Kinetics of the gas phase reaction OH + NO(+M)→HONO(+M) and the determination of the UV absorption cross sections of HONO

Pagsberg, P.; Bjergbakke, E.; Ratajczak, Emil; Sillesen, Alfred

doi:10.1016/s0009-2614(97)00576-9

Cited by 91 publications

(59 citation statements)

References 31 publications

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“…The cross sections are always related to the sum ofthe trans-and cis-HONO concentration due to the large degree of uncertainty on the equilibrium constant (Becker et al, 1995), K = Ptrans1pcis = 3.25 ± 0.30 at 277 K (Bongartz et al, 1991). Several HONO absorption cross section data exist in the literature (Johnston and Graham, 1974;Derwent, 1976, 1977;Stockwell and Calvert, 1978;Perner and Platt, 1979;Vasudev, 1990;Bongartz et al, 1991Bongartz et al, , 1994Febo et al, 1995;Pagsberg et al, 1997;Brust et al, 2000;Stutz et al, 2000), as compared in Table 3. The published data differs significantly, with spectral resolutions in the range of <0.1-1 nm, and various methods of HONO production (refer to Table 3).…”

Section: Absorption Cross Section Datamentioning

confidence: 99%

Measurements of the HONO photodissociation constant

2006

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Measurements of the photodissociation constant for nitrous acid (jHONO) were made at an urban site in Toronto, Canada, during the months of May-July 2005, using an optically thin actinometer. Operating details of the jHONO monitor are reported, along with laboratory tests. Measurements of jHONO were obtained for solar zenith angles ranging from 20-75 0 , under clear and cloudy skies. Maximum error estimates on jHONO under clear skies range from 11 % at sunrise, to 4% at solar noon, with a minimum detection limit of 5.7 x 10-4 /sec for our actinometer. Measured clear-sky values of jHONO were compared with values calculated by a four-stream discrete ordinate radiative transfer (RT) model (ACD TUV version 4.1), and were found to be within better than 10% agreement for solar zenith angles <65 0 • For conditions of scattered cloud, enhancement and suppression of the jHONO values occurred by as much as 16%-70%, and 59%-80%, respectively. The integrated band area of the mr* transition for gas-phase nitrous acid yields an oscillator strength, f = (1.06 ± 0.044) x 10-3 (based on clear-sky data), 19.1 % higher than the value reported by Bongartz et al. (1991).

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Section: Absorption Cross Section Datamentioning

confidence: 99%

Measurements of the HONO photodissociation constant

2006

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“…The gas-phase reaction of NO with the OH radical (Stuhl and Niki, 1972;Pagsberg et al, 1997) mostly determines the daytime HONO concentration. However, recent field measurements (Neftel et al, 1996;Kleffmann et al, 2005;Sörgel et al, 2011;Li et al, 2012Li et al, , 2014Wong et al, 2012) and laboratory studies (Akimoto et al, 1987;Rohrer et al, 2005) reported much larger HONO concentrations than predicted by the gas-phase reactions.…”

Section: Introductionmentioning

confidence: 99%

MAX-DOAS measurements of HONO slant column densities during the MAD-CAT campaign: inter-comparison, sensitivity studies on spectral analysis settings, and error budget

et al. 2017

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Abstract. In order to promote the development of the passive DOAS technique the Multi Axis DOAS -Comparison campaign for Aerosols and Trace gases (MAD-CAT) was held at the Max Planck Institute for Chemistry in Mainz, Germany, from June to October 2013. Here, we systematically compare the differential slant column densities (dSCDs) of nitrous acid (HONO) derived from measurements of seven different instruments. We also compare the tropospheric difference of SCDs (delta SCD) of HONO, namely the difference of the SCDs for the non-zenith observations and the zenith observation of the same elevation sequence. Different research groups analysed the spectra from their own instruments using their individual fit software. All the fit errors of HONO dSCDs from the instruments with cooled large-size detectors are mostly in the range of 0.1 to 0.3 × 10 15 molecules cm −2 for an integration time of 1 min. The fit error for the mini MAX-DOAS is around 0.7 × 10 15 molecules cm −2 . Although the HONO delta SCDs are normally smaller than 6 × 10 15 molecules cm −2 , consistent time series of HONO delta SCDs are retrieved from the measurements of different instruments. Both fits with a sequential Fraunhofer reference spectrum (FRS) and a daily noon FRS lead to similar consistency. Apart from the mini-MAX-DOAS, the systematic absolute differences of HONO delta SCDs between the instruments are smaller than 0.63 × 10 15 molecules cm −2 . The correlation coefficients are higher than 0.7 and the slopes of linear regressions deviate from unity by less than 16 % for the elevation angle of 1 • . The correlations decrease with an increase in elevation angle. All the participants also analysed synthetic spectra using the same baseline DOAS settings toPublished by Copernicus Publications on behalf of the European Geosciences Union. Y. Wang et al.: MAX-DOAS measurements of HONO slant column densitiesevaluate the systematic errors of HONO results from their respective fit programs. In general the errors are smaller than 0.3 × 10 15 molecules cm −2 , which is about half of the systematic difference between the real measurements.The differences of HONO delta SCDs retrieved in the selected three spectral ranges 335-361, 335-373 and 335-390 nm are considerable (up to 0.57 × 10 15 molecules cm −2 ) for both real measurements and synthetic spectra. We performed sensitivity studies to quantify the dominant systematic error sources and to find a recommended DOAS setting in the three spectral ranges. The results show that water vapour absorption, temperature and wavelength dependence of O 4 absorption, temperature dependence of Ring spectrum, and polynomial and intensity offset correction all together dominate the systematic errors. We recommend a fit range of 335-373 nm for HONO retrievals. In such fit range the overall systematic uncertainty is about 0.87 × 10 15 molecules cm −2 , much smaller than those in the other two ranges. The typical random uncertainty is estimated to be about 0.16 × 10 15 molecules cm −2 , which is only 25 % of the total syst...

