Production of peroxy radicals at night via reactions of ozone and the nitrate radical in the marine boundary layer

Salisbury, G.; Rickard, Andrew R.; Monks, P. S.; Allan, B. J.; Bauguitte, Stéphane; Penkett, S. A.; Carslaw, Nicola; Lewis, Alastair C.; Creasey, D. J.; Heard, D. E.; Jacobs, P. J.; Lee, James

doi:10.1029/2000jd900754

Cited by 96 publications

(120 citation statements)

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“…Previous studies showed the night-time concentrations of NO 3 at the surface range from 1 to 40 pptv in rural and clean air masses, averaging about 10 ppt (Carslaw et al, 1997;Allan et al, 1999Allan et al, , 2000Salisbury et al, 2001;Platt et al, 2002). The results from this study are consistent with the concentrations previously measured in the United Kingdom (Aliwell and Jones, 1998).…”

Section: Variation Of [Oh] [No 3 ] In Different Locationsupporting

confidence: 83%

Night‐time NO₃ and OH radical concentrations in the United Kingdom inferred from hydrocarbon measurements

Khan

Ashfold

Nickless

et al. 2008

Atmospheric Science Letters

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The hydrocarbon decay method (Rivett et al., 2003) has been used to analyse hydrocarbon data from four contrasting sites in the United Kingdom to estimate night-time levels of NO 3 and OH. Remarkably consistent results emerge using alkenes, revealing NO 3 and OH levels in the range of 0.01-10 ppt and 1 × 10 4 −1 × 10 6 molecule cm −3 , respectively. Weak seasonal cycles are observed where NO 3 levels peak in spring and OH in summer. Analysis using alkanes suggests that Cl atom levels of around 2 × 10 4 molecule cm −3 may be present. How Cl may be formed at night in such high quantities is unknown and may not be the answer to the disparity between the two methods.

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Section: Variation Of [Oh] [No 3 ] In Different Locationsupporting

confidence: 83%

Night‐time NO₃ and OH radical concentrations in the United Kingdom inferred from hydrocarbon measurements

Khan

Ashfold

Nickless

et al. 2008

Atmospheric Science Letters

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“…Rate constants for the reaction of NO 3 with the measured alkenes were used to calculate the rate of the NO 3 loss and the O 3 reactions with alkenes (cf. Salisbury et al, 2001). The flux of peroxy radicals formed from the alkene reactions from the NO 3 and O 3 channels were compared by correlating all night-time hours of the campaign as shown in Fig.…”

Section: Peroxidesmentioning

confidence: 99%

“…Ozone is one of the major components of photochemical smog, together with contributions from compounds such as carbonyls, peroxy acetyl nitrates (PANs) and various nitrogen oxides. It has been seen in past studies in the relatively clean rural/marine conditions of Mace Head (Salisbury et al, 2001 during the EASE 96 and 97 (Eastern Atlantic Summer/Spring Experiment) and in the very clean air of Cape Grim in Tasmania (Monks et al, 1998(Monks et al, , 2005b 1 at the SOAPEX 2 (Southern Ocean Atmospheric Photochemistry EXperiment) campaign in 1998 that ozone formation is part of a natural cycle that can be easily perturbed by pollution events.…”

Section: Introductionmentioning

confidence: 99%

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Peroxy radical chemistry and the control of ozone photochemistry at Mace Head, Ireland during the summer of 2002

et al. 2006

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Abstract. Peroxy radical (HO 2 + RO 2 ) measurements, using the PEroxy Radical Chemical Amplification (PERCA) technique at the North Atlantic Marine Boundary Layer EXperiment (NAMBLEX) at Mace Head in summer 2002, are presented and put into the context of marine, boundarylayer chemistry. A suite of other chemical parameters (NO, NO 2 , NO 3 , CO, CH 4 , O 3 , VOCs, peroxides), photolysis frequencies and meteorological measurements, are used to present a detailed analysis of the role of peroxy radicals in tropospheric oxidation cycles and ozone formation. Under the range of conditions encountered the peroxy radical daily maxima varied from 10 to 40 pptv. The diurnal cycles showed an asymmetric shape typically shifted to the afternoon. Using a box model based on the master chemical mechanism the average model measurement agreement was 2.5 across the campaign. The addition of halogen oxides to the model increases the level of model/measurement agreement, apparently by respeciation of HO x . A good correlation exists between j (HCHO).[HCHO] and the peroxy radicals indicative of the importance of HCHO in the remote atmosphere as a HO x source, particularly in the afternoon. The peroxy radicals showed a strong dependence on [NO x ] with a break point at 0.1 ppbv, where the radicals increased concomitantly with the reactive VOC loading, this is a lower value than seen at representative urban campaigns. The HO 2 /(HO 2 + RO 2 ) ratios are dependent on [NO x ] ranging between 0.2 and 0.6, with the ratio increasing linearly with NO x . Significant night-time levels of peroxy radicals were measured up to 25 pptv. The contribution of ozone-alkenes and NO 3 -alkene chemistry to night-time peroxy radical production was shown to be on average 59 and 41%. The campaign mean net ozone production rate was 0.11±0.3 ppbv Correspondence to: P. S. Monks (p.s.monks@le.ac.uk) h −1 . The ozone production rate was strongly dependent on [NO] having linear sensitivity (dln(P(O 3 ))/dln(NO)=1.0). The results imply that the N(O 3 ) (the in-situ net photochemical rate of ozone production/destruction) will be strongly sensitive in the marine boundary layer to small changes in [NO] which has ramifications for changing NO x loadings in the European continental boundary layer.

