Exploring the atmospheric chemistry of nitrous acid (HONO) at a rural site in Southern China

Li, X.; Brauers, T.; Häseler, R.; Bohn, Birger; Fuchs, Hendrik; Hofzumahaus, A.; Holland, F.; Lou, Shengrong; Lu, Keding; Rohrer, Franz; Hu, Min; Zeng, Limin; Zhang, Y. H.; Garland, R. M.; Su, Hang; Nowak, Andreas; Wiedensohler, Alfred; Takegawa, N.; Shao, Min; Wahner, Andreas

doi:10.5194/acp-12-1497-2012

Cited by 228 publications

(292 citation statements)

References 67 publications

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“…Zhou et al (2011) also reported the similar levels of HONO (below 100 ppt) from the PROPHET forest, a mixed hardwood forest in northern Michigan (Pellston, MI). However, significantly higher HONO levels (∼ 200 ppt to 2 ppb) were reported by Li et al (2012) from a rural observational site in the Pearl River Delta region near Guangzhou, where comparable NO 2 levels with TRF were observed. The high HONO levels (a few hundred ppt) especially during the daytime have been consistently reported near East Asian megacities such as Beijing , Shanghai (Hao et al, 2006), and Seoul (Song et al, 2009).…”

Section: Observational Resultsmentioning

confidence: 99%

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Impact of isoprene and HONO chemistry on ozone and OVOC formation in a semirural South Korean forest

Kim

Lee³

et al. 2015

Atmos. Chem. Phys.

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Abstract. Rapid urbanization and economic development in East Asia in past decades has led to photochemical air pollution problems such as excess photochemical ozone and aerosol formation. Asian megacities such as Seoul, Tokyo, Shanghai, Guangzhou, and Beijing are surrounded by densely forested areas, and recent research has consistently demonstrated the importance of biogenic volatile organic compounds (VOCs) from vegetation in determining oxidation capacity in the suburban Asian megacity regions. Uncertainties in constraining tropospheric oxidation capacity, dominated by hydroxyl radical, undermine our ability to assess regional photochemical air pollution problems. We present an observational data set of CO, NO x , SO 2 , ozone, HONO, and VOCs (anthropogenic and biogenic) from Taehwa research forest (TRF) near the Seoul metropolitan area in early June 2012. The data show that TRF is influenced both by aged pollution and fresh biogenic volatile organic compound emissions. With the data set, we diagnose HO x (OH, HO 2 , and RO 2 ) distributions calculated using the University of Washington chemical box model (UWCM v2.1) with nearexplicit VOC oxidation mechanisms from MCM v3.2 (Master Chemical Mechanism). Uncertainty from unconstrained HONO sources and radical recycling processes highlighted in recent studies is examined using multiple model simulations with different model constraints. The results suggest that (1) different model simulation scenarios cause systematic differences in HO x distributions, especially OH levels (up to 2.5 times), and (2) radical destruction (HO 2 + HO 2 or HO 2 + RO 2 ) could be more efficient than radical recycling (RO 2 + NO), especially in the afternoon. Implications of the uncertainties in radical chemistry are discussed with respect to ozone-VOC-NO x sensitivity and VOC oxidation product formation rates. Overall, the NO x limited regime is assessed except for the morning hours (8 a.m. to 12 p.m. local standard time), but the degree of sensitivity can significantly vary depending on the model scenarios. The model results also suggest that RO 2 levels are positively correlated with oxygenated VOCs (OVOCs) production that is not routinely constrained by observations. These unconstrained OVOCs can cause higher-than-expected OH loss rates (missing OH reactivity) and secondary organic aerosol formation. The series of modeling experiments constrained by observations strongly urge observational constraint of the radical pool to enable precise understanding of regional photochemical pollution problems in the East Asian megacity region.

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Section: Observational Resultsmentioning

confidence: 99%

“…Sartelet et al, 2012). It should be also noted that HONO has been observed at high levels in the East Asian region even in the daytime (∼ hundreds ppt; Song et al, 2009;Hao et al, 2006;Li et al, 2012). The data analysis has consistently indicated that well-known HONO sources cannot account for the observed level.…”

mentioning

confidence: 85%

Impact of isoprene and HONO chemistry on ozone and OVOC formation in a semirural South Korean forest

Kim

Lee³

et al. 2015

Atmos. Chem. Phys.

