scholarly journals Quantification of the unknown HONO daytime source and its relation to NO<sub>2</sub>

2011 ◽  
Vol 11 (5) ◽  
pp. 15119-15155 ◽  
Author(s):  
M. Sörgel ◽  
E. Regelin ◽  
H. Bozem ◽  
J.-M. Diesch ◽  
F. Drewnick ◽  
...  
Keyword(s):  
Nitrogen Oxides ◽  
Gas Phase ◽  
Water Vapour ◽  
Field Data ◽  
Mixing Ratios ◽  
Photostationary State ◽  
Conversion Frequency ◽  
Photolysis Frequency ◽  
Electronically Excited ◽  
Measured Field

Abstract. During the DOMINO (Diel Oxidant Mechanism In relation to Nitrogen Oxides) campaign in southwest Spain we measured simultaneously all quantities necessary to calculate a photostationary state for HONO in the gas phase. These quantities comprise the concentrations of OH, NO, and HONO and the photolysis frequency of NO2, j(NO2) as a proxy for j(HONO). This allowed us to calculate values of the unknown HONO daytime source. This unknown HONO source, normalized by NO2 mixing ratios and expressed as a conversion frequency (% h−1), showed a clear dependence on j(NO2) with values up to 43 % h−1 at noon. We compared our unknown HONO source with values calculated from the measured field data for two recently proposed processes, the light-induced NO2 conversion on soot surfaces and the reaction of electronically excited NO2* with water vapour, with the result that these two reactions normally contributed less than 10 % (<1 % NO2 + soot + hν; and <10 % NO2* + H2O) to our unknown HONO daytime source. OH production from HONO photolysis was found to be larger (by 20 %) than the "classical" OH formation from ozone photolysis (O(1D)) integrated over the day.

scholarly journals Quantification of the unknown HONO daytime source and its relation to NO<sub>2</sub>

2011 ◽  
Vol 11 (20) ◽  
pp. 10433-10447 ◽  
Author(s):  
M. Sörgel ◽  
E. Regelin ◽  
H. Bozem ◽  
J.-M. Diesch ◽  
F. Drewnick ◽  
...  
Keyword(s):  
Nitrogen Oxides ◽  
Gas Phase ◽  
Water Vapour ◽  
Field Data ◽  
Mixing Ratios ◽  
Photostationary State ◽  
Conversion Frequency ◽  
Photolysis Frequency ◽  
Electronically Excited ◽  
Measured Field

Abstract. During the DOMINO (Diel Oxidant Mechanism In relation to Nitrogen Oxides) campaign in southwest Spain we measured simultaneously all quantities necessary to calculate a photostationary state for HONO in the gas phase. These quantities comprise the concentrations of OH, NO, and HONO and the photolysis frequency of NO2, j(NO2) as a proxy for j(HONO). This allowed us to calculate values of the unknown HONO daytime source. This unknown HONO source, normalized by NO2 mixing ratios and expressed as a conversion frequency (% h−1), showed a clear dependence on j(NO2) with values up to 43% h−1 at noon. We compared our unknown HONO source with values calculated from the measured field data for two recently proposed processes, the light-induced NO2 conversion on soot surfaces and the reaction of electronically excited NO2* with water vapour, with the result that these two reactions normally contributed less than 10% (<1% NO2 + soot + hν; and <10% NO2* + H2O) to our unknown HONO daytime source. OH production from HONO photolysis was found to be larger (by 20%) than the "classical" OH formation from ozone photolysis (O(1D)) integrated over the day.

scholarly journals Measurements of HONO during BAQS-Met

2010 ◽  
Vol 10 (24) ◽  
pp. 12285-12293 ◽  
Author(s):  
J. J. B. Wentzell ◽  
C. L. Schiller ◽  
G. W. Harris
Keyword(s):  
Gas Phase ◽  
Water Vapour ◽  
Nitrous Acid ◽  
Meteorological Parameters ◽  
Border Region ◽  
Night Time ◽  
Mixing Ratios ◽  
Oxidation Chemistry ◽  
Absorption Photometer ◽  
Shed Light

