Ozone production in remote oceanic and industrial areas derived from ship based measurements of peroxy radicals during TexAQS 2006

Sommariva, Roberto; Brown, Steven S.; Roberts, J. M.; Brookes, D. M.; Parker, Alison E.; Monks, Paul S.; Bates, T. S.; Bon, D.; Gouw, J. A. de; Frost, G. J.; Gilman, J. B.; Herndon, S. C.; Kuster, W. C.; Lerner, B. M.; Osthoff, Hans D.; Tucker, S. C.; Warneke, C.; Williams, E. J.; Zahniser, M. S.

doi:10.5194/acp-11-2471-2011

Cited by 15 publications

(17 citation statements)

References 37 publications

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“…Note also that from 13:00 UTC onwards both methods shows a steady decrease in the instantaneous O 3 production rates in all air masses and converge to almost zero rates of O 3 production at 16:00 UTC. It is worth mentioning that the values for instantaneous rates of O 3 production observed are much lower than the 0-160 ppb h −1 range reported by Sommariva et al (2011) during the TexAQS 2006 study. The main reason for this is that NO x levels, in particular for NO were significantly lower during DOMINO (average range: ∼0.1-5 ppbV) compared to the TexAQS study (average range: ∼0.7-15 ppbV).…”

Section: Derivation Of Rates Of Instantaneous Ozone Production Potentialmentioning

confidence: 62%

“…OH mixing ratios were also measured using laser induced fluorescence (Martinez et al, 2010). The second method of estimating the O 3 production potential in an air mass is based on the approach used previously by Sommariva et al (2011) that uses measured mixing ratios of RO 2 , HO 2 and NO and is given by:…”

Section: Derivation Of Rates Of Instantaneous Ozone Production Potentialmentioning

confidence: 99%

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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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Section: Derivation Of Rates Of Instantaneous Ozone Production Potentialmentioning

confidence: 62%

Section: Derivation Of Rates Of Instantaneous Ozone Production Potentialmentioning

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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“…The sensitivity of the LIF-FAGE technique to each type of organic peroxy radical varies with the amount of NO added for the conversion and is dependent on the instrument, but in general, it is highest (up to ∼ 90 %) for β-hydroxy peroxy radicals derived from alkenes and lowest for those derived from small alkanes (Fuchs et al, 2011;Lew et al, 2018;Whalley et al, 2013). This RO 2 interference can be greatly reduced by use of lower NO concentrations or reaction times, yielding conversion efficiencies for isoprene-RO 2 under 20 % (Feiner et al, 2016;Fuchs et al, 2011;Tan et al, 2017;Whalley et al, 2013).…”

Section: Introductionmentioning

confidence: 99%

“…In some cases, because the RH in the amplification chamber can be lower than ambient because of reduced pressure and higher temperatures, the variability in RH can be considered negligible compared to other experimental uncertainties Kartal et al, 2010). In one case the need to apply an RHdependent calibration was disputed (Sommariva et al, 2011) despite strong experimental evidence (Butkovskaya et al, 2007(Butkovskaya et al, , 2005(Butkovskaya et al, , 2009Mihele et al, 1999;Mihele and Hastie, 1998;Reichert et al, 2003). Due to the paucity of XO 2 measurement intercomparisons and these new questions regarding the impact of relative humidity on the traditional chemical amplifier technique, further intercomparisons involving different instruments are required before we have enough confidence in the measurements to interpret modelmeasurement discrepancies as arising from unknown chemistry in models.…”

Section: Introductionmentioning

confidence: 99%

Peroxy radical measurements by ethane – nitric oxide chemical amplification and laser-induced fluorescence during the IRRONIC field campaign in a forest in Indiana

