Measured and simulated vertical profiles of nitrous acid—Part II. Model simulations and indications for a photolytic source

Vogel, Bernhard; Vogel, H.; Kleffmann, Jörg; Kurtenbach, R.

doi:10.1016/s1352-2310(03)00243-7

Cited by 148 publications

(165 citation statements)

References 24 publications

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“…NO 2 hydrolysis on the ground, buildings and vegetation surfaces (R1) is believed to be a major contributor to HONO formation in the atmosphere, especially at night Vogel et al, 2003). Kinetics of reaction (R1) is shown to be first order in NO 2 (Kleffmann et al, 1998; and a function of relative humidity (Stutz et al, 2004).…”

Section: Hono Production Via Heterogeneous Chemistry and Photolytic Pmentioning

confidence: 99%

“…Model predictions are compared to HONO observations from the DOMINO campaign performed in El Arenosillo station (Southern Spain) for the analyzed period (Sörgel et al, 2011). Previous modeling studies have included heterogeneous HONO production on ground surfaces as simple parameterizations considering constant surface to volume ratios (Vogel et al, 2003;Li et al, 2010), or neglecting the relative humidity influence on kinetics (Sarwar et al, 2008). Here, those variables influencing HONO heterogeneous production are characterized in detail and their effects analyzed.…”

Section: Introductionmentioning

confidence: 99%

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Impact of HONO sources on the performance of mesoscale air quality models

Gonçalves

Dabdub

Chang

et al. 2012

Atmospheric Environment

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a b s t r a c tNitrous acid (HONO) photolysis constitutes a primary source of OH in the early morning, which leads to changes in model gas-phase and particulate matter concentrations. However, state-of-the-art models of chemical mechanisms share a common representation of gas-phase chemistry leading to HONO that fails in reproducing the observed profiles. Hence, there is a growing interest in improving the definition of additional HONO sources within air quality models, i.e. direct emissions or heterogeneous reactions. In order to test their feasibility under atmospheric conditions, the WRF-ARW/HERMES/CMAQ modeling system is applied with high horizontal resolution (4 Â 4 km 2 ) to Spain for November 24e27, 2008. HONO modeled sources include: (1) direct emissions from on-road transport; NO 2 hydrolysis on aerosol and ground surfaces, the latter with (2) kinetics depending exclusively on available surfaces for reaction and (3) refined kinetics considering also relative humidity dependence; and (4) photoenhanced NO 2 reduction on ground surfaces. The DOMINO measurement campaign performed in El Arenosillo (Southern Spain) provides valuable HONO observations. Modeled HONO results are consistently below observations, even when the most effective scenario is assessed, corresponding to contributions of direct emissions and NO 2 hydrolysis with the simplest kinetics parameterization. With the additional sources of HONO, PM 2.5 predictions can be up to 14% larger in urban areas. Quantified impacts on secondary pollutants have to be taken as a low threshold, due to the proven underestimation of HONO levels. It is fundamental to improve HONO sources definition within air quality models, both for the scientific community and decision makers.

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Section: Hono Production Via Heterogeneous Chemistry and Photolytic Pmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Impact of HONO sources on the performance of mesoscale air quality models

Gonçalves

Dabdub

Chang

et al. 2012

Atmospheric Environment

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“…Based on experimental data obtained for 3M2NP and applying the assumptions described above, a photolytic HONO formation rate of 100 pptv h À1 is estimated for a maximum J(NO 2 ) value of 10 À2 s À1 in the presence of 1 ppbv of nitrophenols. Results obtained in recent field campaigns 38,[41][42][43] suggested the presence of an additional photolytic HONO source. In one study, 43 the existence of a daytime source of HONO was unequivocally demonstrated based only on experimental observation.…”

Section: Atmospheric Implicationsmentioning

confidence: 99%

The photolysis of ortho-nitrophenols: a new gas phase source of HONO

Bejan

Aal

Barnes

et al. 2006

Phys. Chem. Chem. Phys.

235

291

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Formation of nitrous acid (HONO) in the gas phase has been observed for the first time in a flow tube photoreactor upon irradiation (l = 300-500 nm) of 2-nitrophenol and methyl substituted derivatives using a selective and sensitive instrument (LOPAP) for the detection of HONO. Formation of HONO by heterogeneous NO 2 photochemistry has been excluded, since production of NO 2 under the experimental conditions is negligible. Variation of the surface to volume ratio and the nitrophenol concentration showed that the photolysis occurred in the gas phase indicating that HONO formation is initiated by intramolecular hydrogen transfer from the phenolic OH group to the nitro group. From the measured linear dependence of the HONO formation rate on the reactant's concentration and photolysis light intensity, a non-negligible new HONO source is proposed for the urban atmosphere during the day. Unexpectedly high HONO mixing ratios have been observed recently in several field campaigns during the day. It is proposed that the photolysis of aromatic compounds containing the ortho-nitrophenol entity could help to explain, at least in part, this high contribution of HONO to the oxidation capacity of the urban atmosphere.

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“…23 IBBCEAS measures HONO and NO2 simultaneously, in essentially the same sample air, which offers a great advantage to researchers. As described above, HONO is closely related to NOx in the atmosphere, through reactions (1) and (2), which outlines one of the most important secondary formation processes of HONO. A comparison of IBBCEAS and LOPAP measurements was carried out in ambient air.…”

Section: Introductionmentioning

confidence: 96%

“…Because HONO is photolyzed by near-UV light, HONO is the main OH-radical source in the early morning. 1,2 The hydroxyl radical initiates the oxidation of trace species, resulting in the formation of photochemical oxidants and secondary organic aerosols. Therefore, knowledge concerning the HONO budget aids in our understanding of the photochemistry of the troposphere.…”

Section: Introductionmentioning

confidence: 99%

Validation of in situ Measurements of Atmospheric Nitrous Acid Using Incoherent Broadband Cavity-enhanced Absorption Spectroscopy

Nakashima

Sadanaga

2017

ANAL. SCI.

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Incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) is a useful technique for measuring trace gaseous species in the atmosphere. Recently, IBBCEAS was used to measure concentrations of nitrous acid (HONO) in the troposphere to resolve controversies related to its formation and loss. Here, measurements of HONO and a mixture of HONO and NO2 using IBBCEAS were validated by comparing them with those obtained with a NOx analyzer. Good agreement was found between these methods, given their respective experimental uncertainties. The detection limit of our IBBCEAS instrument was 0.2 ppbv, with a signal-to-noise ratio of 1, and a 5-min integration time.

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Measured and simulated vertical profiles of nitrous acid—Part II. Model simulations and indications for a photolytic source

Cited by 148 publications

References 24 publications

Impact of HONO sources on the performance of mesoscale air quality models

Impact of HONO sources on the performance of mesoscale air quality models

The photolysis of ortho-nitrophenols: a new gas phase source of HONO

Validation of in situ Measurements of Atmospheric Nitrous Acid Using Incoherent Broadband Cavity-enhanced Absorption Spectroscopy

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