Abstract. Measurements of nitrous acid (HONO) were performed as part of the 2007 Border Air Quality and Meteorology Study (BAQS-Met) at the Harrow, Ontario, Canada supersite between 20 June and 10 July 2007. Nitrous acid is an important precursor of the hydroxyl radical and understanding its chemistry is important to understanding daytime oxidation chemistry. The HONO measurements were made using a custom built Long Path Absorption Photometer (LOPAP). The goal of this work was to shed light on sources of daytime HONO in the border region. During the course of the campaign HONO mixing ratios consistently exceeded expected daytime values by more than a factor of 6. Mean daytime mixing ratios of 61 pptv were observed. While HONO decay began at sunrise, minimum HONO values were measured during the late afternoon. There was little difference between the daytime (mean = 1.5%) and night-time (mean = 1.7%) ratios of HONO/NO2, thus there was a very strong daytime source of HONO which is consistent with other recent studies. Correlations of daytime HONO production with a variety of chemical and meteorological parameters indicate that production is dependent on UV radiation, NO2 and water vapour but is not consistent with a simple gas phase process. Apparent rate constants for the production of HONO from photolyticaly excited NO2 and water vapour vary from 2.8–7.8×10−13 cm3 molec−1 s−1, during the campaign. These results appear to be consistent with the heterogeneous conversion of NO2 enhanced by photo-excitation.

scholarly journals Measurements of HONO during BAQS-Met

2010 ◽  
Vol 10 (6) ◽  
pp. 15295-15323 ◽  
Author(s):  
J. J. B. Wentzell ◽  
C. L. Schiller ◽  
G. W. Harris
Keyword(s):  
Gas Phase ◽  
Water Vapour ◽  
Nitrous Acid ◽  
Meteorological Parameters ◽  
Border Region ◽  
Night Time ◽  
Mixing Ratios ◽  
Oxidation Chemistry ◽  
Absorption Photometer ◽  
Shed Light

Abstract. Measurements of nitrous acid (HONO) were performed as part of the 2007 Border Air Quality and Meteorology Study (BAQS-Met) at the Harrow Ontario supersite between 20 June and 10 July 2007. Nitrous acid is an important precursor of the hydroxy radical and understanding its chemistry is important to understanding daytime oxidation chemistry. The HONO measurements were made using a custom built Long Path Absorption Photometer (LOPAP). The goal of this work was to shed light on sources of daytime HONO in the border region. During the course of the campaign HONO mixing ratios consistently exceeded expected daytime values by as much as a factor of 6. Mean daytime concentrations of 61 pptv were observed. While HONO decay began at sunrise, minimum HONO values were not measured until the late afternoon. There was little difference between the daytime (mean=1.5%) and night-time (mean=1.7%) ratios of HONO/NO2. Thus there was a very strong daytime source of HONO which is consistent with other recent studies. Correlations of daytime HONO production with a variety of chemical and meteorological parameters indicate that production is dependent on UV radiation, NO2 and water vapour but is not consistent with a simple gas phase process. Apparent rate constants for the production of HONO from photolyticly excited NO2 and water vapour vary from 2.8–7.8×10−3 molec−1 s−1, during the campaign.

scholarly journals Airborne determination of the temporo-spatial distribution of benzene, toluene, nitrogen oxides and ozone in the boundary layer across Greater London, UK

2015 ◽  
Vol 15 (9) ◽  
pp. 5083-5097 ◽  
Author(s):  
M. D. Shaw ◽  
J. D. Lee ◽  
B. Davison ◽  
A. Vaughan ◽  
R. M. Purvis ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Nitrogen Oxides ◽  
Linear Regression Analysis ◽  
Proton Transfer Reaction ◽  
Mixing Ratios ◽  
Spatially Resolved ◽  
Dual Channel ◽  
Benzene Toluene

Abstract. Highly spatially resolved mixing ratios of benzene and toluene, nitrogen oxides (NOx) and ozone (O3) were measured in the atmospheric boundary layer above Greater London during the period 24 June to 9 July 2013 using a Dornier 228 aircraft. Toluene and benzene were determined in situ using a proton transfer reaction mass spectrometer (PTR-MS), NOx by dual-channel NOx chemiluminescence and O3 mixing ratios by UV absorption. Average mixing ratios observed over inner London at 360 ± 10 m a.g.l. were 0.20 ± 0.05, 0.28 ± 0.07, 13.2 ± 8.6, 21.0 ± 7.3 and 34.3 ± 15.2 ppbv for benzene, toluene, NO, NO2 and NOx respectively. Linear regression analysis between NO2, benzene and toluene mixing ratios yields a strong covariance, indicating that these compounds predominantly share the same or co-located sources within the city. Average mixing ratios measured at 360 ± 10 m a.g.l. over outer London were always lower than over inner London. Where traffic densities were highest, the toluene / benzene (T / B) concentration ratios were highest (average of 1.8 ± 0.5 ppbv ppbv-1), indicative of strong local sources. Daytime maxima in NOx, benzene and toluene mixing ratios were observed in the morning (~ 40 ppbv NOx, ~ 350 pptv toluene and ~ 200 pptv benzene) and in the mid-afternoon for ozone (~ 40 ppbv O3), all at 360 ± 10 m a.g.l.

