Variable lifetimes and loss mechanisms for NO&amp;lt;sub&amp;gt;3&amp;lt;/sub&amp;gt; and N&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;O&amp;lt;sub&amp;gt;5&amp;lt;/sub&amp;gt; during the DOMINO campaign: contrasts between marine, urban and continental air

Crowley, John N.; Thieser, J.; Tang, Mingjin; Schuster, G.; Bozem, Heiko; Beygi, Z. Hosaynali; Fischer, H.; Diesch, J.-M.; Drewnick, Frank; Borrmann, Stephan; Song, Weihua; Yassaa, Noureddine; Williams, Jonathan; Pöhler, Denis; Platt, U.; Lelieveld, Jos

doi:10.5194/acp-11-10853-2011

Cited by 64 publications

(56 citation statements)

References 65 publications

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“…To fully understand the transport and distribution of NO x across a region the daytime chemistry of NO x discussed here must be combined with additional analyses of the nighttime chemistry of NO x and NO y (e.g. Brown et al, 2009;Crowley et al, 2011;Ayres et al, 2015).…”

Section: Discussionmentioning

confidence: 99%

The lifetime of nitrogen oxides in an isoprene-dominated forest

et al. 2016

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Abstract. The lifetime of nitrogen oxides (NO x ) affects the concentration and distribution of NO x and the spatial patterns of nitrogen deposition. Despite its importance, the lifetime of NO x is poorly constrained in rural and remote continental regions. We use measurements from a site in central Alabama during the Southern Oxidant and Aerosol Study (SOAS) in summer 2013 to provide new insights into the chemistry of NO x and NO x reservoirs. We find that the lifetime of NO x during the daytime is controlled primarily by the production and loss of alkyl and multifunctional nitrates ( ANs). During SOAS, AN production was rapid, averaging 90 ppt h −1 during the day, and occurred predominantly during isoprene oxidation. Analysis of the AN and HNO 3 budgets indicate that ANs have an average lifetime of under 2 h, and that approximately 45 % of the ANs produced at this site are rapidly hydrolyzed to produce nitric acid. We find that AN hydrolysis is the largest source of HNO 3 and the primary pathway to permanent removal of NO x from the boundary layer in this location. Using these new constraints on the fate of ANs, we find that the NO x lifetime is 11±5 h under typical midday conditions. The lifetime is extended by storage of NO x in temporary reservoirs, including acyl peroxy nitrates and ANs.

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Section: Discussionmentioning

confidence: 99%

The lifetime of nitrogen oxides in an isoprene-dominated forest

et al. 2016

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“…(8) of Brown et al (2003a): water, which have been examined extensively (e.g., Brown et al, 2009;Thornton et al, 2003;Wahner et al, 1998;Tuazon et al, 1983;Hjorth et al, 1987). However, the homogeneous N 2 O 5 + H 2 O rate constant is negligible for this dataset, especially since at 283 K absolute humidity is low (Brown et al, 2007;Crowley et al, 2011). We calculate relative rates of N 2 O 5 heterogeneous uptake compared to NO 3 reaction with BVOCs (dominated at night by monoterpenes), using typical nighttime monoterpene (MT), MBO, and sesquiterpene (SQT) concentrations (measured by PTR-ToF-MS) of 0.6 ppb, 0.4 ppb, and 0.01 ppb, respectively, and the N 2 O 5 /NO 3 ratio of 4.1.…”

