Ozone deposition to a coastal sea: comparison of eddy covariance observations with reactive air–sea exchange models

• Main Authors: D. C. Loades, M. Yang, T. G. Bell, A. R. Vaughan, R. J. Pound, S. Metzger, J. D. Lee, L. J. Carpenter
• Format: Article
• Language: English
• Published: Copernicus Publications 2020-12-01
• Series: Atmospheric Measurement Techniques
• Online Access: https://amt.copernicus.org/articles/13/6915/2020/amt-13-6915-2020.pdf
• ISSN: 1867-1381; 1867-8548

<p>A fast-response (10 Hz) chemiluminescence detector for ozone (O<span class="inline-formula">₃</span>) was used to determine O<span class="inline-formula">₃</span> fluxes using the eddy covariance technique at the Penlee Point Atmospheric Observatory (PPAO) on the south coast of the UK during April and May 2018. The median O<span class="inline-formula">₃</span> flux was <span class="inline-formula">−</span>0.132 mg m<span class="inline-formula">⁻²</span> h<span class="inline-formula">⁻¹</span> (0.018 ppbv m s<span class="inline-formula">⁻¹</span>), corresponding to a deposition velocity of 0.037 cm s<span class="inline-formula">⁻¹</span> (interquartile range 0.017–0.065 cm s<span class="inline-formula">⁻¹</span>) – similar to the higher values previously reported for open-ocean flux measurements but not as high as some other coastal results. We demonstrate that a typical single flux observation was above the 2<span class="inline-formula"><i>σ</i></span> limit of detection but had considerable uncertainty. The median 2<span class="inline-formula"><i>σ</i></span> uncertainty of deposition velocity was 0.031 cm s<span class="inline-formula">⁻¹</span> for each 20 min period, which reduces with the square root of the sample size. Eddy covariance footprint analysis of the site indicates that the flux footprint was predominantly over water (<span class="inline-formula">&gt;</span> 96 %), varying with atmospheric stability and, to a lesser extent, with the tide. At very low wind speeds when the atmosphere was typically unstable, the observed ozone deposition velocity was elevated, most likely because the footprint contracted to include a greater land contribution in these conditions. At moderate to high wind speeds when atmospheric stability was near-neutral, the ozone deposition velocity increased with wind speed and showed a linear dependence with friction velocity. This observed dependence on friction velocity (and therefore also wind speed) is consistent with the predictions from the one-layer model of Fairall et al. (2007), which parameterises the oceanic deposition of ozone from the fundamental conservation equation, accounting for both ocean turbulence and near-surface chemical destruction, while assuming that chemical O<span class="inline-formula">₃</span> destruction by iodide is distributed over depth. In contrast to our observations, the deposition velocity predicted by the recently developed two-layer model of Luhar et al. (2018) (which considers iodide reactivity in both layers but with molecular diffusivity dominating over turbulent diffusivity in the first layer) shows no major dependence of deposition velocity on wind speed and underestimates the measured deposition velocities. These results call for further investigation into the mechanisms and control of oceanic O<span class="inline-formula">₃</span> deposition.</p>