Seasons ◽

Hydrolysis Of

We coupled the heterogeneous hydrolysis of N2O5 into the newly updated Weather Research and Forecasting model with Chemistry (WRF-Chem) to reveal the relative importance of the hydrolysis of N2O5 and additional nitrous acid (HONO) sources for the formation of nitrate during high PM2.5 events in the North China Plain (NCP) in four seasons. The results showed that additional HONO sources produced the largest nitrate concentrations in winter and negligible nitrates in summer, leading to a 10% enhancement of a PM2.5 peak in southern Beijing and a 15% enhancement in southeastern Hebei in winter. In contrast, the hydrolysis of N2O5 produced high nitrate in summer and low nitrate in winter, with the largest contribution of nearly 20% for a PM2.5 peak in southeastern Hebei in summer. During PM2.5 explosive growth events, the additional HONO sources played a key role in nitrate increases in southern Beijing and southwestern Hebei in winter, whereas the hydrolysis of N2O5 contributed the most to a rapid increase in nitrate in other seasons. HONO photolysis produced more hydroxyl radicals, which were greater than 1.5 &#956;g m-3 h-1 in the early explosive stage and led to a rapid nitrate increase at the southwestern Hebei sites in winter, while the heterogeneous reaction of N2O5 contributed greatly to a significant increase in nitrate in summer. The above results suggest that the additional HONO sources and the heterogeneous hydrolysis of N2O5 contributed the most to nitrate formation in NCP in winter and summer, respectively.

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NH3-promoted hydrolysis of NO2 induces explosive growth in HONO

Atmospheric Chemistry and Physics ◽

10.5194/acp-19-10557-2019 ◽

2019 ◽

Vol 19 (16) ◽

pp. 10557-10570 ◽

Cited By ~ 6

Author(s):

Wanyun Xu ◽

Ye Kuang ◽

Chunsheng Zhao ◽

Jiangchuan Tao ◽

Gang Zhao ◽

...

Keyword(s):

Ph Value ◽

Pollution Abatement ◽

Primary Source ◽

Field Measurements ◽

Control Measures ◽

Oh Radicals ◽

Aerosol Formation ◽

Atmospheric Photochemistry ◽

Secondary Aerosol ◽

Hydrolysis Of

Abstract. The study of atmospheric nitrous acid (HONO), which is the primary source of OH radicals, is crucial with respect to understanding atmospheric photochemistry and heterogeneous chemical processes. Heterogeneous NO2 chemistry under haze conditions has been identified as one of the missing sources of HONO on the North China Plain, and also produces sulfate and nitrate. However, controversy exists regarding the various proposed HONO production mechanisms, mainly regarding whether SO2 directly takes part in the HONO production process and what roles NH3 and the pH value play. In this paper, never before seen explosive HONO production was reported and evidence was found – for the first time in field measurements during fog (usually with 4< pH <6) and haze episodes under high relative humidity (pH ≈4) – that NH3 was the key factor that promoted the hydrolysis of NO2, leading to the explosive growth of HONO and nitrate under both high and relatively lower pH conditions. The results also suggest that SO2 plays a minor or insignificant role in HONO formation during fog and haze events, but was indirectly oxidized upon the photolysis of HONO via subsequent radical mechanisms. Aerosol hygroscopicity significantly increased with rapid inorganic secondary aerosol formation, further promoting HONO production as a positive feedback. For future photochemical and aerosol pollution abatement, it is crucial to introduce effective NH3 emission control measures, as NH3-promoted NO2 hydrolysis is a large daytime HONO source, releasing large amounts of OH radicals upon photolysis, which will contribute largely to both atmospheric photochemistry and secondary aerosol formation.

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Wintertime photochemistry in Beijing: Observations of ROx radical concentrations in the North China Plain during the BEST-ONE campaign

10.5194/acp-2018-359 ◽

2018 ◽

Cited By ~ 2

Author(s):

Zhaofeng Tan ◽

Franz Rohrer ◽

Keding Lu ◽

Xuefei Ma ◽

Birger Bohn ◽

...