Section: Observed and Calculated Ambient No 3 And Lifetimementioning

confidence: 95%

Observations of gas- and aerosol-phase organic nitrates at BEACHON-RoMBAS 2011

et al. 2013

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At the Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS) field campaign in the Colorado front range, July–August 2011, measurements of gas- and aerosol-phase organic nitrates enabled a study of the role of NO_x (NO_x = NO + NO₂) in oxidation of forest-emitted volatile organic compounds (VOCs) and subsequent aerosol formation. Substantial formation of peroxy- and alkyl-nitrates is observed every morning, with an apparent 2.9% yield of alkyl nitrates from daytime RO₂ + NO reactions. Aerosol-phase organic nitrates, however, peak in concentration during the night, with concentrations up to 140 ppt as measured by both optical spectroscopic and mass spectrometric instruments. The diurnal cycle in aerosol fraction of organic nitrates shows an equilibrium-like response to the diurnal temperature cycle, suggesting some reversible absorptive partitioning, but the full dynamic range cannot be reproduced by thermodynamic repartitioning alone. Nighttime aerosol organic nitrate is observed to be positively correlated with [NO₂] × [O₃] but not with [O₃]. These observations support the role of nighttime NO₃-initiated oxidation of monoterpenes as a significant source of nighttime aerosol. Nighttime production of organic nitrates is comparable in magnitude to daytime photochemical production at this site, which we postulate to be representative of the Colorado front range forests

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“…The only exception were O 3 and SO 2 which were measured from a neighboring inlet (< 3 m away) installed on the mast of a mobile van at a height of 10 m above ground (Diesch et al, 2012). As details regarding the measurements of NO, NO 2 , HCHO, OH and HO 2 radicals during the DOMINO campaign have already been described elsewhere (Crowley et al, 2011;Sörgel et al, 2011) only a short description is given below.…”

Section: Simultaneous Ancillary Measurementsmentioning

confidence: 99%

“…4, it should be noted that SO 2 is present at several ppb in air masses from the Huelva and ocean sector, but is almost zero in continental sector air masses. Crowley et al (2011) have discussed the influence of Spain's largest paper mill which is located in Huelva in terms of malodorous sulphur emissions at ppbV level. The SO 2 profile shown in Fig.…”

Section: Figmentioning

confidence: 99%

Constraints on instantaneous ozone production rates and regimes during DOMINO derived using in-situ OH reactivity measurements

et al. 2012

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Abstract. In this study air masses are characterized in terms of their total OH reactivity which is a robust measure of the "reactive air pollutant loading". The measurements were performed during the DOMINO campaign (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) held from 21/11/2008 to 08/12/2008 at the Atmospheric Sounding Station -El Arenosillo (37.1 • N-6.7 • W, 40 m a.s.l.). The site was frequently impacted by marine air masses (arriving at the site from the southerly sector) and air masses from the cities of Huelva (located NW of the site), Seville and Madrid (located NNE of the site). OH reactivity values showed strong wind sector dependence. North eastern "continental" air masses were characterized by the highest OH reactivities (average: 31.4 ± 4.5 s −1 ; range of average diel values: 21.3-40.5 s −1 ), followed by north western "industrial" air masses (average: 13.8 ± 4.4 s −1 ; range of average diel values: 7-23.4 s −1 ) and marine air masses (average: 6.3 ± 6.6 s −1 ; range of average diel values: below detection limit −21.7 s −1 ), respectively. The average OH reactivity for the entire campaign period was ∼18 s −1 and no pronounced variation was discernible in the diel profiles with the exception of relatively high values from 09:00 to 11:00 UTC on occasions when air masses arrived from the north western and southern wind sectors. The measured OH reactivity was used to constrain both diel instantaneous ozone production potential rates and regimes. Gross ozone production rates at the site were generally limited by the availability of NO x with peak values of around 20 ppbV O 3 h −1 . Using the OH reactivity based approach, derived ozone production rates indicate that if NO x would no longer be the limiting factor in air masses arriving from the continental north eastern sector, peak ozone production rates could double. We suggest that the new combined approach of in-situ fast measurements of OH reactivity, nitrogen oxides and peroxy radicals for constraining instantaneous ozone production rates, could significantly improve analyses of upwind point sources and their impact on regional ozone levels.

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Variable lifetimes and loss mechanisms for NO<sub>3</sub> and N<sub>2</sub>O<sub>5</sub> during the DOMINO campaign: contrasts between marine, urban and continental air

Cited by 64 publications

References 65 publications

The lifetime of nitrogen oxides in an isoprene-dominated forest

The lifetime of nitrogen oxides in an isoprene-dominated forest

Observations of gas- and aerosol-phase organic nitrates at BEACHON-RoMBAS 2011

Constraints on instantaneous ozone production rates and regimes during DOMINO derived using in-situ OH reactivity measurements

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