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

2012 ◽  
Vol 12 (3) ◽  
pp. 1497-1513 ◽  
Author(s):  
X. Li ◽  
T. Brauers ◽  
R. Häseler ◽  
B. Bohn ◽  
H. Fuchs ◽  
...  
Keyword(s):  
Atmospheric Chemistry ◽  
Nitrous Acid ◽  
Southern China ◽  
Rural Site ◽  
Pearl River Delta Region ◽  
Additional Source ◽  
Mixing Ratios ◽  
Photolysis Frequency ◽  
The Pearl River

Abstract. We performed measurements of nitrous acid (HONO) during the PRIDE-PRD2006 campaign in the Pearl River Delta region 60 km north of Guangzhou, China, for 4 weeks in June 2006. HONO was measured by a LOPAP in-situ instrument which was setup in one of the campaign supersites along with a variety of instruments measuring hydroxyl radicals, trace gases, aerosols, and meteorological parameters. Maximum diurnal HONO mixing ratios of 1–5 ppb were observed during the nights. We found that the nighttime build-up of HONO can be attributed to the heterogeneous NO2 to HONO conversion on ground surfaces and the OH + NO reaction. In addition to elevated nighttime mixing ratios, measured noontime values of ≈200 ppt indicate the existence of a daytime source higher than the OH + NO→HONO reaction. Using the simultaneously recorded OH, NO, and HONO photolysis frequency, a daytime additional source strength of HONO (PM) was calculated to be 0.77 ppb h−1 on average. This value compares well to previous measurements in other environments. Our analysis of PM provides evidence that the photolysis of HNO3 adsorbed on ground surfaces contributes to the HONO formation.

scholarly journals Reactive quenching of electronically excited NO<sub>2</sub><sup>∗</sup> and NO<sub>3</sub><sup>∗</sup> by H<sub>2</sub>O as potential sources of atmospheric HO<sub><i>x</i></sub> radicals

2018 ◽  
Vol 18 (19) ◽  
pp. 14005-14015 ◽  
Author(s):  
Terry J. Dillon ◽  
John N. Crowley
Keyword(s):  
Gas Phase ◽  
Laser Excitation ◽  
Pulsed Laser ◽  
Work Rate ◽  
Rate Coefficients ◽  
Phase Reaction ◽  
Gas Phase Reaction ◽  
Upper Limit ◽  
Upper Limits ◽  
Electronically Excited

Abstract. Pulsed laser excitation of NO2 (532–647 nm) or NO3 (623–662 nm) in the presence of H2O was used to initiate the gas-phase reaction NO2∗+H2O → products (Reaction R5) and NO3∗+H2O → products (Reaction R12). No evidence for OH production in Reactions (R5) or (R12) was observed and upper limits for OH production of k5b/k5<1×10-5 and k12b/k12<0.03 were assigned. The upper limit for k5b∕k5 renders this reaction insignificant as a source of OH in the atmosphere and extends the studies (Crowley and Carl, 1997; Carr et al., 2009; Amedro et al., 2011) which demonstrate that the previously reported large OH yield by Li et al. (2008) was erroneous. The upper limit obtained for k12b∕k12 indicates that non-reactive energy transfer is the dominant mechanism for Reaction (R12), though generation of small but significant amounts of atmospheric HOx and HONO cannot be ruled out. In the course of this work, rate coefficients for overall removal of NO3∗ by N2 (Reaction R10) and by H2O (Reaction R12) were determined: k10=(2.1±0.1)×10-11 cm3 molecule−1 s−1 and k12=(1.6±0.3)×10-10 cm3 molecule−1 s−1. Our value of k12 is more than a factor of 4 smaller than the single previously reported value.

scholarly journals Diagnosis of processes controlling water vapour in the tropical tropopause layer by a Lagrangian cirrus model

2007 ◽  
Vol 7 (2) ◽  
pp. 5515-5552 ◽  
Author(s):  
C. Ren ◽  
A. R. MacKenzie ◽  
C. Schiller ◽  
G. Shur ◽  
V. Yushkov
Keyword(s):  
Water Vapour ◽  
Specific Humidity ◽  
Mixing Ratio ◽  
Total Water ◽  
Water Mixing ◽  
Tropical Tropopause Layer ◽  
Mixing Ratios ◽  
Aircraft Flight ◽  
Tropical Tropopause ◽  
Ecmwf Model