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“…Therefore it is difficult to estimate the importance of HONO formation on protein surface and its contribution to the HONO budget. In many studies the calculated unknown source strength of daytime HONO formation is within a range of about 200-800 ppt h −1 Acker et al, 2006;Li et al, 2012).…”

Section: Discussionmentioning

confidence: 99%

“…Measured mixing ratios are typically about 1 order of magnitude higher than simulated ones, and an additional source of 200-800 ppt h −1 would be required to explain observed mixing ratios Acker et al, 2006;Li et al, 2012;Su et al, 2008;Elshorbany et al, 2012;Meusel et al, 2016), indicating that estimates of daytime HONO sources are still under debate. It was suggested that HONO arises from the photolysis of nitric acid and nitrate or by heterogeneous photochemistry of NO 2 on organic substrates and soot (Zhou et al, 2001(Zhou et al, , 2002(Zhou et al, and 2003Villena et al, 2011;Ramazan et al, 2004;George et al, 2005;Sosedova et al, 2011;Monge et al, 2010;Han et al, 2016).…”

Section: Introductionmentioning

confidence: 99%

Light-induced protein nitration and degradation with HONO emission

et al. 2017

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Abstract. Proteins can be nitrated by air pollutants (NO 2 ), enhancing their allergenic potential. This work provides insight into protein nitration and subsequent decomposition in the presence of solar radiation. We also investigated lightinduced formation of nitrous acid (HONO) from protein surfaces that were nitrated either online with instantaneous gas-phase exposure to NO 2 or offline by an efficient nitration agent (tetranitromethane, TNM). Bovine serum albumin (BSA) and ovalbumin (OVA) were used as model substances for proteins. Nitration degrees of about 1 % were derived applying NO 2 concentrations of 100 ppb under VIS/UV illuminated conditions, while simultaneous decomposition of (nitrated) proteins was also found during long-term (20 h) irradiation exposure. Measurements of gas exchange on TNMnitrated proteins revealed that HONO can be formed and released even without contribution of instantaneous heterogeneous NO 2 conversion. NO 2 exposure was found to increase HONO emissions substantially. In particular, a strong dependence of HONO emissions on light intensity, relative humidity, NO 2 concentrations and the applied coating thickness was found. The 20 h long-term studies revealed sustained HONO formation, even when concentrations of the intact (nitrated) proteins were too low to be detected after the gas exchange measurements. A reaction mechanism for the NO 2 conversion based on the Langmuir-Hinshelwood kinetics is proposed.

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“…Unfortunately, there have been few studies of the uptake coefficient of R2 (γ HONO ) in China (Li et al 2012b). Tang et al (2014) reported a suggested γ HONO of 10 −4 for the North China Plain, but this has not been tested in other regions in China.…”

Section: Introductionmentioning

confidence: 99%

Exploring Possible Missing Sinks of Nitrate and Its Precursors in Current Air Quality Models —A Case Simulation in the Pearl River Delta, China, Using an Observation-Based Box Model

Dong

Zeng

et al. 2015

SOLA

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Nitrate and its precursor (gaseous HNO 3 ) in China are generally overestimated by current chemical transport models in comparison to in-situ observations. In this study, we used an observation-based box model and in-situ measurements at a rural site in southern China to investigate possible missing sinks of nitrate. We found that a heterogeneous reaction of HNO 3 to NO x on soot can better balance the NO x /HNO 3 chemistry in models and improve model performance with regard to nitrate, particularly where an additional HONO source (the heterogeneous reaction of NO 2 on soot) is incorporated into current models. Through a series of sensitivity simulations, the uptake coefficients of heterogeneous reactions were suggested to be 3.0 × 10 −3 and 1 × 10 −4 for HNO 3 and HONO over southern China in fall, respectively. A 3-D simulation with the suggested uptake coefficients further confirmed that heterogeneous reactions significantly decreased the nitrate concentrations (PNO 3 ) in southern China, by up to 10 μg m −3 (50%−80% of simulated PNO 3 ) in polluted regions (e.g., the Yangtze River). In contrast to nitrate and HNO 3 , NO x concentrations in China were enhanced, which partly explained the underestimation of NO 2 in current models compared to satellite observations.(Citation: Li, J., H. B. Dong, Z. F. Wang, Yele Sun, and Pingqing Fu, 2015: Exploring possible missing sinks of nitrate and its precursors in current air quality models-A case simulation in Pearl River delta of China using an observation-based box model.

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Exploring the atmospheric chemistry of nitrous acid (HONO) at a rural site in Southern China

Cited by 228 publications

References 67 publications

Impact of isoprene and HONO chemistry on ozone and OVOC formation in a semirural South Korean forest

Impact of isoprene and HONO chemistry on ozone and OVOC formation in a semirural South Korean forest

Light-induced protein nitration and degradation with HONO emission

Exploring Possible Missing Sinks of Nitrate and Its Precursors in Current Air Quality Models —A Case Simulation in the Pearl River Delta, China, Using an Observation-Based Box Model

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