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“…Today it is becoming clear that this separation is not generally valid. Recent observations and model studies give evidence of significant levels of OH (and peroxy radicals) during the night [Aliwell and Jones, 1998;Bey et al, 1997;Bey et al, 2001aBey et al, , 2001bCantrell et al, 1997;Carslaw et al, 1997;Faloona et al, 2001;George et al, 1999;Geyer et al, 2003;Kanaya et al, 1999;Mather et al, 1997;Monks et al, 1996;Paulson et al, 1999;Paulson and Orlando, 1996;Platt et al, 1990;Salisbury et al, 2001;Tanner and Eisele, 1995;Tanner et al, 1997].…”

Section: Introductionmentioning

confidence: 99%

Direct observations of daytime NO₃: Implications for urban boundary layer chemistry

et al. 2003

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[1] The nitrate radical (NO 3 ) is the dominant atmospheric oxidant during the night in most environments. During the day, however, NO 3 has thus far been considered insignificant. Here we present daytime measurements of NO 3 by Differential Optical Absorption Spectroscopy near Houston, Texas, during the Texas Air Quality Study 2000. On 3 consecutive days in August/September 2000, NO 3 reached levels from $5 ppt 3 hours before sunset to 31 ppt around sunset. Daytime NO 3 had a negligible effect on the photostationary state (PSS) between O 3 and NO x , with the exception of the last hour before sunset, when it significantly accelerated NO-to-NO 2 conversion. On August 31, chemical reactions involving NO 3 destroyed 8 (±4) ppb O x (= O 3 + NO 2 ) during the day and 27 (±6) ppb at night. NO 3 chemistry contributed 10 (±7)% to the total O x loss during the daytime, and 28% (±18%) integrated over a 24-hour period. It therefore played an important role in the O x budget. NO 3 also contributed significantly to the daytime oxidation of hydrocarbons such as monoterpenes and phenol in Houston. The observed daytime NO 3 mixing ratios can be described as a function of O 3 and NO x . Above [NO x ]/[O 3 ] ratios of 3%, daytime NO 3 becomes independent of NO x and proportional to the square of O 3 . Our calculations indicate that elevated (>1 ppt) NO 3 levels can be present whenever ozone mixing ratios exceed typical urban smog levels of 100 ppb.

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Production of peroxy radicals at night via reactions of ozone and the nitrate radical in the marine boundary layer

Cited by 96 publications

References 57 publications

Night‐time NO₃ and OH radical concentrations in the United Kingdom inferred from hydrocarbon measurements

Night‐time NO₃ and OH radical concentrations in the United Kingdom inferred from hydrocarbon measurements

Peroxy radical chemistry and the control of ozone photochemistry at Mace Head, Ireland during the summer of 2002

Direct observations of daytime NO₃: Implications for urban boundary layer chemistry

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Production of peroxy radicals at night via reactions of ozone and the nitrate radical in the marine boundary layer

Cited by 96 publications

References 57 publications

Night‐time NO3 and OH radical concentrations in the United Kingdom inferred from hydrocarbon measurements

Night‐time NO3 and OH radical concentrations in the United Kingdom inferred from hydrocarbon measurements

Peroxy radical chemistry and the control of ozone photochemistry at Mace Head, Ireland during the summer of 2002

Direct observations of daytime NO3: Implications for urban boundary layer chemistry

Contact Info

Product

Resources

About

Night‐time NO₃ and OH radical concentrations in the United Kingdom inferred from hydrocarbon measurements

Night‐time NO₃ and OH radical concentrations in the United Kingdom inferred from hydrocarbon measurements

Direct observations of daytime NO₃: Implications for urban boundary layer chemistry