Abstract. We have developed a Lagrangian air-parcel cirrus model (LACM), to diagnose the processes controlling water in the tropical tropopause layer (TTL). LACM applies parameterised microphysics to air parcel trajectories. The parameterisation includes the homogeneous freezing of aerosol droplets, the growth/sublimation of ice particles, and sedimentation of ice particles, so capturing the main dehydration mechanism for air in the TTL. Rehydration is also considered by resetting the water vapour mixing ratio in an air parcel to the value at the point in the 4-D analysis/forecast data used to generate the trajectories, but only when certain conditions, indicative of convection, are satisfied. These conditions are imposed to confine what processes contribute to rehydration. The conditions act to restrict rehydration of the Lagrangian air parcels to regions where convective transport of water vapour from below is significant, at least to the extent that the analysis/forecast captures this process. The inclusion of hydration and dehydration mechanisms in LACM results in total water fields near tropical convection that have more of the "stripey" character of satellite observations of high cloud, than do either the ECMWF analysis or trajectories without microphysics. The mixing ratios of total water in the TTL, measured by a high-altitude aircraft over Brazil (during the TROCCINOX campaign), have been reconstructed by LACM using trajectories generated from ECMWF analysis. Two other Lagrangian reconstructions are also tested: linear interpolation of ECMWF analysed specific humidity onto the aircraft flight track, and instantaneous dehydration to the saturation vapour pressure over ice along trajectories. The reconstructed total water mixing ratios along aircraft flight tracks are compared with observations from the FISH total water hygrometer. Process-oriented analysis shows that modelled cirrus cloud events are responsible for dehydrating the air parcels coming from lower levels, resulting in total water mixing ratios as low as 2 μmol/mol. Without adding water back to some of the trajectories, the LACM and instantaneous-dehydration reconstructions have a dry bias. The interpolated-ECMWF reconstruction does not suffer this dry bias, because convection in the ECMWF model moistens air parcels dramatically, by pumping moist air upwards. This indicates that the ECMWF model captures the gross features of the rehydration of air in the TTL by convection. Overall, the ECMWF models captures well the exponential decrease in total water mixing ratio with height above 250 hPa, so that all the reconstruction techniques capture more than 75% of the variance in the measured total water mixing ratios over the depth of the TTL. We have therefore developed a simple method for re-setting the total water in LACM using the ECMWF-analysed specific humidity in regions where the model predicts convection. By picking up the main contributing processes to dehydration and rehydration in the TTL, LACM reconstructs total water mixing ratios along aircraft flight tracks at the top of the TTL, close to the cold point, that are always in substantially better agreement with observations than instantaneous-dehydration reconstructions, and better than the ECMWF analysis for regions of high relative humidity and cloud.

scholarly journals Night-time chemistry above London: measurements of NO<sub>3</sub> and N<sub>2</sub>O<sub>5</sub> from the BT Tower during REPARTEE-II

2010 ◽  
Vol 10 (6) ◽  
pp. 14347-14386
Author(s):  
A. K. Benton ◽  
J. M. Langridge ◽  
S. M. Ball ◽  
W. J. Bloss ◽  
M. Dall'Osto ◽  
...  
Keyword(s):  
Nitrogen Oxides ◽  
Absorption Spectroscopy ◽  
Nitrogen Compounds ◽  
Equilibrium Partitioning ◽  
Night Time ◽  
Positive Correlation ◽  
Mixing Ratios ◽  
Enhanced Absorption ◽  
Cavity Enhanced Absorption Spectroscopy ◽  
The Mean

Abstract. Broadband cavity enhanced absorption spectroscopy (BBCEAS) has been used to measure the sum of concentrations of NO3 and N2O5 from the BT (telecommunications) Tower 160 m above street level in central London during the REPARTEE II campaign in October and November 2007. Substantial variability was observed in these night-time nitrogen compounds: peak NO3+N2O5 mixing ratios reached 800 pptv, whereas the mean night-time NO3+N2O5 was approximately 30 pptv. Additionally, [NO3+N2O5] showed negative correlations with [NO] and [NO2] and a positive correlation with [O3]. Co-measurements of temperature and NO2 from the BT Tower were used to calculate the equilibrium partitioning between NO3 and N2O5 which was always found to strongly favour N2O5 (NO3/N2O5=0.01 to 0.04). Two methods are used to calculate the lifetimes for NO3 and N2O5, the results being compared and discussed in terms of the implications for the night-time oxidation of nitrogen oxides and the night-time sinks for NOy.

scholarly journals Estimating Brewer-Dobson circulation trends from changes in stratospheric water vapour and methane

