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Ozone production during the field campaign RISFEX 2003 in the sea of Japan: analysis of sensitivity and behaviour based on an improved indicator

By Z. Q. Wang, Y. S. Chen, B. Qi and B. Yang

Abstract

The ratio Φ=<i>k</i><sub>HC+OH</sub>[HC]/<i>k</i><sub>NO<sub>x</sub>+OH</sub>[NO<sub>x</sub>] is used as an indicator for the sensitivity of ozone production (<i>P</i>(O<sub>3</sub>)) to HC and NO<sub>x</sub> in the field campaign RISFEX 2003 (RIShiri Fall EXperiment 2003) at Rishiri Island (45.07° N, 141.12° E, and 35 m a.s.l.) in the sea of Japan during September 2003. Four different sensitivity regimes are obtained based on the indicator. The sensitivity is found to show a distinctive pattern in each regime. In Regime I (Φ<1), <i>P</i>(O<sub>3</sub>) almost linearly increases with increasing HC and almost linearly decreases with increasing NO<sub>x</sub>. In Regime II (1<Φ<9 ± 5), there is a less-than-linear increase in <i>P</i>(O<sub>3</sub>) with HC and a less-than-linear decrease with NO<sub>x</sub>. <i>P</i>(O<sub>3</sub>) less-than-linearly increases with both HC and NO<sub>x</sub> in Regime III (9 ± 5<Φ<45 ± 7), and near linearly increases with NO<sub>x</sub> and is nearly constant with increasing HC in Regime IV (Φ>45 ± 7). During the campaign, 91 percent of <i>P</i>(O<sub>3</sub>) data appear in Regime III and IV, indicating that NO<sub>x</sub> is a limiting factor of ozone production. Hence, it may be an efficient strategy to control NO<sub>x</sub> emission for ozone abatement at the site. <br><br> Comparisons between the observed <i>P</i>(O<sub>3</sub>) and the ones modelled have represented general agreement. However, the model tends to underestimate <i>P</i>(O<sub>3</sub>) in Regime II, implying that an important source of peroxy radicals is possibly missed. In Regime IV, the modelled <i>P</i>(O<sub>3</sub>) is systematically larger than the measured one under a low <i>j</i>(O<sup>1</sup>D) condition, which may be caused by the over-estimated yields of peroxy radicals from the reactions of monoterpenes with ozone. A budget analysis indicates that sensitivity of <i>P</i>(O<sub>3</sub>) is declining with HC and enhancing with NO when the condition shifts from Regime II to Regime IV, which is also observed through the analysis of <i>P</i>(O<sub>3</sub>) sensitivity using Φ. Sensitivity studies for <i>P</i>(O<sub>3</sub>) are conducted to determine the effect of NO<sub>x</sub> and monoterpenes on ozone production and the conclusions are very consistent with those derived from the indicator. This study demonstrates that the ratio Φ could be a useful index to ascertain the sensitivity of <i>P</i>(O<sub>3</sub>) to HC and NO<sub>x</sub> in the clean marine boundary layer

Topics: Physics, QC1-999, Chemistry, QD1-999
Publisher: Copernicus Publications
Year: 2010
DOI identifier: 10.5194/acp-10-9579-2010
OAI identifier: oai:doaj.org/article:20852cc27f874f4380b1c04255687915
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