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Seasonal dependence of peroxy radical concentrations at a Northern hemisphere marine boundary layer site during summer and winter: evidence for radical activity in winter

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posted on 2006-12-05, 16:23 authored by Zoe L. Fleming, Paul S. Monks, Andrew R. Rickard, Brian J. Bandy, N. Brough, T.J. Green, C.E. Reeves, Stuart A. Penkett
Peroxy radicals (HO2 +ΣRO2) were measured at the Weybourne Atmospheric Observatory (52ºN, 1ºE), Norfolk using a PEroxy Radical Chemical Amplifier (PERCA) during the winter and summer of 2002. The peroxy radical diurnal cycles showed a marked difference between the winter and summer campaigns with maximum concentrations of 12 pptv at midday in the summer and maximum concentrations as high as 30 pptv (10 min averages) in winter at night. The corresponding nighttime peroxy radical concentrations were not as high in summer (3 pptv). The peroxy radical concentration shows a distinct anti-correlation with increasing NOx during the daylight hours. At night, peroxy radicals increase with increasing NOx indicative of the role of NO3 chemistry. The average diurnal cycles for net ozone production, N(O3) show a large variability in ozone production, P(O3), and a large ozone loss, L(O3) in summer relative to winter. For a daylight average, net ozone production in summer was higher than winter (1.51±0.5 ppbv h−1 and 1.11±0.47 ppbv h−1, respectively). The variability in NO concentration has a much larger effect on N(O3) than the peroxy radical concentrations. Photostationary state (PSS) calculations show an NO2 lifetime of 5 min in summer and 21 minutes in the winter, implying that steady-state NO-NO2 ratios are not always attained during the winter months. The results show an active peroxy radical chemistry at night and that significant oxidant levels are sustained in winter. The net effect of this with respect to production of ozone in winter is unclear owing to the breakdown in the photostationary state.

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Citation

Atmospheric Chemistry and Physics, 2006, 6, pp.5415-5433

Version

  • VoR (Version of Record)

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Atmospheric Chemistry and Physics

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Copernicus on behalf of the European Geosciences Union

issn

1049-331X

eissn

1557-7392

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2006

Available date

2006-12-05

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http://www.atmos-chem-phys.net/6/5415/2006/acp-6-5415-2006.html

Notes

This work is licensed under a Creative Commons License and is also available from http://www.atmos-chem-phys.net/, along with further discussion.

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en

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