2021 ◽  
Author(s):  
Liubov Poshyvailo-Strube ◽  
Rolf Müller ◽  
Stephan Fueglistaler ◽  
Michaela I. Hegglin ◽  
Johannes C. Laube ◽  
...  
Keyword(s):  
Water Vapour ◽  
Meridional Overturning Circulation ◽  
Lagrangian Model ◽  
Satellite Measurements ◽  
Mixing Ratios ◽  
Transit Times ◽  
Sensitivity Studies ◽  
Meridional Overturning ◽  
Gas Measurements ◽  
Stratospheric Water Vapour

Abstract. The stratospheric meridional overturning circulation, also referred to as the Brewer-Dobson circulation (BDC), controls the composition of the stratosphere, which, in turn, affects radiation and climate. As the BDC cannot be directly measured, one has to infer its strength and trends indirectly. For instance, trace gas measurements allow the calculation of average transit times. Satellite measurements provide information on the distributions of trace gases for the entire stratosphere, with measurements of particularly long and dense coverage available for stratospheric water vapour (H2O). Although chemical processes and boundary conditions confound interpretation, the influence of CH4 oxidation on H2O is relatively straightforward, and thus H2O is an appealing tracer for transport analysis despite these caveats. In this work, we explore how mean age of air trends can be estimated from the combination of stratospheric H2O and CH4 data. We carry out different sensitivity studies with the Chemical Lagrangian Model of the Stratosphere (CLaMS) and focus on the analysis of the periods of 1990–2006 and 1990–2017. In particular, we assess the methodological uncertainties related to the two commonly-used approximations of (i) instantaneous stratospheric entry mixing ratio propagation, and (ii) constant correlation between mean age and the fractional release factor of methane. Our results show that the estimated mean age of air trends from the combination of observed stratospheric H2O and CH4 changes may be significantly affected by the assumed approximations. Depending on the investigated stratospheric region and the considered period, the error in estimated mean age of air decadal trends can be large – the discrepancies are up to 10 % per decade or even more at the lower stratosphere. For particular periods, the errors from the two approximations can lead to opposite effects, which may even cancel out. Finally, we propose an improvement to the approximation method by using an idealised age spectrum to propagate stratospheric entry mixing ratios. The findings of this work can be used for improving and assessing the uncertainties in stratospheric BDC trend estimation from global satellite measurements.

scholarly journals Modeling nitrous acid and its impact on ozone and hydroxyl radical during the Texas Air Quality Study 2006

2012 ◽  
Vol 12 (2) ◽  
pp. 5851-5880 ◽  
Author(s):  
B. H. Czader ◽  
B. Rappenglück ◽  
P. Percell ◽  
D. W. Byun ◽  
F. Ngan ◽  
...  
Keyword(s):  
Air Quality ◽  
Hydroxyl Radical ◽  
Gas Phase ◽  
Nitrous Acid ◽  
Organic Materials ◽  
Optical Absorption Spectroscopy ◽  
Ozone Formation ◽  
Mixing Ratios ◽  
Quality Study ◽  
Mist Chamber

Abstract. Nitrous acid (HONO) mixing ratios for the Houston metropolitan area were simulated with the Community Multiscale Air Quality (CMAQ) model for an episode during the Texas Air Quality Study (TexAQS) II in August/September 2006 and compared to in-situ MC/IC (mist-chamber/ion chromatograph) and long path DOAS (Differential Optical Absorption Spectroscopy) measurements at three different altitudes. Several HONO sources were accounted for in simulations, such as gas phase formation, direct emissions, nitrogen dioxide (NO2*) hydrolysis, photo-induced formation from excited NO2* and photo-induced conversion of NO2 into HONO on surfaces covered with organic materials. Compared to the gas-phase HONO formation there was about a tenfold increase in HONO mixing ratios when additional HONO sources were taken into account, which improved the correlation between modeled and measured values. Concentrations of HONO simulated with only gas phase chemistry did not change with altitude, while measured HONO concentrations decrease with height. A trend of decreasing HONO concentration with altitude was well captured with CMAQ predicted concentrations when heterogeneous chemistry and photolytic sources of HONO were taken into account. Heterogeneous HONO production mainly accelerated morning ozone formation, albeit slightly. Also HONO formation from excited NO2 only slightly affected HONO and ozone (O3) concentrations. Photo-induced conversion of NO2 into HONO on surfaces covered with organic materials turned out to be a strong source of daytime HONO. Since HONO immediately photo-dissociates during daytime its ambient mixing ratios were only marginally altered (up to 0.5 ppbv), but significant increase in the hydroxyl radical (OH) and ozone concentration was obtained. In contrast to heterogeneous HONO formation that mainly accelerated morning ozone formation, inclusion of photo-induced surface chemistry influenced ozone throughout the day.

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