Keyword(s):

New York ◽

Primary Production ◽

North China Plain ◽

North China ◽

Oxidative Capacity ◽

Oh Radicals ◽

Peroxy Radicals ◽

The North ◽

The North China Plain ◽

Secondary Pollutants

Abstract. The first wintertime in-situ measurements of hydroxyl (OH), hydroperoxy (HO2) and organic peroxy (RO2) radicals (ROx = OH + HO2 + RO2) in combination with observations of total reactivity of OH radicals, kOH in Beijing are presented. The field campaign “Beijing winter finE particle STudy – Oxidation, Nucleation and light Extinctions” (BEST-ONE) was conducted at the suburban site Huairou near Beijing from January to March 2016. It aimed to understand oxidative capacity during wintertime and to elucidate the secondary pollutants formation mechanism in the North China Plain (NCP). OH radical concentrations at noontime ranged from 2.4 × 106 cm−3 in severely polluted air (kOH ~ 27 s−1) to 3.6 × 106 cm−3 in relatively clean air (kOH ~ 5 s−1). These values are nearly two-fold larger than OH concentrations observed in previous winter campaign in Birmingham, Tokyo, and New York City. During this campaign, the total primary production rate of ROx radicals was dominated by the photolysis of nitrous acid accounting for 46 % of the identified primary production pathways for ROx radicals. Other important radical sources were alkene ozonolysis (28 %) and photolysis of oxygenated organic compounds (24 %). A box model was used to simulate the OH, HO2 and RO2 concentrations based on the observations of their long-lived precursors. The model was capable of reproducing the observed diurnal variation of the OH and peroxy radicals during clean days with a factor of 1.5. However, it largely underestimated HO2 and RO2 concentrations by factors up to 5 during pollution episodes. The HO2 and RO2 observed-to-modeled ratios increased with increasing NO concentrations, indicating a deficit in our understanding of the gas-phase chemistry in the high NOx regime. The OH concentrations observed in the presence of large OH reactivities indicate that atmospheric trace gas oxidation by photochemical processes can be highly effective even during wintertime, thereby facilitating the vigorous formation of secondary pollutants.

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Wintertime photochemistry in Beijing: observations of ROx radical concentrations in the North China Plain during the BEST-ONE campaign

Atmospheric Chemistry and Physics ◽

10.5194/acp-18-12391-2018 ◽

2018 ◽

Vol 18 (16) ◽

pp. 12391-12411 ◽

Cited By ~ 57

Author(s):

Zhaofeng Tan ◽

Franz Rohrer ◽

Keding Lu ◽

Xuefei Ma ◽

Birger Bohn ◽

...

Keyword(s):

New York ◽

Primary Production ◽

North China Plain ◽

North China ◽

Oxidative Capacity ◽

Oh Radicals ◽

Peroxy Radicals ◽

The North ◽

The North China Plain ◽

Secondary Pollutants

Abstract. The first wintertime in situ measurements of hydroxyl (OH), hydroperoxy (HO2) and organic peroxy (RO2) radicals (ROx=OH+HO2+RO2) in combination with observations of total reactivity of OH radicals, kOH in Beijing are presented. The field campaign “Beijing winter finE particle STudy – Oxidation, Nucleation and light Extinctions” (BEST-ONE) was conducted at the suburban site Huairou near Beijing from January to March 2016. It aimed to understand oxidative capacity during wintertime and to elucidate the secondary pollutants' formation mechanism in the North China Plain (NCP). OH radical concentrations at noontime ranged from 2.4×106cm-3 in severely polluted air (kOH∼27s-1) to 3.6×106cm-3 in relatively clean air (kOH∼5s-1). These values are nearly 2-fold larger than OH concentrations observed in previous winter campaigns in Birmingham, Tokyo, and New York City. During this campaign, the total primary production rate of ROx radicals was dominated by the photolysis of nitrous acid accounting for 46 % of the identified primary production pathways for ROx radicals. Other important radical sources were alkene ozonolysis (28 %) and photolysis of oxygenated organic compounds (24 %). A box model was used to simulate the OH, HO2 and RO2 concentrations based on the observations of their long-lived precursors. The model was capable of reproducing the observed diurnal variation of the OH and peroxy radicals during clean days with a factor of 1.5. However, it largely underestimated HO2 and RO2 concentrations by factors up to 5 during pollution episodes. The HO2 and RO2 observed-to-modeled ratios increased with increasing NO concentrations, indicating a deficit in our understanding of the gas-phase chemistry in the high NOx regime. The OH concentrations observed in the presence of large OH reactivities indicate that atmospheric trace gas oxidation by photochemical processes can be highly effective even during wintertime, thereby facilitating the vigorous formation of secondary pollutants.

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