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“…Among the most known chemical sources of HONO is the gas-phase formation from the reaction between OH and nitric oxide (NO) (Pagsberg et al, 1997) and the heterogeneous formation on surfaces from the hydrolysis of nitrogen dioxide (NO 2 ) (Kleffmann et al, 1998;Finlayson-Pitts et al, 2003). Other chemical sources of HONO are described else-where (Kleffmann, 2007;Kleffmann et al, 2005;George et al, 2005;Stemmler et al, 2006Stemmler et al, , 2007Crowley and Carl, 1997;Li et al, 2008Li et al, , 2009Carr et al, 2009;Amedro et al, 2011).…”

Section: Introductionmentioning

confidence: 99%

Impact of updated traffic emissions on HONO mixing ratios simulated for urban site in Houston, Texas

Czader

Choi

et al. 2015

Atmos. Chem. Phys.

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Abstract. Recent measurements in Houston show that HONO traffic emissions are 1.7 % of NO x emissions, which is about twice the previously estimated value of 0.8 % based on tunnel measurements in 2001. The 0.8 % value is widely used to estimate mobile emissions of HONO for air quality modeling applications. This study applies the newly estimated HONO / NO x ratio in the WRF-SMOKE-CMAQ modeling system and estimates the impact of higher HONO traffic emissions on its mixing ratios. Since applied emission inventory resulted in overestimates of NO x mixing ratios and because HONO emissions and chemical formation depend on the magnitude of NO x , thus, before proceeding with HONO emission modifications emissions of NO x were adjusted to reflect current emission trends. The modeled mixing ratios of NO x were evaluated against measured data from a number of sites in the Houston area. Overall, the NO x mean value dropped from 11.11 ppbv in the base case to 7.59 ppbv in the NO x -adjusted case becoming much closer to the observed mean of 7.76 ppbv. The index of agreement (IOA) is improved in the reduced NO x case (0.71 vs. 0.75) and the absolute mean error (AME) is lowered from 6.76 to 4.94. The modeled mixing ratios of HONO were evaluated against the actual observed values attained at the Moody Tower in Houston. The model could not reproduce the morning HONO peaks when the low HONO / NO x ratio of 0.008 was used to estimate HONO emissions. Doubling HONO emissions from mobile sources resulted in higher mixing ratios, and the mean value increased from 0.30 to 0.41 ppbv becoming closer to the observed mean concentrations of 0.69 but still low; AME was slightly reduced from 0.46 to 0.43. IOA for simulation that used the 2001 emission values is 0.63 while for simulation with higher HONO emission it increased to 0.70. Increased HONO emissions from mobile sources resulted in a 14 % increase in OH during morning time at the location of the Moody Tower and 3 % when averaged over an urban area. The increase calculated for daytime was 7 and 1 % for the Moody Tower and the urban area, respectively. The impact on ozone was found to be marginal. This study results shed light on the underestimated HONO and OH in the morning from global/regional chemical transport models with the typical emission of 0.8 % HONO emission out of the total NO x emissions.

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Kinetics of the gas phase reaction OH + NO(+M)→HONO(+M) and the determination of the UV absorption cross sections of HONO

Cited by 91 publications

References 31 publications

Measurements of the HONO photodissociation constant

Measurements of the HONO photodissociation constant

MAX-DOAS measurements of HONO slant column densities during the MAD-CAT campaign: inter-comparison, sensitivity studies on spectral analysis settings, and error budget

Impact of updated traffic emissions on HONO mixing ratios simulated for urban site in Houston, Texas

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