et al. 2019

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Peroxy radicals were measured in a mixed deciduous forest atmosphere in Bloomington, Indiana, USA, during the Indiana Radical, Reactivity and Ozone Production Intercomparison (IRRONIC) during the summer of 2015. Total peroxy radicals ([XO 2 ] ≡ [HO 2 ] + [RO 2 ]) were measured by a newly developed technique involving chemical amplification using nitric oxide (NO) and ethane (C 2 H 6 ) followed by NO 2 detection by cavity-attenuated phase-shift spectroscopy (hereinafter referred to as ECHAMP -Ethane CHemical AMPlifier). The sum of hydroperoxy radicals (HO 2 ) and a portion of organic peroxy radicals ([HO * 2 ] = [HO 2 ] + α i [R i O 2 ], 0 < α < 1) was measured by the Indiana University (IU) laser-induced fluorescence-fluorescence assay by gas expansion instrument (LIF-FAGE). Additional collocated measurements include concentrations of NO, NO 2 , O 3 , and a wide range of volatile organic compounds (VOCs) and meteorological parameters. XO 2 concentrations measured by ECHAMP peaked between 13:00 and 16:00 local time (LT), with campaign average concentrations of 41 ± 15 ppt (1σ ) at 14:00 LT. Daytime concentrations of iso-prene averaged 3.6 ± 1.9 ppb (1σ ), whereas average concentrations of NO x ([NO] + [NO 2 ]) and toluene were 1.2 and 0.1 ppb, respectively, indicating a low impact from anthropogenic emissions at this site.We compared ambient measurements from both instruments and conducted a calibration source comparison. For the calibration comparison, the ECHAMP instrument, which is primarily calibrated with an acetone photolysis method, sampled the output of the LIF-FAGE calibration source which is based on the water vapor photolysis method and, for these comparisons, generated a 50 %-50 % mixture of HO 2 and either butane or isoprene-derived RO 2 . A bivariate fit of the data yields the relation [XO 2 ] ECHAMP = (0.88± 0.02; [HO 2 ] + [RO 2 ]) IU_cal + (6.6 ± 4.5) ppt. This level of agreement is within the combined analytical uncertainties for the two instruments' calibration methods.A linear fit of the daytime (09:00-22:00 LT) 30 min averaged [XO 2 ] ambient data with the 1 min averaged [HO * 2 ] data (one point per 30 min) yields the relation [XO 2 ] = (1.08±0.05)[HO * 2 ]−(1.4±0.3). Day-to-day variability in the Published by Copernicus Publications on behalf of the European Geosciences Union. 9564 S. Kundu et al.: Peroxy radical measurements by ethane [XO 2 ]/[HO * 2 ] ratio was observed. The lowest [XO 2 ]/[HO * 2] ratios between 13:00 and 16:00 LT were 0.8 on 13 and 18 July, whereas the highest ratios of 1.1 to 1.3 were observed on 24 and 25 July -the same 2 d on which the highest concentrations of isoprene and ozone were observed. Although the exact composition of the peroxy radicals during IRRONIC is not known, zero-dimensional photochemical modeling of the IRRONIC dataset using two versions of the Regional Atmospheric Chemistry Mechanism (RACM2 and RACM2-LIM1) and the Master Chemical Mechanism (MCM 3.2 and MCM 3.3.1) all predict afternoon [XO 2 ]/[HO * 2 ] ratios of between 1.2 and 1.5. Differences bet...

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“…This difference between oceanic and continental free troposphere vanishes in the upper troposphere, where O 3 production prevails (Klonecki and Levy, 1997;. Studies that infer net ozone production at least in part from in situ measurements are rare and often limited to the boundary layer (Ren et al, 2013;Liu et al, 2012;Sommariva et al, 2011;Kleinman et al, 2005;Kanaya et al, 2002;Kleinman, 2000;Zanis et al, 2000;Penkett et al, 1997;Cantrell et al, 1996). A number of studies based on aircraft measurements have been performed, using in situ O 3 , CO, NO x , volatile organic compounds (VOCs) and radiation measurements in combination with a box model to calculate HO x and RO x radical levels to study NOPR in the free troposphere (Kuhn et al, 2010;Kondo et al, 2004;Davis et al, 2003;DiNunno et al, 2003;Ko et al, 2003;Reeves et al, 2002;Olson et al, 2001;Schultz et al, 1999;Crawford et al, 1997a, b;Davis et al, 1996;Jacob et al, 1996).…”

Section: Introductionmentioning

confidence: 99%

Chemical processes related to net ozone tendencies in the free troposphere

et al. 2017

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Abstract. Ozone (O 3 ) is an important atmospheric oxidant, a greenhouse gas, and a hazard to human health and agriculture. Here we describe airborne in situ measurements and model simulations of O 3 and its precursors during tropical and extratropical field campaigns over South America and Europe, respectively. Using the measurements, net ozone formation/destruction tendencies are calculated and compared to 3-D chemistry-transport model simulations. In general, observation-based net ozone tendencies are positive in the continental boundary layer and the upper troposphere at altitudes above ∼ 6 km in both environments. On the other hand, in the marine boundary layer and the middle troposphere, from the top of the boundary layer to about 6-8 km altitude, net O 3 destruction prevails. The ozone tendencies are controlled by ambient concentrations of nitrogen oxides (NO x ). In regions with net ozone destruction the available NO x is below the threshold value at which production and destruction of O 3 balance. While threshold NO values increase with altitude, in the upper troposphere NO x concentrations are generally higher due to the integral effect of convective precursor transport from the boundary layer, downward transport from the stratosphere and NO x produced by lightning. Two case studies indicate that in fresh convective outflow of electrified thunderstorms net ozone production is enhanced by a factor 5-6 compared to the undisturbed upper tropospheric background. The chemistry-transport model MATCH-MPIC generally reproduces the pattern of observation-based net ozone tendencies but mostly underestimates the magnitude of the net tendency (for both net ozone production and destruction).

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Ozone production in remote oceanic and industrial areas derived from ship based measurements of peroxy radicals during TexAQS 2006

Cited by 15 publications

References 37 publications

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

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

Peroxy radical measurements by ethane – nitric oxide chemical amplification and laser-induced fluorescence during the IRRONIC field campaign in a forest in Indiana

Chemical processes related to net ozone tendencies in the free troposphere

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